17HDP ICMSE Proceedings

9 th I nte r n ation a l S e m i n a r on
Pro ce ss H y d ro m e ta llu rgy

·
I nte r n ation a l Con fe r e n ce on
M e ta l S o lv e nt E x tr ac tion
Editors
Fernando Valenzuela
Jesús Casas · Pía Hernández · Patricio Martínez · Sergio Rivera
9 th I nte r n ation a l S e m i n a r on
Pro ce ss H y d ro m e ta llu rgy
·
I nte r n ation a l Con fe r e nce on
M e ta l S olv e nt E xtr ac tion
J u n e 2 1 -2 3 • sa n t i ag o, ch i l e
c h i e f e d i t o r
Fe r n a n d o Va le nzu e l a
e d i t o r s
J e sú s Ca sa s · Pí a H e r n á n d e z · Patr i ci o M a r tí n e z · S e rg i o Ri v e r a
Copyright
© Gecamin, Chile. All rights reserved.
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Cover and book design by Estudio Vicencio

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Author’s disclaimer
Any views and opinions presented in the abstracts
published in these proceedings are solely those of
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of Gecamin. The authors take full and exclusive
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and accuracy of the information published herein.
This information is not intended nor implied to
be a substitute for professional advice. The editors
are not responsible for any damage to property
or persons that may occur as a result of use of
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CONTENTS
Organizers
Committees
Foreword
Preface
Acknowledgments
Plenarie s
Recent Updates on the Hydrometallurgical Processing of Primary Copper Sulfides
Ahmad Ghahreman
Challenges in 20 Years of Operation of the Leaching Plant, Solvent Extraction and

Electrowinning at Toquepala
José Tenorio and José Arenas
Path to a Cultural Transformation with “C+” Gabriela Mistral Division, Codelco

Alejandro Flores and Nelson Salazar
Scale Up of Hydrodynamic and Metallurgical Parameters in Heap Leaching Operations

Jorge Menacho
Iron Phase Control during Pressure Leaching of Copper in Sulfate Solutions at Elevated
Temperatures
Corby Anderson, Camille Fleuriault and Scott Shuey
PLCC Project: Autoclave Technology Applied to Complex Copper Concentrates

Nelson Parra, Marcelo Acuña and Orlando Fuentes
CHAPTER 1
INNOVATION, DEVELOPMENT AND PROCESS IMPROVEMENT
Economic Recovery and Upgrade of Metals from Middling and Tailings Streams
Paul Voigt, Daniel Mallah, Mike Hourn, Virginia Lawson, Greg Anderson and Glenn Stieper
Copper Ore Leaching with Pre-Treatment

María Taboada, Pía Hernández, Aldo Padilla, Osvaldo Herreros, Rafael Quiroz and Teófilo Gráber
Insights on the Behavior of Arsenic Species on Activated Carbon during Catalytic Arsenic Oxidation
Rebecca Radzinski and Ahmad Ghahreman
CHAPTER 2
INSTRUMENTATION, MODELING, OPTIMIZATION AND AUTOMATIC PROCESS CONTROL
Phenomenological Modelling of Industrial Heap and Dump Bioleaching
Roberto Collao and Roberto Bobadilla
Speciation and Conditioning of Copper Leach Solutions

Jesús Casas, José Luis Campos, Leonardo Romero, Patricia Piña and Roberto Bobadilla
Application of an Operative Model of Excellence for the Optimization of Hydrometallurgical Plants

Reinaldo Mendoza and María Veas
Dynamic Simulation of Operational Variables for Optimal Design
of a Processing Plant Adaptation
Verónica Escobar, Sebastián Gálvez and José Guerra
Multizone Process Water Metering using Distributed Acoustic Sensing (DAS)

Daniel Finfer, Phil Newman, Neil Rein and Mohammad Amir
CHAPTER 3
BASE METAL, PRECIOUS METAL, NON-METALLIC ELEMENTS, SALINE COMPOUNDS
AND RARE EARTH HYDROMETALLURGY
Cyanidation of Silver Telluride (Ag2Te): Effect of Lead(II) Concentration, Particle Size and
Presence of Pyrite
Adrián González, Fabiola Nava and Alejandro Uribe
Leaching of Auriferous Minerals with Hypochlorite Salts and Recovery with Activated Carbon:
Polydopamine Composite
David Meza, Juan Benavides, Ernesto de la Torre and Alicia Guevara
An Effective New Leaching Aid Successfully Tested with Copper Ores

Jack Bender
Development of an Active Carbon: Polydopamine Composite to Increase the Adsorption Capability of

Ions [AuCl4]- and Cu2+
Juan Benavides and Ernesto de la Torre
Silver Leaching From Jarosite by Thiourea in Acid Media: Effect of Copper and Sulfur on the Stability
of the Thiourea-Silver System
Dandy Calla, Fabiola Nava and Juan Fuentes
Oxygen Mass Transfer in the Albion Process™: from the Laboratory to the Plant
Paul Voigt, Mike Hourn and Daniel Mallah
Advanced Control System to Maximize Copper Recovery in Heap Leaching Operations

Francisco Troncoso, Jorge Menacho, Cristian Domínguez, Víctor Cabezas, Patricio Camacho and
Adrián Freitte
Oxidation Plant Optimization at Empresa Nacional de Minería

Manuel Carmona, Luis Collao, Miguel González and Gleny Espinoza
Development of a Geometallurigcal Model for the Oxides of Mantoverde, Chile

Ximena Madariaga, Romke Kuyvenhoven, Javier Pizarro and Orlando Rojas
CHAPTER 4
LEACHING AND BIOLEACHING OF SULFIDE CONCENTRATES AND MINERALS
Compatibility and Enhancement of Bioleaching of Primary Copper Sulfide Ore in the
Presence of Chloride
Patricia Piña, Yasna Gallardo and Roberto Bobadilla
Bioleaching of Enargite: Copper Recovery with Microorganisms from Arsenic-Containing Ores

Patricio Martínez and Roberto Bobadilla
Pre-Treatment with Sodium Chloride and Sulfuric Acid of a Bornitic Concentrate and Later
Leaching in Chloride Solution
Fabiana Bahamonde, Matías Gómez and Patricio Navarro
Environmental Benefits of the CESL Process for the Treatment of High-Arsenic Copper Concentrates
Darren Schwartz, Susan Stocker and Vanya Omaynikova
Outotec Process Solutions and Equipment for Hydrometallurgical Treatment of Cu Sulfides

Janne Karonen, Kaarlo Haavanlammi, Boris Merino and Claudio Rodríquez
New Electrolytic Process to Remove Copper Impurities from Molybdenite Concentrate by

Simultaneously Electrowinning Copper and Regenerating a Ferric Chloride Leaching Agent
Jaime Simpson
BioCobre® Technology: an Improved Methodology for Leaching Mineral Concentrates

Raimundo Bordagorry, Juan Rivadeneira, Gustavo Rodríguez and Miguel Herrera
The Evolution of Complex Ores in the Copper Industry: Lessons Learned from the Gold
Industry and the Acceptance of Pressure Hydrometallurgical Flowsheets
William McCombe, Kevin Fraser, Brad Hewitt and Frank Cheuk
The FLSmidth® ROL Process: BASF-FLS Pilot Plant Testing

David Chaiko, Jack Bender, Carlos Eyzaguirre, Sara Rocks, Chase Dickinson and Frank Baczek
CHAPTER 5
FUNDAMENTALS AND OPERATION OF SOLVENT EXTRACTION AND ION EXCHANGE
High Chloride in PLS and their Impact on Copper Solvent Extraction
Héctor Yáñez, Leonor Ardiles and Cristóbal del Río
Effect of Degradation Products on the Performance of Hydroxyoxime Extractant

Wang Chaohua, Ji Shangjun, Xu Zhigang, Zou Qian, Peng Xue, Ren Jiao and Yang Zheng
Effect of PLS Characteristics and Extractant Concentration on the Iron Transfer in

Copper SX Plant
Tang Qiming, Li Feng, Liu Dan, Yang Qi-hua, Zhou Shu-rong, Wang Jing-hong and
Chen Shi-min
Study on the Effect of Diluent on the Performance of Extractant

Wang Chaohua, Xu Zhigang, Zou Qian, Ji Shangjun, Wang Fei, Peng Xue and Ren Jiao
Study on the Effect of Modifiers on the Extraction Performance of

the Hydroxyoxime Extractants
Ji Shangjun, Xu Zhigang, Zou Qian, Luo Xing, Yu Li-yan, Xiao Xue-mei and Jiang Xue
Separation of Didymium from Lanthanum by Liquid-Liquid Extraction using

Organophosphorus Acids and Acetic Acid
João Silva and Ysrael Vera
Nitronium Ion Inhibition in Aqueous Solution: The Final Answer to Oxime Nitration in SX
Rodrigo Zambra, David Acevedo, José Becerra, Matthew Soderstrom and Laurent Cohen
A New Phase Dispersion and Superior Phase Separation System
Daniel Ernt
Aqueous Two-Phase System of Poly (Ethylene Glycol) 4000 and Ferric Sulfate at 323.15 K
Islamán Villalobos, Yahaira Barrueto, Katiuska Garnica and Yecid Jiménez
The Mith of Aromatic Compounds in Metallurgical Grade Kerosenes

Guillermo Stephens, Sergio Valladares and David Belmar
CHAPTER 6
LEACHING AND SOLVENT EXTRACTION IN CHLORIDE MEDIUM
Leaching of Primary Copper Sulfides in Chloride-Ferrous Medium
Karina Salinas, Juan Alvarez, Cynthia Torres, Camila Córdova and Osvaldo Herreros
In Situ Acid Generation: a Potential Option for Copper Oxide Heap Leaching Process
Felipe Hilário, Barbara Cardoso, Danielly Couto, Geysa Pereira and Rogério Ribeiro
Saline Tailings: AMD Production, Microbial Changes and the Effect of Washing with LAR-2® as
Remediation Strategy
Cristián Pugh, Bernardo González, Juan Rivadeneira, Hector Ayala, Raimundo Bordagorry, and
Gustavo Rodríguez
SX Operation under High Chloride Content Conditions

Rodrigo Zambra, Mauricio Morales, Matthew Soderstrom and Laurent Cohen
CHAPTER 7
DESIGN AND OPERATION OF SOLVENT EXTRACTION AND
ELECTROWINNING CIRCUITS
Measurments in Intercell Busbar with Four Contact Points for Copper Electrowinning Plant
Chi Zhang and Junyi Wu
Development of a Low Resistance, Low Corrosion Cathode Plate for Electrowinning and
Electrorefining
Nigel Aslin, Christian Pasten, Addin Pranowo and Graham Heferen
New Electrolytic Process for Copper Electrowinning and Simultaneous Generation of Ferric Ion for
Sulfide Leaching
Jaime Simpson and Víctor Araya
Elimination of Air Pollution by Acid Mist in Copper Electrowinning Plants from Copper Oxide Ores©
Víctor Vidaurre
Development and Implementation of SELE® Technology in EW Tank House, Radomiro Tomic

Mario Núñez, Felipe Lagno and Sergio Cortés
Start-Up Solvent Extraction – Electrowinning

José Aldana
De Nora’s Mixed Metal Oxide (MMO) Self-Protected Anode Technology Platform for Metal
Electrowinning
Carl Brown, Félix Prado, Piero Casanello, Luciano Iacopetti, Michele Perego, Giuseppe Faita, Paolo
Perrone and Alice Calderara
Chapter 8
RECYCLING OF METALS AND ALLOYS
Acid Leaching and Precipitation of Metals from Spent Li-Ion Batteries
Diana Endara and Sebastián Armas
Neodymium Recovery from Post-Consumer Computer Hard Drive Magnets using H3 PO4 and
HCl Solutions
Raquel Ibarra and Ernesto de la Torre
A Sustainable Process for the Recovery of Valuable Metals from Spent LiNi1/3Co1/3Mn1/3O2 Batteries
Liping Xu, Conghao Sun, Tao Zhou and Xiangping Chen
Selective Extraction of Lithium from Waste Cathode Materials of Spent Lithium-Ion Batteries using
Phosphoric Acid
Liping Xu, Conghao Sun, Tao Zhou and Xiangping Chen
Chapter 9
Treatments of Acid Drainage and Mine Waters
Underground Acid Drainage Treatment in Mina San José Oruro
Gerardo Zamora, Elvis Trujillo and Milton Salas
Adsorption: An Interesting Hydrometallurgical Option to Remove Ions from Mine Waters

Fernando Valenzuela, Carlos Basualto, Gonzalo Montes, Viviana Ide and Geraldine Quintana
editors
ORGANIZERS
The Hydroprocess-ICMSE 2017 Seminar was organized by KopperChem, Universidad de

Antofagasta, Colorado School of Mines and Gecamin, Chile.
Kopper Chemical Industry, KopperChem

Kopper Chemical Industry Corp., (KopperChem) is a national high-tech enterprise based
in China and the subsidiary of Hallochem Group which integrates R&D, manufacturing,
marketing and systems engineering services into one enterprise. Its products and services
spread worldwide, with offices and branches in Hong Kong, Chile, Peru, Zambia, Congo, USA,
UK, Iran and other regions and countries.
As a supplier of Fortune 500, KopperChem is one of the world’s largest manufacturer of
solvent extraction reagents, provides the most complete series of extractants and engineering
services, including Mextral series solvent extraction reagents and diluents, which are widely
used in hydrometallurgy of copper, zinc, cobalt, nickel, precious metals and rare earth metals,
etc.,as well as wastewater treatment, secondary resources recovery, etc.
KopperChem focuses on continuous development, provides a personalized service tailored
to each customer. The range of services include Engineering consultation, engineering design,
EPC, technology research and development, etc. in the field of metal solvent extraction, from
initial feasibility study, plant operation to lifelong service.
KopperChem concerns for the environment, health and safety, follows business ethics,
provides healthy and happy work environment and development opportunities for employees,
provides global customers with the most satisfactory products and services, to achieve economic,
resource and environmental harmony and sustainable development.
Our product: Solvent extraction reagents
Our specialty: Metal solvent extraction technology
Our goal: Do the most professional metal solvent extraction technology
Our mission: Provide global customers with the most healthy solvent extraction reagents
and technology
Learn more by visiting www.mextral.com
Universidad de Antofagasta, Department of Chemical Engineering and Min-

eral Processes
Universidad de Antofagasta is a state, regional, secular and pluralistic institution dedicated
to the training of professionals with a deep sense of responsibility to the environment and
a solid formation in human values. Created in 1981 from the union of Universidad Técnica
del Estado and Universidad de Chile. Its story has been developed together with the north
of Chile and its main industry, mining. In this area, Universidad de Antofagasta has the
Department of Chemical Engineering and Mineral Processes, who teaches undergraduate and
graduate students, in order to have professionals with metallurgical-chemical training with
all the advantages of the breadth of knowledge on industrial processes that grants chemical
engineering and mineral processes according to the needs of the mining industry. One of the
great strengths of the Department is to train students in research and innovation in production
processes of metal ores (copper, molybdenum, rhenium and others) and industrial minerals
(lithium, boron, nitrates). The Department develops projects related to the use of sea water
and solar energy in sustainable mining processes and the use of industrial minerals such as
alternative energy storage sources.
The Department teaches graduate programs of Master in Engineering Sciences, majoring
in Process Minerals and PhD in Mineral Processing Engineering, both accredited for six years,
currently with more than 60 students, 15 graduated Doctors and 25 Masters.
In the area of mining processes, the Department has successfully consolidated its work
in scientific and technological research, through various consultancies and projects for the
mining industry, and formation of advanced human capital with postgraduate courses through
its training. This work is reflected in the development of Fondecyt, Fondef, Innova Corfo,
FIC-Regional and publications in mainstream journals (ISI) projects.
More information at www.uantof.cl
Colorado School of Mines, Kroll Institute for Extractive Metallurgy

KIEM was established in 1974 in accordance with a bequest from William J. Kroll, world
renowned extractive metallurgist best known for his inventions of processes for the production
of titanium and zirconium. The financial resources of Dr. Kroll’s bequest were intended to
provide for the establishment of a Center for Excellence in Extractive Metallurgy at the Colorado
School of Mines. Since its inception, the Kroll Institute has provided financial support to
both undergraduate and graduate students at CSM, many of whom, subsequently, have made
important contributions, nationally and internationally, to the fields of mining, minerals,
metals and advanced materials.
Today, the mission of the Kroll Institute is to support the minerals, metals and materials
industries through the following activities:
· Maintain expertise and research capabilities important to the minerals, metals and
materials industries in extractive metallurgy, mineral processing, recycling and waste
minimization.
· Perform cutting edge research
· Train process engineers for industry
· Develop short courses
· Develop specialty conferences
KIEM is responsible for teaching, research and service in mineral processing and extractive
metallurgy at the Colorado School of Mines.
Learn more by visiting kiem.mines.edu
Gecamin
Powering professional development for operational excellence
Founded in 1998, Gecamin organizes highly technical, international seminars, conferences and
congresses that focus on generating interdisciplinary collaboration within multiple industrial sectors.
In its 19 year history, Gecamin has organized technical and international conferences for the
mining industry for more than 23,000 professionals in areas like Geology and Mining, Mineral
Processing, Hydrometallurgy, Sustainability and Environment, Water and Energy, Maintenance
and Automation, and Human Capital. Starting this year, it will be broadening its focus to include
other industries like pulp and paper, agroindustry, geosynthetics and retail among others.
During 2016, Gecamin organized 15 conferences joining 2,704 professionals from 40
countries, 667 being delegates from mining operations. Of the 16 events, each published a
book of presentations and contributed to a total number of 742 technical presentations.
Learn more about Gecamin conferences by visiting www.gecamin.com
COMMITTEES
Organizing Committee Celmer, Fluor, Chile • Virginia Ciminelli, National

Executive Committee Institute of Science and Technology on Mineral
Resources, Water and Biodiversity. INCT-Acqua, Brazil •
Chair William Culver, New York State University, USA •
Felipe Lagno, Plant Manager, Radomiro Tomic Division, Julio Flores, Mantos Copper, Chile • Teófilo Gráber,
Codelco, Chile Universidad de Antofagasta, Chile • Marcelo Jo, Jo y
Loyola Consultores de Procesos, Chile • Wenying Liu,
Executive Director
University of British Columbia, Canada • Luis Moreno,
Carlos Barahona, General Manager, Gecamin, Chile
Royal Institute of Technology, Sweden • Felipe Núñez,
Technical Chair Yamana Gold, Chile • Mario Núñez, Radomiro Tomic

Division, Codelco, Chile • Joe Pezo, Minera El Brocal,
Fernando Valenzuela, Head Professor, Universidad de
Peru • Juan Luis Pizarro, Salvador Division, Codelco,
Chile
Chile • Dave Robinson, CSIRO, Australia • Petrus
Technical Co - Chair Van Staden, Mintek, South Africa • Jorge Stanislav,
Xu Zhigang, Vice General Manager, KopperChem, China Minera Escondida, Chile • Ernesto de la Torre, Escuela
Politécnica Nacional, Ecuador • Julio César Tremolada,
Seminar Coordinator
Iberometex, Peru • Chi Zhang, Peking Brotech Company,
Oliver Allendes, Gecamin, Chile
China
Directing Members Committee

Percy Mayta, Past President 2016, High Service Corp., Chile •
Fernando Acevedo, Pontificia Universidad Católica
Ronie Lau, Plant Manager, Mantoverde, Mantos Copper,
de Valparaíso, Chile • Juan Álvarez, Independent
Chile • Manuel Carmona, Plant Manager, Empresa Nacional
Consultant, Chile • Allie Anderson, Colorado School
de Minería, Chile • Sergio Castro, Technical Manager,
of Mines, USA • Leonor Ardiles, BASF, Chile • José Luis
Antofagasta Minerals, Chile • Nelson Salazar, Plant Manager,
Arenas, Byohydro, Chile • Carlos Basualto, Universidad
Gabriela Mistral Division, Codelco, Chile • Gustavo Tapia,
de Chile • Juan José Becker, Amec Foster Wheeler,
Process and Technology Innovation Manager, Antofagasta
Chile • Tom Boundy, Colorado School of Mines, USA •
Minerals, Chile • Arturo Albornoz, Project Manager, Minera
Germán Cáceres, Universidad Andrés Bello, Chile •
Biolantánidos, Chile • Svetlana Ushak, Head of Department
Brett Carlson, Colorado School of Mines, USA •
Chemical Engineering and Mineral Processing Universidad de
Héctor Carreño, Chuquicamata Division, Codelco,
Antofagasta, Chile • Zou Qian, Chairman, KopperChem, China •
Chile • Jesús Casas, Universidad Adolfo Ibáñez, Chile •
Corby Anderson, Professor of Metallurgical and Materials
Luis Cisternas, Universidad de Antofagasta, Chile •
Engineering, Colorado School of Mines, USA
Martha Claros, Universidad de Antofagasta, Chile •
Robinson Constanzo, Pontificia Universidad Católica
Advisory Committee de Valparaíso, Chile • Davor Cotoras, Universidad de
Isaías Almaguer, Industrias Peñoles, Mexico • Juan Chile • Ismail Duman, Istanbul Technical University,
Carlos Álvarez, Barrick Zaldívar, Chile • David Alvear, Turkey • Daniel Ernt, MineXTech, USA • Humberto
Ministro Hales Division, Codelco, Chile • Francisco Estay, Arcadis, Chile • Juan Carlos Gentina, Pontificia
Arriagada, Arcadis, Chile • Antonio Ballester, Universidad Católica de Valparaíso, Chile • Ahmad
Universidad Complutense de Madrid, Spain • Dick Ghahremaninezhad, Queen’s University, Canada •
Mario Grágeda, Universidad de Antofagasta, Chile • University, China • Héctor Yáñez, BASF, Chile •
Nélida Heresi, JRI Ingeniería, Chile Pía Hernández, Rodrigo Zambra, Solvay, Chile • Wensheng Zhang,
Universidad de Antofagasta, Chile • Fabián Hurtado, CSIRO, Australia • Jaime Zúñiga, Barrick, Chile
SNC-Lavalin, Chile • Ricardo Jeldres, Universidad
de Antofagasta, Chile • Wen Jiankang, GR INM, Editorial Committee
China • Yecid Jiménez, Universidad de Antofagasta,
Chile • Liu Jing, Tsinghua University, China • Jae- Chief Editor
chun Lee, Korea Institute of Geoscience and Mineral Fernando Valenzuela, Universidad de Chile
Resources, Korea • Claudio Leiva, Universidad Católica
del Norte, Chile • Yang Limei, GR INM, China •
EDITORS
Li Linyan, Tsinghua University, China • Adalbert
Jesús Casas, Universidad de Chile, Chile • Pía
Lossin, Aurubis, Germany • Juan Pablo Mardones,
Hernández, Universidad de Antofagasta, Chile •
SQM, Chile • Patricio Martínez, CodelcoTech, Chile •
Patricio Martínez, CodelcoTech, Chile • Sergio Rivera,
Paola Matus, Fundación Chile • Ramón Mendoza,
Universidad Nacional Andrés Bello, Chile
Southern Peru Copper Corporation, Peru • Marcelo
Montenegro, CICITEM, Chile • Gonzalo Montes, COPY EDITORs
Universidad de Chile • Stephen Neethling, Imperial
Oliver Allendes, Gecamin, Chile
College London, UK • Rafael Padilla, Universidad
Bárbara Alcayaga, Gecamin, Chile
de Concepción, Chile • Christian Pastén, Glencore,
Chile • Fernando Penna, Tecnocomposites, Chile • REVIEWERS
Tang Qiming, KopperChem, China • Sergio Fernando Acevedo, Pontificia Universidad Católica de
Rivera, Universidad Nacional Andrés Bello, Chile • Valparaíso, Chile • Allie Anderson, Colorado School
Claudio Rodríguez, Outotec, Chile • María of Mines, USA • Leonor Ardiles, BASF, Chile • Juan
Cristina Ruiz, Universidad de Concepción, Chile • Álvarez, Independent Consultant, Chile • José Luis
Felipe Sagredo, Radomiro Tomic Division, Codelco, Arenas, Byohydro, Chile • Carlos Basualto, Universidad
Chile • Marcelo Saldaña, Chuquicamata Division, de Chile • Juan José Becker, Amec Foster Wheeler,
Codelco, Chile • Hunter Sceats, Colorado School of Chile • James Besa, Chen Minerals & Engineering,
Mines, USA • Doug Schriner, Colorado School of Mines, Zambia • Tom Boundy, Colorado School of Mines, USA •
USA • Andrés Soto, Universidad San Sebastián, Chile • Germán Cáceres, Universidad Andrés Bello, Chile •
Eric Spiller, Colorado School of Mines, USA • María Jesús Casas, Universidad Adolfo Ibáñez, Chile •
Elisa Taboada, Universidad de Antofagasta, Chile • David Chaiko, F L Smidth, USA • Luis Cisternas,
Zhou Tao, Central South University, China • Jaime Universidad de Antofagasta, Chile • Martha Claros,
Tapia, Universidad Arturo Pratt, Chile · Patrick Taylor, Universidad de Antofagasta, Chile • Davor Cotoras,
Colorado School of Mines, USA • Tomás Vargas, AMTC, Universidad de Chile • Teófilo Gráber, Universidad de
Universidad de Chile • David Vázquez, Industrias Antofagasta, Chile • Juan Carlos Gentina, Pontificia
Peñoles, Mexico • Mariajose Vega, DICTUC, Chile • Universidad Católica de Valparaíso, Chile • Nélida
Álvaro Videla, Pontificia Universidad Católica de Chile • Heresi, JR I Ingeniería, Chile • Pía Hernández,
Héctor Vilches, Minera Amalia, Chile • Liu Xin, Universidad de Antofagasta, Chile • Fabián Hurtado,
Tsinghua University, China • Wang Xuejun, Tsinghua SNC-Lavalin, Chile • Ricardo Jeldres, Universidad de
Antofagasta, Chile • Yecid Jiménez, Universidad de
Antofagasta, Chile • Marko Lampi, Outotec, Finland •
Jae-chun Lee, Korea Institute of Geoscience and
Mineral Resources, Korea • Claudio Leiva, Universidad
Católica del Norte, Chile • Xiaorong Liu, Shanghai
Institute of Technology, China · Juan Pablo Mardones,
S QM , Chile • Patricio Martínez, CodelcoTech,
Chile · Jorge Menacho, De Re Metallica Ingeniería,
Chile • Gonzalo Montes, Universidad de Chile •
Rafael Padilla, Universidad de Concepción, Chile •
Nelson Parra, Ecometales, Chile • Patricia Piña,
CodelcoTech, Chile • Fernando Penna, Tecnocomposites,
Chile • Sergio Poblete, B A S F, Chile • Sergio
Rivera, Universidad Nacional Andrés Bello, Chile •
Claudio Rodríguez, Outotec, Chile • Julio Romero,
Universidad de Santiago de Chile • Leonardo Romero,
Universidad Católica del Norte, Chile • María Cristina
Ruiz, Universidad de Concepción, Chile • Felipe
Sagredo, Radomiro Tomic Division, Codelco, Chile •
Marcelo Saldaña, Chuquicamata Division, Codelco,
Chile • Doug Schriner, Colorado School of Mines, USA •
Hunter Sceats, Colorado School of Mines, USA •
Eric Spiller, Colorado School of Mines, USA • Jaime
Tapia, Universidad Arturo Pratt, Chile • María Elisa
Taboada, Universidad de Antofagasta, Chile • Patrick
Taylor, Colorado School of Mines, USA • Svetlana
Ushak, Universidad de Antofagasta, Chile • Fernando
Valenzuela, Universidad de Chile • Tomás Vargas,
AMTC, Universidad de Chile • Ysrael Vera, Center for
Mineral Technology, Brazil • Héctor Vilches, Minera
Amalia, Chile • Héctor Yáñez, BASF, Chile • Rodrigo
Zambra, Solvay, Chile • Xu Zhigang, KopperChem, China
FOREWORD
am honored to welcome all professionals, academics and students to the 9th International
Seminar on Hydrometallurgical Processes, Hydroprocess 2017, and the International
Conference on Metal Solvent Extraction, ICMSE 2017. I trust that this seminar will be a
source of exchange of knowledge, best practices and experiences for each of you.
It is recognized by all mining professionals the great contributions that hydrometallurgy
has given to the mining industry and to the processes of benefit of minerals. Clean
production; recovery of metals of high purity; processing of low-grade minerals; treatment
of effluents and stabilization of impurities are just a few examples of the areas of action
and contribution of hydrometallurgy in the development and consolidation of the mining
industry in Chile and the world.
As hydrometallurgists we have faced, for some years, important challenges. The already
known depletion of leachable reserves and other facts like decreasing labor productivity; the
scarcity of water resources; and greater (and more stringent) environmental regulations.
We seek that this seminar, through interesting presentations from various places of the
planet coupled with the exchange of experiences and fruitful technical discussions, will
give us tools to become part of these interesting challenges and overcome them.
I hope to enjoy this seminar, to participate actively, and above all, to surrender our
experience and knowledge to make of these days a contribution to the mineral industry.
Thank you very much and be all very welcome.
Felipe Lagno
Chair
Hydroproce s s - ICMSE 2017
9th International Seminar on Process Hydrometallurgy
International Conference on Metal Solvent Extraction
PREFACE
Hydroprocess-ICMSE 2017, held from June 21-23, 2017 at the Hotel Grand Hyatt at Santiago,
is the ninth of a series of international seminars on process hydrometallurgy initiated in
2006 by Gecamin in Chile. Hydroprocess-ICMSE 2017 has been designed to provide an
international forum where hydrometallurgy professionals can analyze and discuss the most
recent innovations and developments concerning the processing of ore, concentrates and
other materials in aqueous solutions. Undoubtedly, this consolidated seminar is recognized
in the region, given the high number of paper submissions and the diverse assortment of
technical subjects covered. The number of countries, companies, universities and research
centers that are represented, also speak of the importance of this event. Participation, despite
the difficulties faced by the industry, exemplifies the vitality of this seminar for professionals
to update and exchange best practices, new technologies and experiences.
For this version of the seminar, we had the opportunity of developing Hydroprocess along-
side the International Conference on Metal Solvent Extraction, ICMSE, from KopperChem,
China. We are grateful for the opportunity of bringing experience and knowledge from the
East to Latin America. There are 7 papers by Chinese authors, both academic and profession-
als. Chinas has quickly become a relevant player in the industry, and we are pleased to have
shared this seminar with them.
The Hydroprocess-ICMSE proceedings contain 58 abstracts written by delegates from 13
different countries. With a thematic distribution of papers that includes the most relevant
areas of modern hydrometallurgy, such as: hydrometallurgy of base metals, gold and silver
and saline compounds, solvent extraction and electrometallurgical processes, biohydrometal-
lurgy, leaching of sulfide concentrates and ores, innovation in hydrometallurgical processes,
recycling of metals and alloys and industrial case studies; among others.
We expect that the seminar and these proceedings will be of interest to the international
mining hydrometallurgical community highly engaged to comply with the primary spirit of
this special version of the seminar. Hydroprocess-ICMSE 2017 are the ideal for all hydromet-
allurgical professionals to gather, discuss and cooperate to continue making hydrometallurgy
profitable for the future and discovering news trends in the mining business.
I would like to thank all the professionals from different countries that have selflessly
collaborated with us. My deepest thanks to the Gecamin staff for their efforts and enthusiasm
in making Hydroprocess-ICMSE a success. Finally, I expect all delegates to this seminar to
have had a nice stay in Santiago and have enjoyed their participation. We look forward to
seeing you in 2018.
Fernando Valenzuela
Technical Chair and Chief Editor
HYDROPROCESS - ICMSE 2017
ACKNOWLEDGEMENTS
The Executive Organizing Committee acknowledges with gratitude the efforts of all the
authors for contributing a large variety of high quality, detailed and innovative papers to
the technical program. We also would like to thank the reviewers, the employees from
Gecamin, and all those involved in the creation of these proceedings for their assistance.
The support of the Organizing, Editorial, Advisory and Technical Committees has been
greatly appreciated, as has been the support of the Hydroprocess-ICMSE 2017 Chair and
the different Chairs of technical sessions.
The Executive Organizing Committee also wishes to thank the following sponsors or
their generous support:
Platinum: Outotec
Gold: KopperChem, IXOM
Silver: RSR Anodes, Quemetco Metals, Transmin Metallurgical Consultants, Solvay,
Pultrusion Technique, Relix water, Desert King, Verne, Ancor Tecmin, SAX, Bruker,
Solmax, CML Comercializadora
Socials: BASF, FLSmidth, Metalex
Official Material: BASF
Others: Copec and Axxa Chemicals
Institutional Partners: SMI ICE Chile, International Centre of Excellence; Sociedad
Nacional de Minería (Sonami), Chile; Consejo Minero, Chile; Servicio Nacional
de Geología y Minería (sernageomin), Chile; The Brazilian Mining Association
(IBRAM); Instituto de Ingenieros de Minas del Perú; Australian Government; Women
in Mining Chile; UK Trade and Investment; Minnovex, Chile; Asociación Gremial de
Suministradores Técnicos y de Ingeniería para la Minería e Industria (SUTMIN), Chile;
Alianza Valor Minero, Chile
Official Media: Revista Nueva Minería y Energía, Chile
Media Partners: Direcmin, Chile; El Inversor Energético y Minero, Argentina; Panorama
Minero, Argentina
Finally, we would like to thank all the delegates who attended the seminar and exchanged
their valuable knowledge and expertise, thus contributing to the great success of this 9th
edition of the International Seminar on Process Hydrometallurgy and the International
Conference on Metal Solvent Extraction, Hydroprocess-ICMSE 2017. We are looking
forward to seeing you all again during the next version of Hydroprocess, in the year 2018.
Executive Organizing Committee

Hydroproce s s - ICMSE 2017
PLENARIES
Recent Updates on the Hydrometallurgical
Processing of Primary Copper Sulfides
Ahmad Ghahreman
Queen’s University, Canada
ABSTRACT
Hydrometallurgical processes for the chloride treatment of copper sulfide ores and concentrates are
under development.
Leaching of the copper sulfide minerals in the chloride media has advantages over sulfate media.
Smaller scale of operation, increased leaching kinetics and higher recovery of the valuable metals
are some of the benefits of the chloride leaching media over other similar media. On the opposite
side, the corrosive characteristics of chloride solutions, selective leaching of copper, and efficient
copper recovery from PLS are some of the challenges with the chloride leaching processes.
Impurity removal from the chloride solutions, and regeneration and recycling of hydrochloric acid
and chloride reagents are among the other challenges with chloride processing.
In this paper, the metallurgy of primary copper sulfide ores and concentrates leaching in chloride
media is reviewed. An update on the recent developments of the chloride processing of sulfide
ores and concentrates is presented.
There is no full article associated with this abstract.
1
Challenges in 20 Years of Operation of the Leaching
Plant, Solvent Extraction and Electrowinning at
Toquepala
José Luis Tenorio and José Arenas
Toquepala, Southern Copper, Peru
SUMMARY
Southern Copper produces about 55 million pounds per year of copper cathode Grade A LME
(London Metal Exchange Market) in its SX-EW Plant at Toquepala Peru, began operations in
November 1995. Copper is recovered by leaching piles copper oxide ores at the Cuajone mine with
an acid leaching and leaching deposits (dumps) sulphide ore crushed low-grade copper with an
acid-iron-bacterial leaching at the Toquepala mine.
During the 20 years of operation of the hydrometallurgical process of Toquepala, they have been
considerable changes mainly in the type of mineral that reaches our leachable deposits, changing
the variables of the process; so it was necessary to work continuously improve and optimize
processes (design, mineral processing, change of reagents and ranges of operating variables) mainly
for handling solutions with low grades of copper in the PLS (pregnant leach solution) in order to
maintain production and obtain high purity cathodes higher copper 99, 999%. With the
implementation of an Integrated Management System (SIG) and working under standards of safety,
quality and environmental system cathode quality are ensured.
1
Path to a Cultural Transformation with “C+”
Gabriela Mistral Division, Codelco Chile

Alejandro Flores and Nelson Salazar
Gabriela Mistral Division, Codelco Chile
ABSTRACT
Codelco Chile as a major producer of a Copper, a worldwide traded commodity, was severely
affected by the steady decline in price seen in last five years. It also saw a progressive decline in ore
grades as well as steady rise in the costs of critical inputs. Codelco’s Gabriela Mistral division has to
adjust its way of managing the business-; a new approach has to be adopted to drive productivity
gains in the operation.
C + is the trademark that Codelco Chile Corporation called the implementation of the Lean
management system to achieve operational excellence in its assets.
Two-digit improvement in safety, production and costs are the new business objectives. Challenging
yet attainable goals were to be achieved, all at once and in a short period. New challenges call for
new methods to drive continuous improvement in operating systems and processes. Gabriela Mistral
division is then pursuing two well-defined objectives:
1) Diagnose its operating system with the aims of identifying and removing bottlenecks. This can be
achieved by attacking root cause of production losses. The aspiration was set 126.000 tons per day
(46 Mton per year) on the basis of a study of technical limits of the plant for treatment of copper ore
to be deposited in leaching piles.
2) Adopt a new management system based on Lean Management, which through standardized tools
and practices to be carried out by senior leadership, managers, foremen and operators has the
objective of generating continuous improvement on the operating system. It runs on an influence
model led by the leaders of the division.
Gabriela Mistral division has been in this transformational journey for 18 months, implementing it in
different functional areas such as Operations and Maintenance as well as at different stages of the
production process such as Mine and Plant. Significant impact has been achieved, with production
steadily increasing towards the aspiration defined.
1
Scale Up of Hydrodynamic and Metallurgical
Parameters in Heap Leaching Operations
Jorge Menacho
De Re Metallica Ingeniería, Chile
ABSTRACT
Main current procedures to scale up results from column and box experiments to industrial heap
leach operations are fully discussed with emphasis in the advantages and limitations in each case.
Hydrodynamic fundamentals in heap leaching are reviewed with regard to gather the correct
experimental data and its further projection to industrial scale. Main flow design as well as
metallurgical parameters are identified and the way to project experimental results to industrial
heap leach plants is presented.
The scale up of heap leaching data is sensitive to actual kinetic pattern such that fast dissolution
minerals respond to the irrigation ratio, m3/t, while slow kinetics minerals are also sensitive to the
leaching time. Appropriate test must be designed such that both criteria are simultaneously
satisfied.
Main irrigation practices are discussed according to the physical and chemical quality of the
expected materials to be provided by the mine. Design of wetting ramps, maximum irrigation rate,
heap height and the use of intermittent strategy are explained in detail from fundamental and
practical viewpoint.
Specific study cases are presented to support the proposed methodologies and a set of practical
recommendations are finally given to engineers facing new projects as well as optimizations trials
in existing operations.
1
Iron Phase Control During Pressure Leaching of
Copper in Sulfate Solutions at Elevated
Temperatures
Camille Fleuriault1, Corby Anderson1, and Scott Shuey2
1. Kroll Institute for Extractive Metallurgy, Colorado School of Mines, USA
2. Newmont Mining, USA
ABSTRACT
Iron can be precipitated out of leaching solutions by using high pressure processes. The focus of this
study was on the various iron phases forming during the pressure oxidation of copper in a sulfate
system. Artificial solutions were produced from sulfuric acid, copper and iron sulfates in an attempt
to recreate the matrix composition and conditions used for copper sulfides autoclaving. The influence
of the following factors was investigated: initial free acidity, initial copper concentration and initial
iron concentration. There were three solid species formed in the autoclave: hematite, Basic Iron
Sulfate (BIS) and hydronium jarosite. Free acid is the main factor influencing the composition of the
residue. The increase of BIS content in the residue is not gradual and occurs over a change of a few
grams per liter of sulfuric acid. Increasing copper sulfate concentration in the solution hinders the
formation of BIS. This effect seems to be related to the buffering action of copper sulfate, decreasing
the overall acid concentration and thus extending the stability range of hematite. Increasing iron
concentration on the precipitate chemistry seems to promote BIS formation. At high iron level, the
most noticeable effect is the inhibition of jarosite. The results were reported within a Cu-Fe-S ternary
system and modeled. The modeling confirmed the experimental observations.
1
PLCC Project: Autoclave Technology Applied to
Complex Copper Concentrates
Nelson Parra, Marcelo Acuña and Orlando Fuentes
EcoMetales Limited, Chile
ABSTRACT
In recent years arsenic content in copper concentrates has increased along with environmental
restrictions for their transport and processing. China has set a benchmark maximum of 0.5% for the
arsenic content in copper concentrates and in the future it is expected that this value is going to be
more restrictive. Smelting process disposes part of the arsenic as calcium arsenite which is not a
stable compound and in the future changes will have to be made to dispose this arsenic as a stable
compound.
Under this scenery is being developed the Complex Concentrate Leaching Project (PLCC), which
allows the treatment of copper concentrates with high arsenic content (>0.5%) through a high
pressure (2873 kPa) and temperature (220°C) leaching process within an autoclave. Through the
addition of high purity oxygen and cooling water to control the temperature is possible to dissolve
over 99% of copper and arsenic compounds. Dissolved arsenic is then precipitated as ferric
arsenate, which is a stable compound that passes all the environmental tests. The oxidized slurry
from the autoclave is depressurized, cooled and afterwards sent to a solid/liquid separation stage
generating a high copper PLS solution and an arsenical residue. The PLS is sent to a solvent
extraction plant to produce copper cathodes where it is previously mixed with heap/dump PLS
solutions. On the other hand, the arsenical residue is stored on a deposit or sent to a silver recovery
process that will be developed in a future stage.
This work describes the progress to date of the PLCC project highlighting: the laboratory and
piloting tests work and principal results, process description, advantages and strengths of the
project and it’s insertion within the Northern District of Codelco or other companies in different
countries in order to be a solution for the treatment of complex copper concentrates.
1
INTRODUCTION
Between years 2000 and 2015 world copper production from concentrates has increased
approximately from eleven to fifteen millions of metric tonnes per year. In 2014 Chile produced
26.5% of the total copper from concentrates and in the future it is expected that copper production
in Chile will raise, mainly associated to production of concentrates (Figure 2).
Figure 1 Copper Production from Concentrates (Source: Cochilco 2016)
Figure 2 Copper Production in Chile (Source: Cochilco 2016)
2
In recent years arsenic content in copper concentrates has increased along with environmental
restrictions for their handling, transport and processing (Figure 3). China has set a benchmark
maximum of 0.5% for the arsenic content in copper concentrates and in the future it is expected that
this value is going to be more restrictive.
Figure 3 Complex Copper Concentrates Production (Source: Wood & Mackenzie)
Under this scenery is being developed the Complex Concentrate Leaching Project (PLCC), which
allows the treatment of copper concentrates with high arsenic content (>0.5%) through a high
pressure (2873 kPa) and temperature (220°C) leaching process within an autoclave. This work
describes the progress to date of the PLCC project highlighting: the laboratory and piloting tests
work and principal results, process description, advantages and strengths of the project and it’s
insertion within the Northern District of Codelco or other companies in different countries in order
to be a solution for the treatment of complex copper concentrates.
PROJECT HISTORY
Between 2011 and 2012 the Division of Codelco Radomiro Tomic (DRT) made a conceptual study
including alternatives for processing their future concentrates. The alternatives studied included
the Albion, Galvanox, CESL and a medium pressure and temperature oxidation (MPOX) processes.
Preliminary experimental work was done and it was concluded that pressure leaching technologies
(CESL and MPOX) were the most cost effective and better developed at that time when compared
to atmospheric leaching options studied. During 2012 DRT continued their studies comparing CESL
and a high pressure and temperature oxidation (TPOX) process, considering that the latter
generates more sulfuric acid than MPOX process that could be used in their own heap/dump
leaching facilities or in the facilities of Division of Codelco Chuquicamata (DCH). Initially a 700
3
ktpy plant capacity and CESL process were defined but it was decided to move forward
considering a demonstrative plant as a first phase of the confirmation of the feasibility of their
concentrate leach project.
During 2013 a new conceptual study was made comparing CESL and TPOX processes considering
different demonstrative plant capacities (20 to 150 ktpy), plant location and PLS destination. As a
result a 150 ktpy plant capacity considering TPOX process was defined, located beside EcoMetales
facilities or in DRT, and the PLS could be sent to SX plant in DCH or in DRT.
During 2013 DRT developed a scoping study analysing the use of pressure leaching of copper
concentrates with arsenic from different Divisions of Codelco: DCH, DRT, Ministro Hales (DMH)
and Salvador (DSAL). Due to the potential of treating complex copper concentrates with these
technologies Codelco assigned EcoMetales to continue developing the project considering the
TPOX process. During 2014 a prefeasibility study was done that included laboratory and piloting
test work considering complex concentrates from DCH and DMH, roaster dust from DMH and
acidic effluent from sulphuric acid plant (EPAS) from DCH. In this study it was evaluated the plant
capacity; different concentrates, dust and EPAS proportions in the feed; location of the plant and
waste disposal; and PLS destination. Laboratory tests were also conducted at a scoping level to
evaluate the silver and gold recovery from TPOX process residues. During 2016 a feasibility study
was done for the TPOX process applied to DCH and DMH concentrates and roaster dust from
DMH. Laboratory and pilot test were conducted to confirm the design and operational parameters
for the autoclave and different water qualities and cooling (temperature and time) of the residue
were studied in order to improve arsenic precipitation. Batch tests were also made with the TPOX
residues to evaluate a process for recovering gold and silver. In both prefeasibility and feasibility
studies Hatch made the engineering design.
In the following chapters it is described the test work done and their principal results considering
both prefeasibility (2014) and feasibility (2016) studies, the process flowsheet, advantages and
strengths of the project and it’s insertion within the Northern District of Codelco or other
companies in different countries in order to be a solution for the treatment of complex copper
concentrates.
LABORATORY AND PILOTING TEST WORK

During the development of the prefeasibility (2014) and feasibility (2016) laboratory studies and
pilot test work were done by Sherritt Technologies (Fort Saskatchewan, Canada) and SGS
(Lakefield, Canada) respectively. In both campaigns a 40 L autoclave (Table 1) was used for the
pilot tests with an average flow rate of 4 kg/h. Initial laboratory tests were done in a 2,5 L (Sherritt)
and 2,0 L (SGS) autoclaves in order to determine the operational conditions of the autoclave
(prefeasibility) and to optimize the arsenic deportment (feasibility).
The pilot campaigns considered the use of DCH and DMH concentrates plus roaster dust from
DMH, the latter being only tested at a pilot level during the feasibility stage. The pilot campaigns
for the prefeasibility and feasibility last for 240 h and 320 h respectively. During the pilot testwork
the following aspects were analysed:
- Autoclave: Residence time, different ratios between concentrates and dust and cooling
water quality and different proportions of EPAS solution in the feed.
4
- Solid/Liquid Separation: Three different suppliers made pilot tests with the TPOX residues
in order to specify the thickening and filtration stages.
- Rheological Tests: Rheological tests were done for the concentrates and roaster dust in
order to determine pulp density for preparation and mixing stages.
- Environment Tests: TPOX residues were submitted to TCLP, SPLP, inflammability,
corrosion, toxicity (chronic and acute) and reactivity tests.
- Corrosion: Coupons of different materials were inserted in the autoclave, flash tanks and
thickener in order to define materials of construction.
- Gases: Gases from the autoclave and flash tank were collected and submitted to analysis
including moisture content, total particulate, multimetal scan, VOC scan, O 2, N2, CO2, SO2,
CO, NOx, NO, NO2, H2S and arsine.
Table 1 Pilot Autoclave Characteristics
Item Sherritt SGS
Volume [L] 40 40
Type Horizontal Horizontal
N° of Compartments 5 / 4(*) 5
N° of Agitators 6 6
Agitation [rpm] 750 – 1.050 500 – 600
(*) From periods one to four the autoclave run with five compartments and from periods five to eight with four
compartments.
RESULTS
From the laboratory and piloting tests the following principal results were obtained:
- Autoclave operational conditions:
o Residence Time: 60 min
o Oxygen Overpressure: 500 kPa
o Total Pressure: 2873 kPa
o Temperature: 220 °C
- Copper recovery is a function of the molar ratio between iron and arsenic in the concentrate
and quench solution fed to the autoclave. A molar ratio above 10 ensure a copper extraction
over 98,5%. No difference was observed in the copper extraction by adding arsenic in
concentrate or adding an equivalent amount as EPAS solution.
5
Figure 4 Copper Extraction
- In order to minimize arsenic redisolution the oxidized slurry from the autoclave must be
cooled to 40°C rapidly (30 minutes from flash tank to thickeners).
- Water of quality equivalent to a desalinated water showed higher arsenic deportment (90%)
in comparison to process water.
- Arsenic precipitates as a ferric arsenate (type II) compound. TCLP, SPLP, inflammability,
corrosion, toxicity (chronic and acute) and reactivity tests were done to the TPOX residue
concluding that the residue is stable and not dangerous according to Chilean
environmental regulations (DS.148).
- Solid / Liquid separation tests done showed that the solid separates adequately. The design
considers a high rate thickener followed by a press filter. Flocculant is added to the
thickening stage (100 g/t) to improve solid decantation. The underflow generated has a
pulp density of 45% to 50%. The filtration stage considers two washing stages with a 99%
washing efficiency and generates a cake with a humidity of 20% to 25%.
- Minor scales were formed during the piloting campaign according to Hatch’s experience in
high pressure oxidation projects. Scale formation at an industrial level would be minor and
can be controlled with an adequate agitation design and maintenance program.
- The tests considered a wide range for arsenic (1.1% - 5.6%) and copper (25.6% - 32.0%). Also
a wide range for copper mineralogies was analysed. The results showed that the process is
flexible, allowing processing different proportions between DCH and DMH concentrates (0
to 100% for each concentrate).
- PLS solutions from the piloting tests were sent to Cytec facilities in Phoenix (USA) together
with PLS and organic solutions from DCH and DRT plants. Mixtures between autoclave
and plant PLS were analysed considering future mining plans. Results showed copper
recovery similar to the current ones considering a greater organic/liquid ratio (up to 1.5)
and extractant (up to 32% v/v) in the organic.
6
Figure 5 Copper Distribution in Piloting Campaign
TPOX residues were submitted to bench scale tests to evaluate gold and silver recovery. Lime boil
and cyanidation tests done showed that extractions of silver and gold up to 80% and 98%
respectively can be achieved. A preliminary flowsheet was defined including also SART process to
generate a copper/silver residue, AVR process to recover cyanide and a carbon column to recover
gold. Future work is required in order to define a technical and economically process at a
prefeasibility level.
PROCESS DESCRIPTION
Based on the results of the pilot campaigns the process shown in Figure 6 was developed. The
process considers a separate reception and storage area for the concentrates and dust with one day
total storage capacity for each material. Concentrates are repulped at 70% pulp density and dust at
45% pulp density. Both slurries are then transferred to a mixing tank and then to the autoclave feed
storage tank which has 24 h storage capacity.
The slurry from the autoclave feed storage tank is fed to the first compartment of the autoclave
which works at a temperature of 220 °C and a total pressure of 2873 kPa. In order that sulphide
species get oxidized high purity oxygen is fed in each compartment. The residence time in the
autoclave is 45 to 60 min after which copper is dissolved (> 98.5%) and arsenic is first dissolved and
then precipitated as ferric arsenate (type II).
The oxidized slurry is transferred to two flash tanks that operate in parallel in order to depressurize
the slurry from 2873 kPa to 100 kPa and then it is transferred to a tank from where it is pumped to a
heat exchanger circuit (three circuits of four heat exchanges operating and one circuit in stand by)
which cools the slurry from 97°C to 40°C. The depressurization in the flash tanks generates steam
that goes out from the flash tank along with entrainments of slurry. The gases from both flash tanks
are fed to a gas cleaning system which is composed of two cyclones, a quench tower and scrubber.
Each cyclone receives the gas from one flash tank. The gases from both flash tanks are transferred to
a quench tower where cooling water is added to clean and cool the gas. The gas from the quench
tower is fed to the scrubber where water is added and 99% of the particulate material is recovered
before the gas is released to the atmosphere. In the quench water part of the vapour is condensed
7
and recovered as hot water. This water and the water from the scrubber are sent to a cooling system
in order to recycle part of this cold water to the quench tower.
The cooled slurry from the heat exchanger circuit is fed to a thickener where flocculant is added to
improve the solid / liquid separation. The underflow from the thickener has 45% to 50% pulp
density is fed to a set of two filter presses which works alternately. The filter is washed in two
stages with a washing efficiency of 99%. The final arsenical residue with 20% humidity is
transported with trucks to waste disposal.
The PLS overflow from the thickener is fed to a clarifier where flocculant is added to separate
remaining solids in the PLS. The underflow from the clarifier is recycled to the thickener and the
clean PLS is fed to a diluent treatment stage to recover remaining solids and surfactants in the PLS.
The clean PLS is fed to a storage pond with 12 h capacity and it is pumped to an existing PLS pond
in DRT where it mixes with heap leaching PLS before is fed to the SX plant.
Autoclave Vent
Concentrate Gas Cleaning
Gas Gas to
System
Atmosphere
DMH Dust
Repulping Gas Water
Water
Cold
Water
Oxygen Thickener
High Slurry S Residue to
Flash
Pressure Cooling HX Filtration Disposal
Cooling Tank Feed Tank
Water Leaching L Or
Water
Ag/Au Recovery
Tank
Hot Water
Solids to Solids and

SX Treatment Tensoactives Clarifier
Plant Removal
PLS
PLS to
SX/EW
Water
Heap
SX
Raffinate Leaching Ripios to
PLS Pond
Disposal
EW Cu
Cathodes
Figure 6 PLCC Block Diagram
CAPEX, OPEX AND ADVANTAGES OF PLCC PROJECT

The basic engineering done during the feasibility study indicated a total capital cost for the PLCC
project of 324 USD and an operational cost of 24 ¢USD/lb Cu .
The main advantages of the PLCC project are:
- Impurities such as antimony, arsenic, bismuth and mercury among others are co-
precipitated with iron oxides in the autoclave.
- The arsenical residue generated in the process is environmentally stable and classified as
non-dangerous according to Chilean regulations (DS-148).
8
- High copper recovery reaching over 99% for concentrates and 98.7% for mixtures of
concentrate (90%) and roaster dust (10%).
- No contaminants (SO2 and As) are released to the atmosphere.
- Robust and flexible process that is capable of processing different type of materials and
mixtures of concentrates, roaster dust and matte.
- Low make up water consumption (0.3 m3/t concentrate).
- Part of the heat generated in the autoclave can be used in the current facilities of
Ecometales generating fuel oil savings.
INSERTION OF THE PROJECT IN CODELCO OR OTHER COMPANIES

The PLCC project can be a complement to the actual smelting refining process used in the Northern
District of Codelco or other companies taking into consideration the following aspects:
- PLCC gives flexibility to the smelter and roaster allowing the treatment of copper
concentrates with high contents of impurities.
- PLCC has competitive cost compare to the alternative of selling or blending copper
concentrates.
- PLS solution generated in the process can be sent to an existing SX/EW plant to recover
copper as cathodes.
- Weak acid generated in the autoclave can be used in heap or dump leaching after copper
recovery in SX/EW plant.
- Arsenic is deported as a non-dangerous and stable compound.
- The process can also be applied to clean concentrates maintaining its efficiency and
competitiveness.
- Make up water is lower than smelting – roasting and refining processes.
- Heat generated in the autoclave can be used to heat solutions from existing facilities.
9
REFERENCES
Bruce, R. Mayhew, K., Demopoulous, G.P., Heidel, A. Arsenic Stability and Characterization of
CESL Process Residues.
Cantallopts J. Mercado de Concentrados de Cobre. Expomin, abril 2016.
Dreisinger, D., 2006. Copper leaching from primary sulfides: Options for biological and chemical
extraction of copper. Hydrometallurgy, 83 (2006) 10-20.
Marsden, J., Brewer, R. 2003. Hydrometallurgical processing of copper concentrates by Phelps
Dodge at the Bagdad mine in Arizona. Proceedings of the ALTA copper conference. Melbourne,
Australia 2003. ALTA Metallurgical Services.
Marsden, J., et al. 2007a. Medium-temperature pressure leaching of copper concentrates Part I:
Chemistry and initial process development. Minerals & Metallurgical Processing, Vol.24, No.4,
pp.193-204.
McDonald, R.G, Muir, D.M Pressure Oxidation leaching of chalcopyrite. Part I: Comparison of high
and low temperature reaction kinetics and products. Hydrometallurgy 86 (2007), pp: 191-205.
10
CHAPTER 1
Innovation,
Development and
Process Improvement
Economic Recovery and Upgrade of Metals from
Middling and Tailings Streams
Paul Voigt1, Daniel Mallah2, Mike Hourn1, Virginia Lawson1, Greg Anderson1 and Glenn
Stieper1
1. Glencore Technology, Australia
2. Glencore Zinc, Australia
ABSTRACT
As mine head grades decline and orebodies become more complex, traditional mineral processing
techniques and flowsheets to achieve saleable concentrate become more difficult to design and
construct. Mines with lower quality concentrates or concentrates with penalty elements are
particular under threat. The economics of these operations are far more susceptible to metal price,
concentrate treatment terms and the availability of other, cleaner concentrates. Additional value
may be realised for these orebodies through improved recovery by producing a low grade
middling concentrate for further processing, in conjunction with a saleable concentrate.
The most cost effective way to reduce impurity levels is to do so as early as possible in the mining
value chain. Technologies such as fine grinding and fine particle flotation are well established as
effective methods for impurity rejection in mineral processing. What is normally overlooked is how
a hydrometallurgical process could also be integrated in the overall flowsheet to achieve higher
overall recovery at the mill. In the base metals environment, this is mainly because
hydrometallurgical processes are associated with production of metal or use of expensive and toxic
precipitating agents once the minerals of interest are solubilised. These processes can be very
expensive, particularly with rising power costs and poor economies of scale in capital costs
associated with low production rates from middling streams.
Glencore Technology (GT) has recent experience in the treatment of middling and low grade
concentrate streams as well as tailings streams to compliment a concentrator flowsheet in a
refractory gold and base metals setting. The value proposition is the isolation of a low grade
middlings concentrate from the primary circuit or the tailings stream for upgrading to an
intermediate product with an equal or higher grade than the primary concentrate to allow blending
for sale. This allows plants to operate on a more favourable part grade-recovery curve while
avoiding the expense of metal production. For existing operations this is particularly attractive
since it can be added on with no process interruptions.
Two case studies are examined showing flowsheets and costings to arrive at the value proposition
of the GT low grade treatment flowsheet.
1
INTRODUCTION
One significant challenge facing the gold and base metals mining industries is the globally observed
trend of reducing mined head grades. This challenge is faced with existing operating assets and
presents a significant hurdle in the justification for new projects. Figure 1 shows global trends in
mined head grade from the mid 1800’s to 2010 (CSIRO 2015).
Figure 1 Mined head grades for base metals and gold
New projects or orebodies within existing operations, where reasonably good head grades can be
maintained, tend to defy this globally observed trend through a corresponding increase in
geological and metallurgical complexity. This is important for miners because metal input can be
maintained without increasing milling rates however for a given flowsheet the quantity and quality
of metal outputs will be compromised. While throughput of high-grade, complex orebodies can
maintain input metal units they may not achieve target grade or recovery, and may even introduce
penalty elements to the concentrate (Munro 2015), effecting economic viability.
By way of example, challenges faced with complex ore treatment in a flotation concentrator where
the concentrate would be directed to a smelter include:
 Inability to find an economic operating point on the grade recovery curve such that both grade
or recovery is not achieved for economic sale to a smelter
2
 Sacrificing the final product concentrate grade by inclusion of a middling concentrate that
serves to increase overall recovery but negatively impacts grade and introducing penalty
elements
 Inability to separate the economic minerals in an orebody rendering the production of a bulk
concentrate with poor terms of sale to a smelter
Figure 2 illustrates the general trend of how grade versus recovery curves have become less defined
as recovery increases.
Figure 2 Less defined grade recovery curves lead to lower concentrate grade to achieve target recovery
In general, the gradient of the grade recovery curve has decreased resulting in a non-optimal
operating position on the curve. This is a reflection of the general increasing complexity of ore to
maintain mined head grade. The reason the ore complexity is reflected in Figure 2 is that minerals
become more difficult to separate from one another and are recovered together, (Young 1997).
Certain ore-types cannot be upgraded with mineral processing techniques to produce a concentrate
for downstream treatment in smelters. One example of these ores are the highly weathered or
oxidised ores that are treated via heap leaching or whole ore leaching for copper and cobalt
recovery. This processing method suits certain ore types and where sufficient infrastructure can be
established at low cost. For example, heap leachable ore, requires ore with minimum levels of
competency and permeability when it is stacked. The mineralisation must be such, that it is readily
acid leached, with sufficiently low net acid consumption to be economic. A separate plant is then
required to recover the copper once leached into solution, and then solvent extraction and electro-
winning plants are required to produce saleable copper cathode. This flowsheet is conditional on
the availability of reliable and relatively cheap power.
3
Ore types that don’t fit neatly into conventional flotation or heap leaching flowsheets have
traditionally been relegated to waste. These ores are generally referred to as Complex Ores.
Increasingly, these ore types can no longer be viewed as waste due to the contained metal content
and high costs of pre-stripping this material where it overlies more economic deposits. Often these
pre-stripping costs can make a project uneconomic unless metal can be recovered from this waste
material.
TREATMENT OF COMPLEX ORES THROUGH THE CONCENTRATOR

During the mining boom of 2004 to 2009 the challenges of increasing metal prices coupled with the
increasingly long lead times to bring a project to production led to mining companies adopting a
strategy of a standard concentrator design (Combes 2011). The standard concentrator would allow
significant improvement in the design and procurement phases of a project, and allow projects to
be implemented faster to take advantage of rising metal prices. A common circuit used in a
standard concentrator design is reflected in a simplified flowsheet in Figure 3.
Figure 3 Conceptual flotation plant
The standard concentrator is a valid concept where a number of concentrators are envisaged to be
built across projects with identical geological and metallurgical characteristics. The standard
concentrator is still an excellent concept where there will be some variation between projects where
some slight modification to the standard concentrator can be tolerated. When processing complex
ores, however, where a single deposit may have multiple complex metallurgical domains, it
becomes very difficult to design a single flowsheet that can treat all ore types while maximising
economic performance.
Figure 2 shows that treatment of ore with increasing complexity in a set flowsheet will result in a
compromise between recovery and grade or contamination of the final concentrate with deleterious
metals and gangue. This can significantly impact the economics of a mining operation, (Munro
2015).
4
MODIFICATION OF THE CONCENTRATOR FOR COMPLEX ORES
Modifications made from the conventional flowsheet for the treatment of complex ores generally
comprises two approaches. The first is increasing the extent of grinding. This is based on the
premise that when grade or recovery of an economic mineral is not obtained it is not liberated from
gangue and does not have exposed surfaces to float. While there is some focus on the primary
grind, usually when ore complexity increases, concentrate re-grinding, using a fine grinding mill
such as the IsaMillTM is included in the circuit (Burford 2007). This style of flowsheet is reflected in
Figure 4.
Figure 4 Modification of the conventional flowsheet for fine grinding
The addition of concentrate regrinding to a flotation circuit as shown in Figure 4 is based entirely
on increasing liberation. Once the minerals are liberated they must then be floated which can create
further issues as finer particles have slower flotation kinetics compared to courser particles, and
require more residence time to achieve the same recovery.
The second modification to the standard flowsheet commonly used is an increase of residence time
through the installation of more flotation capacity or modification of the circuit configuration as
reflected in Figure 5.
5
Figure 5 Modification of the conventional flowsheet for circuit configuration or longer residence time
For fine particle flotation, a properly designed circuit may have the benefits of reducing
recirculating loads, reducing reagent demand, as well as improved metallurgy. Examples such as
McArthur River Mines routinely produce average zinc concentrate less than 10um in size, (Pease
2004). Alternatively, different flotation equipment can be added to the flowsheet such as the
Jameson Cell which is well documented in the literature and proven in the field for improved fine
particle flotation compared to a mechanical cell (Young 2006).
The basic modifications to the conventional flotation flowsheet are all validated when they result in
improvements in the grade and recovery of the valuable metals to economic levels. Some extremely
complex ore types, however, will still not respond fully to such modifications and there is a need
for a more encompassing approach.
A further complication occurs when designing a new project or modifying an existing operation for
the treatment of a more complex ore, where the circuit design is based on the treatment of the most
complex metallurgical domain in the orebody. This leads to circuit complexity that is not needed
for a large percentage of the ore treated. Due to the mining sequence and certain ore types not
stockpiling well, the more complex ores will not be treated in discrete campaigns. The result can be
the installation of excess flotation and re-grinding capacity that is not utilised all of the time,
resulting in an inefficient use of capital.
GT PROCESS FOR THE TREATMENT OF COMPLEX ORES

Over the past 20 years there have been significant advances in technology and equipment in the
fields of mineral processing and hydrometallurgy in the mining industry. GT has been at the
forefront of these advances with the following technologies:
 IsaMillTM – A high efficiency fine grinding technology in a horizontally stirred mill utilising
inert ceramic media
 Jameson CellTM – A high intensity pneumatic flotation machine with no moving parts
generating fine bubbles
6
 Albion ProcessTM – Fine grinding followed by atmospheric leaching technology for refractory
and base metals concentrates, including low cost recovery of base metals from solution to high
grade concentrates with low grade reagents
The Albion ProcessTM is a patented technology developed by Glencore in 1994. The Albion
ProcessTM consists of two key steps. The first step is ultrafine grinding of a sulphide concentrate,
using Glencore Technology’s IsaMill TM, to particle sizes in the range 80 % passing 10 – 15 microns.
The second step is an oxidative leach of the finely ground sulphides at atmospheric pressure to
breakdown the sulphide matrix and liberate base and precious metals prior to metal recovery.
There are currently five Albion ProcessTM plants operating globally in base and precious metals
duties.
As a response to the increasing ore complexity, GT proposes a flowsheet that is a combination of
these recent advances in mineral processing and hydrometallurgy processes. A conventional
flotation flowsheet is still adopted when designing for new projects or existing operations
encountering increasing ore complexity but with the addition of a hydrometallurgical processing
step to deal with the low grade concentrates bled from the flotation circuit to smooth our variations
in plant operation. One version of the concept is illustrated in Figure 6.
Figure 6 GT concept for complex ore treatment
Figure 6 shows how the conventional flowsheet may be modified in an example where the
concentrate reporting to the cleaner circuit is treated through an IsaMill™ and then a Jameson Cell
prior to the Cleaner bank, obtaining grade, however the recovery is not at target levels meaning
that further cleaning must be employed to achieve recovery. The Cleaner and Cleaner Scavenger
banks provide further recovery, however the combined concentrate is below target, resulting in an
overall dilution of the concentrate grade. In the modified flowsheet, a Jameson cell treats the
Cleaner Scav tailings to recover a low grade concentrate. This low grade concentrate is bled from
the circuit and processed in a dedicated hydrometallurgical plant. Complex middling particles
recovered in the Jameson cell are removed from the circuit and are not recirculated through the
flotation plant.
The fine grinding stage prior to the cleaning circuit allows for high pull rates from the Rougher and
Scavenger, improving primary circuit recovery. The use of the Jameson Cell allows for good quality
7
concentrate to be produced after fine grinding, with the wash water on the cell reducing the
recovery of non-gangue particles.
The operation of the Cleaner and the Cleaner Scav enables the operation to balance the grade and
recovery to be achieved from the circuit. Too high a recovery from this circuit recovers not only
wanted liberated valuable mineral, but also the locked and complex particles towards the end of the
circuit, unnecessarily diluting the concentrate. There is also the possibility of penalty elements that
could be recovered in the concentrate with too high recovery rates. Therefore recovery needs to be
controlled to prevent these particles from being recovered and left in the Cleaner Scav tails.
The Cleaner Scav tails are treated with a Jameson Cell, further increasing circuit recovery, but
targeting complex particles that cannot be collected to concentrate in their current state due to the
low concentration of valuable minerals.
The concentrate collected from the Jameson Cell doesn’t need to be high grade to be economically
treated through the Albion ProcessTM. Grades down to 5% copper in concentrate have found to be
economic. One issue with including the Albion ProcessTM in the flowsheet is how to recover the
metals that are leached into solution at low cost. This is achieved through a process developed by
GT for zinc, copper, nickel and cobalt where either lime or limestone is used to continuously
precipitate the base metals at controlled pH. A common problem with this type of precipitation
process is the co-precipitation of gypsum. GT has developed procedures to overcome this issue by
carefully controlling the process conditions such that the gypsum grows to particle sizes
significantly coarser than the base metal oxides, and can be separated by hydrocyclone, as
illustrated in Figure 7.
Figure 7 Integration of the Albion ProcessTM into the mineral processing flowsheet
When applied to a copper circuit, the feed material to the Albion Process TM would be a low grade
5% copper middling concentrate which is then leached to solution and precipitated as a 45%
copper oxide concentrate. This high grade intermediate can then be sold for use in a range of
industries, or alternatively blended with the final concentrate product for sale.
8
CASE STUDIES FOR THE GT PROCESS
Two case studies are presented to illustrate the concept and high level information has been
provided on the incremental improvement that can be achieved by incorporating the Albion
ProcessTM into the concentrator flowsheet for processing a low grade middling stream.
Case 1 – Copper NW Queensland

Case 1 relates to an opportunity for brownfields expansion of mining and concentrator operations
at a mine in North Queensland. The ore complexity at the operation will increase for a short
duration due to the need to mine through mainly transitional/weathered ore zones with a variable
base of oxidation, resulting in some primary zones intermixed with the transitional ores. The
variation in the contact zone between the transitional and primary ores is such that the ores cannot
be separated and must be treated together. They are in a quantity such that the contained metal
units from both transitional and primary ore must be recovered to justify the overall project.
The main copper bearing minerals comprise native copper, chalcopyrite and chalcocite with minor
chrysocolla and malachite. The sulphide gangue comprises mainly pyrite with minor pyrrhotite,
galena and sphalerite.
The ore presented to the process typically grades 1 to 2% copper with varying mineralogy. Within
the feed some of the ore types can be recovered to a concentrate grading greater than 25% copper,
however for the pure transitional ores, the maximum copper concentrate grade is only 5% copper.
The transitional concentrates, however, contain predominantly leachable minerals, and lend
themselves to be separated to a middlings stream for separate hydrometallurgical processing. A
simplified flowsheet is illustrated in Figure 8.
Figure 8 Copper treatment flowsheet
The simplified flowsheet in Figure 8 indicates a pathway for liberated copper sulphide mineralogy
to report to a final cleaner concentrate to achieve on specification concentrate at +26% copper grade
for sale. The material that is not amenable to upgrading, diluted by both sulphide and non-sulphide
gangue is recovered in both the scavenger concentrate and the cleaner tailings as a 5% Cu middling
9
concentrate that is treated through the Albion ProcessTM. Even at low feed grades the
hydrometallurgy treatment option is economical since the final intermediate copper oxide
produced grades approximately 50% copper and overall circuit grade and recovery are maximised.
The mineral processing and hydrometallurgy flowsheet adds between 4% to 30% copper recovery
at target grade depending on what material is treated. The project allows access to a further 6.0 Mt
of high grade primary ore. The treatment of the transitional cap alone has an IRR of approximately
25%.
Case 2 – Zinc NW Queensland

This application of the GT flowsheet to zinc processing is treatment of historical zinc tailings. It was
acknowledged that significant zinc was contained in the tailings but when the tailings were re-
floated a zinc grade of around 10% had to be accepted for any economic recovery levels due to both
sulphide and non-sulphide gangue. A number of hydrometallurgy flowsheet options were
considered to treat the low grade concentrate, however these options were marginal economically
due to the high cost of installing expensive processing equipment to recover the final zinc metal
product. The GT approach overcame these economic and technical limitations. A simplified
flowsheet is illustrated in Figure 9.
Figure 9 Zinc treatment flowsheet
The flotation tailings can be re-floated in a conventional flowsheet to produce a 10% zinc
concentrate at 90% recovery. The resulting concentrate is fed to an IsaMill TM for grinding to 80%
passing 20 micron or below and then to the Albion ProcessTM oxidative leach for the extraction of
zinc. The oxidative leach achieves zinc recoveries of up to 99.5%. Glencore has installed two
Albion ProcessTM plants to recover zinc from a bulk concentrate, in Spain and Germany, and has
experience in the design of these plants (Hourn 2012).
Once in solution, rather than producing metal, the GT precipitation process was used with either
lime or limestone to produce a zinc oxide at a grade between 50 to 60% zinc. Strategically, since
most zinc roast-leach-electrowinning plants are limited at the roaster, such a zinc product can be
treated by conventional zinc refineries to maximise cellhouse capacity or operate during roaster
downtime.
10
The plant was sized to produce 100ktpa contained zinc metal but could be easily scaled down if
required. The project IRR was 30%.
CONCLUSION
GT has developed novel flowsheet configurations for the treatment of complex ores through minor
modification to conventional flowsheets with minimal process disruption and integration with
hydrometallurgy unit operations. The flowsheets presented are just examples and many other
variations are possible.
In the mining value chain, value can be most easily added when complexity in ores can be
overcome at the earliest part of the chain as practicable. This starts in the mine with grade control,
understanding metallurgical domain definition and optimising blast patterns. In the mineral
processing sphere this can start with screening and dense medium separation through to grind size
and reagent use. In extractive metallurgy this can mean blending with different feeds, additional
plant and equipment through to by-product waste disposal. The final product is sold in the market
relative to the product quality of other producers. The authors recognise that most value can be
added through addressing complex ore treatment as early as possible in the value chain and this
paper focuses on blending hydrometallurgical techniques with minerals processing to address ore
complexity in the concentrator.
REFERENCES
Burford B.D., Clark L.W. 2007. IsaMill technology used in efficient grinding circuits. VIII
International Conference on Non-Ferrous Ore Processing, Poland, May 2007.
Combes M. 2011. Xstrata Copper – Antapaccay Project, 18th September
http://www.glencore.com/assets/media/doc/speeches_and_presentations/xstrata/2011/xcu-speech-
201109184-analystvisitperu.en2.pdf
CSIRO 2015 – Producing more with less, Resourceful – Bringing CSIRO research to the minerals
industry, Issue 7, June 2015
Hourn M., Turner D.W. 2012.Commercialisation of the Albion Process. ALTA, Perth, Australia,
June, 2012.
Munro P.D. 2015. Base metal concentrate sales contracts – Change Pavlov and the Dog. MetPlant,
Perth, Australia, September, 2015
Pease J.D., Young M.F., Curry D., Johnson N.W. 2004. Improving fines recovery by grinding finer.
MetPlant, Perth, Australia, September, 2004
Young M.F., Pease J.D., Johnson N.W., Munro P.D. 1997. Developments in milling practice at the
lead/zinc concentrator of Mount Isa Mines Limited from 1990. Ausimm 6 th Mill Operators
Conference, Madang, PNG, October 1997
Young M.F., Barnes K.E., Anderson G.S., Pease J.D. 2006. Jameson Cell: The “comeback” in base
metals applications using improved design and flow sheets, 38 th Annual Meeting of the Canadian
Mineral Processors, Ottawa, Canada, 2006
11
Insights on the Behavior of Arsenic Species on
Activated Carbon during Catalytic Arsenic Oxidation
Rebecca Radzinski and Ahmad Ghahreman
Queen’s University, Canada
ABSTRACT
A novel and robust process which uses activated carbon and oxygen to catalyze arsenic oxidation in
acidic solutions was investigated. It is important to oxidize arsenic prior to removing it from
hydrometallurgical streams because arsenate species are more efficiently and effectively removed
as precipitates compared to arsenite species. Previous studies show that hydrogen peroxide is
formed on the activated carbon surface when aerated with oxygen in acidic solutions. This study
investigates how hydrogen peroxide formed affects the oxidation of arsenic in solution and the
speciation of arsenic on the carbon surface. Arsenic adsorption and desorption tests were
conducted to gain further insights into the adsorption and desorption behaviour of arsenic species
on activated carbon during catalytic arsenic oxidation.
It was determined that arsenic exists in the pentavalent and trivalent state on the activated carbon
surface before arsenate appears in the solution. Arsenate begins to appear in solution once the
adsorption of total arsenic on the carbon surfaces plateaus as the carbon reaches its saturation point.
Desorption experiments indicate that arsenite is more readily desorbed than arsenate as the
speciation of arsenic in solutions containing arsenite and arsenate were 46.3-46.6% arsenate and the
remainder arsenite.
1
INTRODUCTION
Arsenic is a hazardous element that is often found with sulfide minerals containing gold, copper
and silver. The mining and processing of these ores can mobilize arsenic which subsequently puts
the environment at risk of contamination. Arsenic is found in many drinking water aquifers and it
affects 144 million people globally (Clancy, Hayes, & Raskin, 2013).
Arsenic can exist as different oxidation states, but in the mining and mineral processing industries
the trivalent (arsenite) and pentavalent (arsenate) species are the most common. Typically, arsenic
is mobilized in the processing streams as arsenic oxyanions (Gallegos-Garcia, Ramírez-Muñiz, &
Song, 2012). The speciation of arsenic affects the solubility, toxicity and mobility of the arsenic
compounds. When arsenate is precipitated from solution via metal cations, the metal arsenate will
often take the form of: Mn(AsO4)m·H2O (Ritcey, 2005). The majority of the arsenic immobilization
processes currently used industrially require arsenic to be in its pentavalent state prior to fixation.
Arsenic production rose from 20 tonnes/year to 60 tonnes/year between 2000-2012 but arsenic
consumption for niche industries decreased from 20 tonnes/year to 5 tonnes/year between 2004-
2012 (González-Contreras, Weijma, & Buisman, 2012). Due to the decreasing commercial demand
for arsenic the arsenic that is mobilized during metallurgical operations must be immobilized and
stored where it will not pose health, safety or environmental risks (Zhang, Yuan, Wang, Jia, &
Demopoulos, 2015).
The oxidation of arsenic in the presence of oxygen without the aid of a catalyst is very slow
(Molnár, Virčíkova, & Lech, 1994). A strong oxidant can be used to oxidize arsenic under ambient
conditions. However, a novel method for arsenic oxidation which does not require the addition of
an oxidant was developed by Barrick Gold Corporation. This new process is conducted in highly
acidic conditions, at ambient pressure and temperature, and can oxidize up to 99% of arsenic in less
that twenty-four hours (Choi, Ghahremaninezhad, & Ahern, 2014a, 2014b).
An investigation by Radzinski et al. (2016) on the activated carbon-catalyzed arsenic oxidation
process showed that arsenic adsorbed onto the activated carbon during column tests. The test was
run for five days and the arsenic concentration exiting the column was always lower than the
concentration entering the column (Radzinski, Nazari, Ghahremaninezhad, & Choi, 2016).
The purpose of this investigation is to gain further insights into the adsorption and desorption
behaviour of arsenite and arsenate in acidic media.
METHODOLOGY
Solution and material preparation

Granular activated carbon used in the experiments was supplied by Barrick Gold Corporation. The
activated carbon was produced by Calgon Carbon Corporation and is their “Gold Plus” variety.
The activated carbon was derived from coconut shells. Prior to using the activated carbon in
experiments, it was stirred by an overhead mixer for twenty-five hours in deionized water. The
carbon-water mixture was then poured over a 16-mesh screen and wet screened to get rid of the
carbon fines produced through the attrition process. The carbon was then stored in a large bucket
with deionized water until it was required for experimental purposes.
2
Arsenic stock solutions were created by dissolving the respective arsenic oxide in a 2 L Erlenmeyer
flask that had previously been filled with deionized water and 20 cm3 of concentrated sulfuric acid.
The arsenic reagents used were: arsenic trioxide (99.5% on a metals basis from Alfa Aesar) and
arsenic pentoxide (99.9% on a metals basis from Alfa Aesar). Aliquots of the stock solutions were
taken as required for the experiments and diluted with deionized water.
Experimental procedures
Three 200 cm3 solutions were prepared for the arsenic adsorption shake tests: (i) 2 g/L As (III),
(ii) 2 g/L As (V), and (iii) 2 g/L As (III) and 2 g/L As (V). The pH of each solution was adjusted via
sulfuric acid addition to a pH of 1.0 ± 0.1. Three 90.0 g samples of pretreated activated carbon were
placed in their respective 250 cm3 Erlenmeyer flasks. The respective solution was added to its flask
and the flasks were shaken on a table shaker at 200 rpm for the first 0.25 h and 250 rpm for the
remainder of the test. At specific time points samples were taken for total arsenic and arsenic
speciation analysis. Total arsenic was measured via ICP analysis and arsenic speciation was
determined via colorimetric titration. The pH and dissolved oxygen (DO) were also measured at
the specific timepoints.
Three 100 cm3 solutions were prepared for the arsenic desorption shake tests: (i) 1.8 g/L As (III),
(ii) 1.8 g/L As (III) and 1.8 g/L As (V), and (iii) 0.9 g/L As (III) and 0.9 g/L As (V). The pH of each
solution was adjusted via sulfuric acid addition to a pH of 1.0 ± 0.1. The respective solution and a
45.0 g sample of pretreated activated carbon were added to an Erlenmeyer flask. The mixture was
shaken on a shake table at 250 rpm for one hour. The filtrate was separated from the carbon via
vacuum filtration. The carbon was then shaken with 100 cm3 of 1.0 M sulfuric acid for five minutes.
The solution which was used to strip the carbon of adsorbed arsenic was separated from the
carbon. The initial arsenic solution, the filtrate and the stripped solutions were all assayed for
arsenic and the corresponding arsenic speciation.
RESULTS AND DISCUSSION
Arsenic adsorption
Adsorption tests for arsenic onto activated carbon were performed over a four hour period with
samples taken at 0, 0.25, 0.5, 0.75, 1, 1.5, 2, 3 and 4 h. The pH of the flasks increased whereas the DO
in solution decreased, as presented in Table 1.
3
Table 1 Initial and final pH and DO of the adsorption tests
Flask Initial As Initial pH Final pH Initial DO [mg/L] Final DO [mg/L]

concentration
1 2 g/L As (III) 1.0 2.0 8.2 7.3
2 2 g/L As (V) 1.0 2.0 8.5 7.1
3 2 g/L As (III) 1.0 1.8 8.4 7.4

2 g/L As (V)
It is expected to have an initial DO of approximately 8 mg/L at ambient conditions. As can be seen

in Figure 1, in the first hour of testing the DO fluctuated between 7.1-7.9 mg/L and the final DO at
the end of the test ranged from 7.1-7.4 mg/L depending on the flask. This set of tests did not have
any oxygen introduced into the system via sparging so it is likely that the oxygen being consumed
was either being adsorbed onto the activated carbon surface, it was being integrated into functional
groups on the carbon surface, or it was reacting to form hydrogen peroxide and subsequently
oxidizing arsenic.
7
Dissolved Oxygen [mg/L]
2
Flask 1: As (III)
1 Flask 2: As (V)
Flask 3: As (III) and As (V)
0
0 40 80 120 160 200 240
Time [min]
Figure 1 DO of the three flasks studied in arsenic adsorption shake tests
Previous experiments studying the catalytic ability of carbon in a system containing ferrous ions
show that iron is oxidized by either hydrogen peroxide produced by the carbon or by the catalytic
ability of carbon (Ahumada et al., 2002).
4
The arsenic adsorbed on the activated carbon surface did not vary significantly between the flasks.
At four hours, the flask with 2 g/L As (III) had 64% arsenic adsorbed, the flask with 2 g/L As (V)
had 66% arsenic adsorbed, and the flask with 2 g/L As (III) and 2 g/L As (V) had 61% arsenic
adsorbed. Although statistically there is likely no significant difference, the final amount of arsenic
adsorbed gives an indication that arsenate has a higher affinity to adsorb onto the carbon surface
under the conditions used in this set of tests. A previous study has similar findings as it indicated
that arsenate is more easily adsorbed onto activated carbon than arsenite (Lorenzen, van Deventer,
& Landi, 1995). Interestingly, another study shows that activated carbon which has been
impregnated with copper increases arsenite adsorption onto the activated carbon surface
(Rajakovic, 1992). Figure 2(a) and (b) show a comparison of the arsenic oxidized in solution and the
total arsenic adsorbed, on a percentage basis, of the flasks containing 2 g/L As (III) and 2 g/L As (III)
& 2 g/L As (V), respectively.
100
(a)
90
80
70
Percentage [%]
60
50
40
30
20
10 Arsenic oxidized in solution
Astot adsorbed
0
0 40 80 120 160 200 240
Time [min]
100
(b)
90
80
70
Percentage [%]
60
50
40
30
20
10 Arsenic oxidized in solution
Astot adsorbed
0
0 40 80 120 160 200 240
Time [min]
Figure 2 Total arsenic adsorbed and the amount of arsenic oxidized in solution, on a percentage basis for
(a) the flask with 2 g/L As (III) and (b) the flask with 2 g/L As (III) and 2 g/L As (V)
5
Arsenate starts to appear more substantially in solution once a plateau has been reached of the total
arsenic adsorbed for both graphs included in Figure 2. The reason for arsenate not appearing in
solution at an earlier time is likely due to arsenate having a higher affinity to adsorb onto carbon
compared to arsenite. A series of arsenic desorption tests were then conducted to determine if
arsenate appears on the activated carbon surface prior to it first appearing in solution.
Arsenic desorption
A full arsenic balance was not obtained for the arsenic desorption tests because the amount of
arsenic recovered at the end of the test did equal the amount of carbon adsorbed on the activated
carbon. The low recoveries are due to requiring a longer contact time between the carbon and
sulfuric acid at a higher temperature. The method used was selected because the authors wanted to
maintain the system conditions as similar to the initial stage of the desorption test as possible.
However, the speciation of arsenic desorbed gives insight into which arsenic oxidation state is
preferentially desorbed from the activated carbon surface. Three flasks were prepared with varying
arsenic concentrations (Table 2).
Table 2 Initial conditions and arsenic recovery from carbon for arsenic desorption shake tests
Flask Initial As Initial pH % As recovered

concentration from carbon
A 1.8 g/L As (III) 1.0 24.8
B 1.8 g/L As (III) 1.1 25.3
1.8 g/L As (V)
C 0.9 g/L As (III) 1.1 21.4

0.9 g/L As (V)
The stripped solution compositions are presented in Figure 3. Interestingly, the flask which initially
only had arsenite has some arsenate that has desorbed from the carbon surface. This implies that
the carbon has a limited ability to oxidize arsenic without adding oxygen into the system. As well,
this finding also means that arsenate exists on the surface of activated carbon before it appears in
solution: Figure 2(a) does not show any arsenate in solution until after one hour, but this test
confirms that there is arsenate in the system but it has not yet desorbed into solution.
6
Figure 3 Arsenic speciation in the stripped solution for each of the desorption test flasks
The stripped solution of the two flasks initially containing both oxidation states of arsenic are
46.3-46.5% arsenate and 53.5-53.7% arsenite, which is a 7.0-7.5% difference. This shows that the
interactions binding arsenite to activated carbon are slightly weaker than the interacting holding
arsenate to activated carbon.
CONCLUSION
Arsenic adsorption and desorption tests show that arsenate exists on the activated carbon surface
prior to it appearing in solution. In arsenic adsorption tests the arsenate starts to appear in solution
once the adsorption of total arsenic onto the activated carbon surface reaches a plateau. The DO in
the solutions decrease by less than 1 mg/L over four hours and this consumed oxygen is likely
adsorbing onto the carbon surface as adsorbed oxygen or as part of an oxygenated surface
functional group. A full arsenic balance was not completed in the desorption tests, but from
analyzing the arsenic stripped from the activated carbon it is apparent that arsenite has weaker
interactions holding it to the carbon surface compared to arsenate because 46.3-46.5% of the arsenic
in solution was arsenate and the remainder was arsenite.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the financial support of this study by Natural Sciences and
Engineering Research Council of Canada Discovery Grant RGPIN-2015-05718.
7
REFERENCES
Ahumada, E., Lizama, H., Orellana, F., Suarez, C., Huidobro, A., Sepulveda-Escribano, A., &
Rodriguez-Reinoso, F. (2002). Catalytic oxidation of Fe(II) by activated carbon in the presence of
oxygen. Effect of the surface oxidation degree on the catalytic activity. Carbon, 40, 2827–2834.
Choi, Y., Ghahremaninezhad, A., & Ahern, N. (2014a). Method for arsenic oxidation and removal
from process and waste solutions. Barrick Gold Corp., US 2014/0356261 (WO2014191833 A1).
Choi, Y., Ghahremaninezhad, A., & Ahern, N. (2014b). Process for activated carbon-assisted
oxidation of arsenic species in process solutions and waste waters. In COM 2014 - Conference of
Metallurgists (pp. 1–9). Canadian Institute of Mining, Metallurgy and Petroleum.
Clancy, T. M., Hayes, K. F., & Raskin, L. (2013). Arsenic waste management: A critical review of
testing and disposal of arsenic-bearing solid wastes generated during arsenic removal from
drinking water. Environmental Science and Technology, 47(19), 10799–10812.
http://doi.org/10.1021/es401749b
Gallegos-Garcia, M., Ramírez-Muñiz, K., & Song, S. (2012). Arsenic Removal from Water by
Adsorption Using Iron Oxide Minerals as Adsorbents: A Review. Mineral Processing and Extractive
Metallurgy Review, 33(5), 301–315. http://doi.org/10.1080/08827508.2011.584219
González-Contreras, P., Weijma, J., & Buisman, C. J. N. (2012). Continuous bioscorodite
crystallization in CSTRs for arsenic removal and disposal. Water Research, 46(18), 5883–92.
http://doi.org/10.1016/j.watres.2012.07.055
Lorenzen, L., van Deventer, J. S. J., & Landi, W. M. (1995). Factors affecting the mechanism of the
adsorption of arsenic species on activated carbon. Minerals Engineering, 8(4–5), 557–569.
http://doi.org/10.1016/0892-6875(95)00017-K
Molnár, L., Virčíkova, E., & Lech, P. (1994). Experimental study of As(III) oxidation by hydrogen
peroxide. Hydrometallurgy, 35(1), 1–9. http://doi.org/10.1016/0304-386X(94)90013-2
Radzinski, R., Nazari, A. M., Ghahremaninezhad, A., & Choi, Y. (2016). The effect of ferrous and
cupric ions on the oxidation efficiency of activated carbon-catalyzed oxidation of arsenic species
from process solutions. In Copper 2016, The Ninth International Copper Conference hosted by MMIJ and
JMIA. Kobe: The Mining and Materials Processing Institute of Japan.
Rajakovic, L. V. (1992). The Sorption of Arsenic onto Activated Carbon Impregnated with Metallic
Silver and Copper. Separation Science and Technology, 27(11), 1423–1433.
http://doi.org/10.1080/01496399208019434
Ritcey, G. M. (2005). Tailings management in gold plants. Hydrometallurgy, 78(1–2 SPEC. ISS.), 3–20.
http://doi.org/10.1016/j.hydromet.2005.01.001
Zhang, D., Yuan, Z., Wang, S., Jia, Y., & Demopoulos, G. P. (2015). Incorporation of arsenic into
gypsum: Relevant to arsenic removal and immobilization process in hydrometallurgical industry.
Journal of Hazardous Materials, 300, 272–280. http://doi.org/10.1016/j.jhazmat.2015.07.015
8
Copper Ore Leaching with Pre-Treatment
María E. Taboada1,2, Rafael Quiroz2, Pía C. Hernández1, Aldo Padilla1, Osvaldo Herreros1
and Teófilo Graber1,2
1. Universidad de Antofagasta, Chile
2. CICITEM, Centro de investigación Científico Tecnológico para la Minería, Chile
ABSTRACT
The effects of adding ferric and ferrous ions with seawater, sodium chloride and sulfuric acid in the
pre-treatment of a mixed copper ore was studied, followed by leaching with acid and chloride
solution and the addition of cupric and iron ions.
A mixed ore from northern Chile was used, which contains mainly atacamite (0.37%), chalcopyrite
(0.18%) and chalcocite (0.10%) as copper minerals, as well as iron ores like hematite (1.21%) pyrite
(1.12%) and limonite (0.17%), with a size below 3/8 inch.
Leaching was carried out at room temperature in acrylic mini-columns, 40 cm in high by 9.5 cm in
diameter and with a 3-kilogram mineral load.
The results show that pre-treatment in a chloride medium yields extraction levels of between 62 and
67%, the highest rate being the pre-treatment with the addition of ferrous ions. Following leaching,
the extraction values were close 80% recovery of copper, with similar levels among the treatments.
The column with the addition of ferrous ions had the highest level of extraction at 79.2%, while the
column with the lowest level of extraction was one to which no iron ions were added to the leaching
solution. It also had the slowest recovery kinetics of any of the columns.
The addition of iron and chloride improved leaching kinetics, with extraction of around 95% of oxides
and 20% of sulfide minerals. The mineralogical characterization of the residues indicated that 20%,
which was chalcopyrite, was partially leached during the leaching cycle.
1
INTRODUCTION
Copper is recovered from oxidized minerals by hydrometallurgy using acid solutions in the leaching
stage, while copper sulfide minerals are treated by pyrometallurgy. In recent years the focus in
treating copper sulfide minerals has shifted to hydrometallurgical methods like leaching with
chloride ions (Watling, 2014, Senanayake, 2009) or sea water (Torres et al., 2015, Hernández et al.,
2015, Moreno et al., 2011), which contribute to dissolving the copper.
Oxidized minerals of copper leached in piles are treated previously by agglomeration and curing,
which also contribute to dissolve the copper (Lu et al., 2017, Dhawan et al., 2013). Agglomeration is
used to bring together fine and coarse particles to increase the permeability of the mineral, while
curing inhibits the dissolution of some silicates and accelerates copper extraction. Concentrated
sulfuric acid is added to the crushed mineral during curing to initiate reactions with soluble metals
and gangue minerals and to prevent the formation of a silica gel by dehydration (Dhawan et al., 2013).
The moisture content of the mineral for the agglomeration is in the range of 5 to 10%, while the acid
curing period generally lasts 1 to 5 days (Cruz et al., 1980). Curing and agglomeration improve the
copper extraction rate and reduces acid consumption.
Fe3+ ions are commonly used as an oxidant in leaching copper sulfide minerals to dissolve the sulfur
from the copper (Domic, 2001). Sullivan (1930) studied dissolving chalcocite minerals using ferric
ions and proposed the following reactions (1) and (2):
Cu2 S + 2Fe3+ → CuS + Cu2+ + 2Fe2+ (1)
CuS + 2Fe3+ → Cu2+ + 2Fe2+ + S (2)
It has been reported that Fe2+ ions contribute to extract copper from chalcopyrite according to the
following chemical reaction (3) (Hiroyoshi et al., 2000):
CuFeS2 + 3Fe2+ + 8H + + 2O2 = Cu2+ + 4Fe3+ + 2S + 4H2 O (3)
The presence of sulfuric acid in leaching mixed copper minerals is important for two reasons, firstly
for leaching the oxides in the ore and secondly to dissolve species that contain iron from the gangue
in which the ferric ion is the main oxidant of copper sulfides. Miki et al.(2011) determined that
dissolution of chalcocite does not increase with increased concentrations of the acid. A concentration
of 0.1 M de H+ was sufficient for leaching in an oxidant-chloride medium. Cheng and Lawson (1991)
determined that increasing the concentration of H2SO4 from 2 g/l to 50 g/l increased the dissolution
of chalcocite, but that a concentration of 50 g/l of H2SO4 was sufficient given that no additional effect
was observed at higher concentrations.
With respect to leaching copper sulfide minerals in an acid-chloride medium (Senanayake, 2009,
Watling, 2014), several researchers have reported more rapid copper leaching kinetics than in the
absence of chloride ions as this favors the formation of a porous layer around the particle instead of
a passivation layer and it is argued that the formation of complex chloride-copper species are
beneficial for dissolving copper from sulfide minerals.
Pretreatment of the mixed copper ore and subsequent irrigation will allow obtain better copper
extraction than ore without pretreatment, moreover, lower energy consumption could be obtained
using a pretreatment stage (repose time) because reduce the irrigation time. The pretreatment process
doesn’t need additional equipment only need space necessary to complete the repose time.
2
The objective of this study is to determine the effect of ferric and ferrous ions on both the pre-
treatment and leaching stages of a mixed copper mineral containing chalcocite, chalcopyrite and
atacamite.
EXPERIMENTAL DEVELOPMENT
Mineral
The mineral size was reduced below -3/8”, with a P80 of 10.9 mm. This size was used for all the
experimental tests. Mineral acid consumption was 25 kg H2SO4/t mineral, obtained by atomic
absorption spectrometry (AAS). This value was used as a reference for the experimental tests Table
1 shows the mineralogical characterization as determined by optical microscopy of the copper
minerals.
Table 1 Mineralogical characterization
Minerals Formula % Weight % Cu

Atacamite Cu2Cl(OH)3 0.37 0.24
Chalcopyrite CuFeS2 0.18 0.06
Chalcocite Cu2S 0.13 0.10
Covellite CuS 0.05 0.03
Bornite Cu5FeS4 0.01 <0.01
Total 0.44
Pre-treatment tests
Four pre-treatment tests were conducted (A tests) using the conditions detailed in Table 2. 3 kg of ore
with the same size distribution was used. The ore, with 6% moisture (seawater was used as a solvent),
was placed in mini-column 9.5 cm in diameter and 40 cm high and left to stand for the desired time.
Ferric, ferrous and chloride ions were added in the agglomeration stage, along with sulfuric acid and
seawater. The methodology of adding reactive agents was different for test A4, with the addition of
solid NaCl together with concentrated H2SO4. Following this, the sample was left to stand for 7 days,
and then seawater was added to obtain a moisture level of 6%, after the sample continued standing
until completing the full 30 days.
Finally, the leached ore was washed with fresh water and dried. The residue was then analyzed for
copper extraction.
Table 2 Pre-treatment test conditions.
A1 A2 A3 A4*
H2SO4 (kg/t) 25 25 25 25
NaCl (kg/t) 50 50 50 50
Fe2(SO4)3*9.2H2O (kg/t) - 25 - -
FeSO4*7H2O(kg/t) - - 25 -
3
Curing time (days) 30 30 30 30
*Tests with addition of different reactive agents
Leaching tests
After obtaining the results of the A tests, 6 leaching tests (B1 to B6) were conducted with pre-treated
ores. The ores were agglomerated under the conditions shown in Table 3. They were then left to stand
for 30 days, followed by leaching for 30 days followed by a washing step for 3 days.
The agglomerated ores were irrigated for 12 hours with peristaltic pumps at a rate of 8 L/h/m2 for all
the tests. The system was an open cycle in which solutions did not recirculate.
Periodically 50 mL samples of the outgoing solution were taken for chemical analysis for total Cu,
total Fe and H+. These data provided the copper extraction rate and acid consumption rates as a
function of time.
Following the leaching, the ores were left to stand for 2 days to drain the solution completely. At the
end of the tests, the gravel was dried at 60 °C and analyzed for total and soluble Cu and total Fe
(AAS).
Table 3 Experimental conditions of leaching tests using pretreated ore
Pre-treatment B1 B2 B3 B4* B5 B6
H2SO4 (kg/t) 25 25 25 25 25 25
NaCl (kg/t) 50 50 50 50 50 50
Fe2(SO4)3*9.2H2O (kg/t) - 25 - - - -
FeSO4*7H2O (kg/t) - - 25 - - -
Leaching Solution
Cu2+ (g/L) 0.5 0.5 0.5 0.5 0.5 0.5
Cl (g/L)
- 80 80 80 80 80 80
H2SO4 (g/L) 10 10 10 10 10 10
Fe2+ (g/L) - 2 2 2 2 -
Fe3+ (g/L) 2 - - - - -
*Tests with the addition of different reactive agents
Pre-treatment´s Results
The results of the A tests (see Table 2 and 4) show that the best rates of Cu extraction in the pre-
treatment were obtained when ferrous and ferric ions were added to the ore in pre-treatment step.
(Tests A3 and A2).
4
Table 4 Pre-treatment extraction rates
A1* A2 A3 A4
Ext. CuT (%) 62.8 65.8 67.9 61.8
*Tests done in triplicate with a standard deviation of 0.8%
Comparing tests A1 and A4, it is evident that the addition of reactive agents did not significantly
increase copper extraction. This could be because test A4 generated gaseous HCl, which does not
have sufficient contact with the mineral to effect copper extraction. As well, the quantity of sulfuric
acid that did not react was not sufficient to increase copper extraction.
Table 4 shows that the copper extraction was slightly higher in test A3 than A2, which is attributed
to the oxidizing of Fe2+ into Fe3+ during the standing time due to the effect of oxygen in the
surroundings and the addition of sulfuric acid. The ferric ions react with chalcocite, resulting in a
higher extraction rate.
In general, from Table 4 is observed that a repose time of 30 days at room temperature in an iron-
chloride-acid medium allow obtain upon 61% copper extraction.
Results of the Leaching

The results of the copper extraction methods were similar, with recovery rates close to 80% in a range
between 75-79 % Cu extractions. The lowest extraction rate was in column B6, which also presented
the slowest kinetic rate owing to the fact that iron ions were not added to the leaching solution or the
pre-treatment.
Table 5 Leaching conditions and extraction rates
Leaching B1 B2 B3 B4* B5 B6
Cu2+ (g/L) 0.5 0.5 0.5 0.5 0.5 0.5
Cl- (g/L) 80 80 80 80 80 80
H2SO4 (g/L) 10 10 10 10 10 10
Fe2+ (g/L) - 2 2 2 2 -
Fe3+ (g/L) 2 - - - - -
Ext. CuT (%) 77.5 78.3 79.2 77.1 75.8 75.3
The mineralogical characterization of the gravels showed that the 20% that was not leached during
the leaching cycle was chalcopyrite.
5
80
75
Copper Extraction (%)
70
B1
B2
65 B3
B4
60 B5
B6
55
50
30 32 34 36 38 40 42 44 46
Time (days)
Figure 1 Cu extractions (%) vs time (days) in columns leaching.
From the Figure 1, a time of 45 days of pre-treatment-leaching is enough to obtain the maximum
copper extraction for all tests. The most of copper was extracted from pretreatment stage. This could
be beneficial because the pretreatment stage only need a big area of land to complete the repose time.
CONCLUSSIONS
- The “A” pre-treatment tests determined that best conditions for Cu extraction involve adding
ferrous ions (test A3), which resulted in a recovery rate of 67.9%.
- The copper extractions obtained in the tests of pre-treatment and leaching were in a range of 75-79
%. The highest extractions were obtained in the tests with addition of iron in a chloride medium.
- The lowest recovery rates were in tests that did not involve adding iron ions.
- More than half of the copper in the ore can be solubilized with a standing time of 30 days under the
tested conditions due to the curing process.
- A pretreatment stage could be beneficious on an industrial scale due to the reduction of the energy
consumption by a decrease of the irrigation time in leaching.
ACKNOWLEDGMENTS
The authors acknowledge to Gobierno Regional de Antofagasta project FIC-R BIP30412829-0 and
Fondecyt Project No 1140169for financing.
6
REFERENCES
CRUZ, A., LASTRA, M. & MENACHO, J. 1980. SULPHURIC ACID LEACHING OF COPPER
SILICATE ORE. Society of Petroleum Engineers of AIME, (Paper) SPE, 61-70.
CHENG, C. Y. & LAWSON, F. 1991. The kinetics of leaching chalcocite in acidic oxygenated sulphate-
chloride solutions. Hydrometallurgy, 27, 249-268.
DHAWAN, N., SAFARZADEH, M. S., MILLER, J. D., MOATS, M. S. & RAJAMANI, R. K. 2013.
Crushed ore agglomeration and its control for heap leach operations. Minerals Engineering, 41, 53-70.
DOMIC, E. 2001. Hidrometalurgia: Fundamentos, procesos y aplicaciones. Chile, Andros Impresos.
HERNÁNDEZ, P., TABOADA, M., HERREROS, O., TORRES, C. & GHORBANI, Y. 2015.
Chalcopyrite dissolution using seawater-based acidic media in the presence of oxidants.
Hydrometallurgy, 157, 325-332.
HIROYOSHI, N., MIKI, H., HIRAJIMA, T. & TSUNEKAWA, M. 2000. A model for ferrous-promoted
chalcopyrite leaching. Hydrometallurgy, 57, 31-38.
LU, J., DREISINGER, D. & WEST-SELLS, P. 2017. Acid curing and agglomeration for heap leaching.
MIKI, H., NICOL, M. & VELÁSQUEZ-YÉVENES, L. 2011. The kinetics of dissolution of synthetic
covellite, chalcocite and digenite in dilute chloride solutions at ambient temperatures.
MORENO, P., ARAL, H., CUEVAS, J., MONARDES, A., ADARO, M., NORGATE, T. & BRUCKARD,
W. 2011. The use of seawater as process water at Las Luces copper–molybdenum beneficiation plant
in Taltal (Chile). Minerals Engineering, 24, 852-858.
SENANAYAKE, G. 2009. A review of chloride assisted copper sulfide leaching by oxygenated
sulfuric acid and mechanistic considerations. Hydrometallurgy, 98, 21-32.
TORRES, C., TABOADA, M., GRABER, T., HERREROS, O., GHORBANI, Y. & WATLING, H. 2015.
The effect of seawater based media on copper dissolution from low-grade copper ore. Minerals
Engineering, 71, 139-145.
WATLING, H. 2014. Chalcopyrite hydrometallurgy at atmospheric pressure: 2. Review of acidic
chloride process options. Hydrometallurgy, 146, 96-110.
7
CHAPTER 2
Instrumentation,
Modeling,
Optimization,
and Automatic
Process Control
Phenomenological Modelling of Industrial Heap and
Dump Bioleaching
Roberto Collao and Roberto Bobadilla
CodelcoTech, Chile
ABSTRACT
Heap and dump bioleaching are operational units with physical, chemical, mineralogical and
microbiological processes, which are interconnected at different scales. Consequently, in the search
to understand and optimize these processes it is impossible to approach intuitively and therefore, it
is necessary to systematically integrate knowledge by means of phenomenological modelling. During
several years, BioSigma has developed a phenomenological model that accurately predicts the
performance of its technologies applied in the bioleaching of heaps and dumps, in terms of copper
recovery and other important biohydrometallurgical parameters such as acid consumption and iron
recovery. The model is one-dimensional in liquid and gas flow, and includes kinetic laws for primary
and secondary sulphides, copper oxides, pyrite and gangue minerals. The model also includes
transport of ionic species and microorganisms, chemical speciation, attachment/detachment and
growth of iron- and sulphur-oxidizing microorganisms, oxygen balances in liquid and gas phases
and heat conservation. The model allows the user to find reaction parameters by means of automatic
calibration with experimental results. The heap bioleaching model was successfully calibrated and
validated using experimental data from tests made in columns and heaps, and it is capable of
reproduce and predicts the most important process variables. The model is currently used
industrially to assess heap/dump bioleaching performance on different industrial projects and
scenarios, including the effect of mineralogy, particle size distribution, irrigation rate, microbial
addition, heap height, aeration rate, temperature of the irrigated solution, and the application of anti-
evaporation film among others. In conclusion, BioSigma have developed a state of the art tool which
is available to be used by the industry to improve copper extraction operations.
1
INTRODUCTION
Heap and dump bioleaching has been recognized as an attractive alternative process for treating low
grade sulfide copper ores, due to its low capital and operating costs, and its low environmental
impact. This technology is also considered suited for the extraction of zinc, nickel and the
pretreatment of refractory gold ores (Leahy, Davidson, Schwarz, 2005; Ogbonna, Petersen, Dixon,
2005). However the underlying physical, chemical, mineralogical and biological processes associated
to heap and dump bioleaching are actually rather complex, and are interconnected at different scales.
Consequently, in the search to understand and optimize these processes it is impossible to approach
intuitively and therefore, it is necessary to systematically integrate knowledge by means of
phenomenological modelling.
To understand the underlying process and to optimize the bioleaching of copper ores in heaps and
dumps, numerous heap leach models have been developed over time. The models encountered in
the state of the art commonly include phenomena like solid-liquid reaction, liquid and gas transport,
equilibrium reactions in solution, advective and diffusive transport of species, bacterial growth
kinetics, and heat conservation (Bennett et al., 2012; Bouffard, 2008; Leahy, Schwarz, Davidson, 2004;
Leahy, Schwarz, Davidson, 2006; Leahy, Schwarz, 2009; Ogbonna, Petersen, Dixon, 2005; Ogbonna,
Petersen, Laurie, 2006; Petersen, Dixon, 2002; Robertson, 2017; Vilcáez, Suto, Inoue, 2008). For several
years BioSigma has developed a phenomenological model for heap and dump bioleaching process
that includes all previously mentioned phenomena, but also has the advantage to include the
following:
 The possibility to simulate the leaching of a complex ore with the simultaneous dissolution
of copper sulphide minerals such as chalcocite, covellite, bornite and chalcopyrite,
concomitant with the dissolution of a copper oxide mineral, pyrite and two gangue
minerals.
 The possibility to simulate an ore leaching in a wide size particle distribution, associating
to each fraction size the chemical and mineralogical composition, and the liberation degree
of copper minerals.
 The option to adjust automatically some selected model’s parameters using experimental
data in the calibration process.
The model has been programmed in SCILAB, an open source mathematical software which allows
to manage in a user friendly manner the input information by means of dialogue boxes and standard
spreadsheets, and the model’s results by means of standard computer windows.
The model has been successfully used to forecast biohydrometallurgical parameters of interest in
industrial heap/dump bioleaching operations, such as copper recovery, iron recovery, acid
consumption and effluent solution composition, the scaling of experimental results from
biohydrometallurgical assays done in lab-, bench- and/or pilot-scale to the operation of industrial
heaps and dumps, and to analyse the sensitivity of the process to design variables and operational
condition such as heap height, particle size distribution, microbiology, mineralogy and chemical
composition grade, irrigation rate and irrigation/rest cycles, aeration rate, temperature of the
irrigated solution, and the application of anti-evaporation film among others.
2
PHENOMENOLOGICAL MODEL
In the following sections is described the phenomena considered in the model developed by
BioSigma, and some basic and general equations are shown.
Fluid Dynamics of the Liquid and Gas Phases

The bioleaching heap model developed by BioSigma includes the fluid dynamics in one dimension
of the liquid phase, corresponding to the vertical direction in which the solution percolates. The
border condition considers the irrigation rate of the process at the top of the heap, and it is assumed
there are no pressure gradients at the bottom of the heap. The fluid dynamics of the liquid phase is
modelled by means of the continuity equation, the Darcy equation and the van Genuchten equations
(Silva & Fuentealba, 2000)
The model also includes the fluid dynamics of the gas phase in one dimension, corresponding to the
vertical direction in which the air rises through the heap by forced or natural convection. The flux of
air inside the heap is estimated by means of a momentum conservation equation and the continuity
equation (Leahy, Schwarz, Davidson, 2006; Rojas, 2015). The body force component of the
momentum equation take into account the Darcy resistance induced by the porous bed to the air flow
and the effect of gravity over the gas. Boussinesq approximation is used to estimate the effect of
temperature over the gas density (Leahy, Schwarz, Davidson, 2006).
Balance of Species in Solution

The bioleaching heap model includes balances of species in the liquid phase or solution, in one
dimension, corresponding to the vertical direction in which the solution percolates. The species
modelled are Cu2+, Fe2+, Fe3+, H+, SO42-, dissolved oxygen and free microorganisms. The balances
incorporate the movement of species by advection and dispersion mechanisms (Leahy, Davidson,
Schwarz, 2005).
Besides advection and dispersion, the balances of species in solution include a term of
generation/consumption. In the case of ionic species in solution, it represents the generation or
consumption due to the dissolution of minerals. In the case of dissolved oxygen, it represents the
consumption of oxygen by microorganisms and the oxygen transfer from the air to the solution. In
the case of microorganisms, it represents the growth of microorganisms and the adhesion and
desorption mechanisms (Leahy, Davidson, Schwarz, 2005).
Minerals Dissolution
To model the mineral dissolution reactions involved in the leaching of a low grade ore, it is assumed
that the ore particles are perfect spheres, the grains of the mineral species of interest are dispersed in
an unreacted gangue matrix, there is a shrinking core composed of unreacted grains, and the leaching
agents (Fe3+, H+) diffuse through the pores of the gangue matrix of the reacted zone (Madsen, Groves,
Wadsworth, 1974).
In the case of copper sulphide minerals and pyrite, the conversion is calculated with the following
equation, in which it is assumed kinetic control:
2
𝑑𝛼𝑖 3(1−𝛼𝑖 ) ⁄3 𝑣
= (1)
𝑑𝑡 𝜌𝑟 𝑟𝑖0
3
The kinetic laws (v) used in the model are deduced from the electrochemical phenomena associated
with the dissolution of minerals (Ahmadi et al., 2012; Bolorunduro, 1999).
The first copper released by chalcocite and the first two coppers released by bornite, are modelled by
the following kinetic law:
0.5
𝑣 = 𝛽(𝑇)𝑎𝐹𝑒3+ (2)
The second copper released by chalcocite, the last three coppers released by bornite and the
dissolution of natural covellite and pyrite, are modelled by the following kinetic law:
𝑎 0.5
𝑣 = 𝛽(𝑇) (𝑎𝐹𝑒3+ ) (3)
𝐹𝑒2+
In the case of chalcopyrite, the kinetic law used takes into account the ratio between the activity of
free ferric and ferrous ions (solution redox potential is a logarithmic function of that ratio) and
temperature (Petersen & Dixon, 2006):
𝑎 𝜑𝐴 𝑎 𝜑𝐵 𝑎
𝑣 = 𝛽(𝑇) {𝑘𝐴 (𝑎𝐹𝑒3+ ) + 𝑘𝐵 (𝑎𝐹𝑒3+) 𝑒𝑥𝑝 [− (𝑎𝐹𝑒3+)⁄𝑅𝑐𝑟 (𝑇)]} (4)
𝐹𝑒2+ 𝐹𝑒2+ 𝐹𝑒2+
In the case of copper oxide or gangue minerals, the conversion is calculated with the following
equation, in which it is assumed mixed control and kinetic law of order one respect to the activity of
free protons:
2
𝑑𝛼𝑖 3𝐷𝑒 𝛽(𝑇)𝑎𝐻+ (1−𝛼𝑖 ) ⁄3
= 2 [(1−𝛼 )1⁄3 −(1−𝛼 )2⁄3 ]
(5)
𝑑𝑡 𝜌𝑟 𝐷𝑒 𝑟𝑖0 +𝜌𝑟 𝜎𝐺𝛽(𝑇)𝑟𝑖0 𝑖 𝑖
The temperature dependence of the kinetic constants is modeled with the Arrhenius equations
(Ahmadi et al., 2012).
The activities of free ferric, ferrous and protons, used in the kinetic laws, are calculated by means of
a speciation model that it is included in the general model developed by BioSigma.
Solution Speciation
The speciation model considers the definition of chemical components and species in solution.
Components are selected such that all species can be formed by the components. The components
included in the model are Cu2+, Fe2+, Fe3+, H+, OH- and SO42-.
The species concentrations are calculated by means of equilibrium equations as a function of
components concentration (Carrasco, 1998; Casas et al., 2000). Equilibrium constants were estimated
with the HSC Chemistry software. Other basic equations of the speciation model are the total molar
balances of each component of the system. To take into account the deviations from ideal behaviour
of the ionic mixture in solution, the model uses activity coefficient factors based on the extended
Debye-Hückel equation (Dry & Bryson, 1988).
Respect to iron precipitation, it is considered in the model that precipitation of ferric ions occurs if
𝑙𝑜𝑔[𝐹𝑒 3+ ] > 𝑙𝑜𝑔[𝐹𝑒 3+ ]𝑐𝑟 , according to a kinetic described by a rate law of one order respect to the
ferric ions concentration (Leahy & Schwarz, 2009). [Fe3+]cr is a critical concentration of ferric ion over
which precipitation occurs, and depends on the pH of the solution.
4
Heap Energy Balance
The heat balance of the heap/dump considers the transfer of heat by conduction in the three-phase
bed and advection by the liquid and gas phases, and the heat production by the dissolution of
minerals (Dixon, 2000).
The boundary condition at the top of the heap takes into account the effect of irrigated solution and
the atmospheric conditions, such as ambient temperature and humidity, wind, and solar irradiation,
and their daily and seasonal variation.
The equations used to estimate the global heat transfer coefficient in the surface at the top of the heap,
gives the option to include the effect of an anti-evaporation film and the effect of buried drippers on
the heat balance.
The boundary condition at the bottom of the heap considers the air that is injected to the heap or the
air that rises due to natural convection.
Balance of Microorganisms
The model considers the growth and maintenance of iron-oxidizing and sulfur-oxidizing
microorganisms, the adhesion and desorption to and from ore particles, respectively, and the
movement of microorganisms in solution by dispersion and advection (Leahy, Davidson, Schwarz,
2005).
Specific growth rates of microorganisms are modelled by Monod-type equations. Ferrous ions and
dissolved oxygen are considered limiting substrates for iron-oxidizing microorganisms. Elemental
sulfur (produced as a residue in the leaching of copper sulfide minerals) and dissolved oxygen are
considered limiting substrates for sulfur-oxidizing microorganisms. In both types of microorganisms
the model includes the effect of temperature in the maximum specific growth rate by means of the
Ratkowski equation (Franzmann et al., 2005)
The activity of iron-oxidizing microorganisms (growth and maintenance) affects the concentration of
ferrous and ferric ions, protons, and dissolved oxygen, and the activity of sulfur-oxidizing
microorganisms (growth and maintenance) affects the concentration of elemental sulfur, protons,
sulfate and dissolved oxygen.
Balance of Oxygen in Solution and Gas

The bioleaching heap model developed by BioSigma includes the oxygen balances in the liquid and
in the gas phases. The balances in the solution and gas phase (air) takes into account the transfer of
oxygen through the heap/dump by dispersion and advection, and the transfer between solution and
air. Also the balance in the solution takes into account the consumption by microorganisms.
The Henry’s law constant used in the model is calculated as a function of temperature, and the
volumetric oxygen mass transfer coefficient was estimated with equations that takes into account the
size of ore particles and the solution irrigation rate (Tromans, 1998).
5
AUTOMATIC CALIBRATION
The model developed by BioSigma gives the option to adjust automatically some selected model’s
parameters using experimental data. In this calibration process, it is reduced the difference between
model results and experimental results, defined as the following total error ET:
𝐸𝑇 = 𝑥𝐶𝑢𝑅 𝐸𝐶𝑢𝑅 + 𝑥𝐴𝐶 𝐸𝐴𝐶 + 𝑥𝐹𝑒𝑅 𝐸𝐹𝑒𝑅 + 𝑥𝐹𝑒2+ 𝐸𝐹𝑒2+ + 𝑥𝐹𝑒3+ 𝐸𝐹𝑒3+ + 𝑥𝑋𝐿 𝐸𝑋𝐿 + 𝑥𝑋𝐴 𝐸𝑋𝐴
+ ∑𝑗 𝑥𝐶𝑢,𝑗 𝐸𝐶𝑢,𝑗 (6)
Where ECuR, EAC, EFeR, EFe2+, EFe3+, EXL, EXA, and ECu,j, are the errors associated to copper recovery, acid
consumption, iron recovery, ferrous ions concentration, ferric ions concentration, concentration of
microorganisms in the effluent solution, concentration of microorganisms attached to ore particles,
and concentration of mineral specie j in the ore. xi are weighting factors associated to the previously
mentioned errors. Each error is calculated with an equation of the following type:
𝜙 2
𝑒𝑥𝑝,𝑖,𝑘−𝜙𝑚𝑜𝑑,𝑖,𝑘
𝐸𝑖 = ∑𝑘 ( ) (7)
𝑀𝑎𝑥(𝜙𝑒𝑥𝑝,𝑖 )
exp,i,k is the experimental result of variable i (copper recovery, acid consumption,…) in time tk, mod,i,k
is the model result of variable i in time tk and Max(exp,i) corresponds to the maximum experimental
value of variable i. The total error ET is minimized using the function fminsearch of SCILAB software.
The function computes the minimum of function ET with the Nelder Mead algorithm (Mathews &
Fink, 1999).
The parameters selected in the calibration process depend on which errors we are interested to
minimize. For example, if the interest is to minimize the error associated to copper recovery
prediction, the kinetic rate constants of copper sulfides and copper oxides must be selected.
MODEL APPLICATION
In this section some results using the bioleaching heap model developed by BioSigma are showed.
The model was calibrated using information obtained in two heaps which were part of a semi-
industrial test executed in the north of Chile (Heaps 1 & 2). The heaps were designed and operated
according to BioSigma’s technologies for the treatment of copper sulphide minerals. Table 1 shows
the main characteristics of Heaps 1 and 2.
Figures 1 to 4 present the results of the model after its calibration with information of the Heap 1. The
figures show that the model developed by BioSigma is satisfactorily adjusted to the experimental
results obtained in the semi-industrial Heap 1, such as copper recovery, acid consumption, iron
recovery, iron concentration in the effluent solution, and the sequential dissolution of mineral species.
Besides the model satisfactorily predict the solution redox potential and the pH of the effluent
solution (Figure 4). The model was also satisfactorily calibrated with the data obtained in the
operation of the semi-industrial Heap 2 (results not shown here)
6
Table 1 Main characteristics of Heap 1 and Heap 2
Parameter Heap 1 Heap 2
Heap height 7.7 m 9.5 m

Total copper grade 0.46 % 0.44 %
Chalcocite 11.7 % Chalcocite 4.50 %
Covellite 0.80 % Covellite 3.70 %
Bornite 35.6 % Bornite 51.8 %
Chalcopyrite 36.4 % Chalcopyrite 35.7 %
Chalcopyrite
Copper oxide 36.4
15.5 % Chalcopyrite
Copper oxide 36.4
4.30 %
Total iron grade Chalcopyrite
0.67 % 36.4 % Chalcopyrite
0.67 % 36.4 %
Copper oxide
Covellite 15.5
0.80%% Copper oxide 15.5
Covellite 0.80%%
Particle size Chalcopyrite
Run off mine 36.4 % Chalcopyrite
100 % < 1 ½ inch36.4 %
Copper oxide 15.5 % Copper oxide 15.5 %
Bornite 2 35.6 % Bornite 2 35.6 %
Average irrigation rate Chalcopyrite
5.7 L/h/m 36.4 % Chalcopyrite
5.6 L/h/m 36.4 %
Average injection air Chalcopyrite
0.6 Nm3/h/m2 36.4 % Chalcopyrite
0.6 Nm3/h/m2 36.4 %
Figure 1 Copper recovery and acid consumption of Heap 1. Blue points represent experimental results and
red points represent the model predictions after its calibration with experimental information
7
Figure 2 Iron recovery (model and experimental results) and ferrous and ferric ions concentration in effluent
solutions of Heap 1. Mod: model prediction; Exp: experimental result
Figure 3 Conversion of copper minerals and conversion of gangue minerals of Heap 1 (model results). Cc:
chalcocite; Cv: covellite; Bn: bornite; Cp: chalcopyrite; OxCu: copper oxide; Py: pyrite; Gg-Fe: gangue minerals
that contain iron; Gg: gangue minerals
8
Figure 4 Redox potential Eh and pH in effluent solutions of Heap 1. Green points represent experimental
results and blue points represent the model predictions after its calibration with experimental information
Figures 5 and 6 show the evolution in time of ferric ion concentration in solution inside the heap and
the concentration of microorganisms attached to ore particles, associated to the calibration of the
model with information of Heap 2.
Top of
the heap
Bottom of
Concentration (g/L)
the heap
Figure 5 Profiles of ferric ion concentration inside the heap. Prediction using parameters obtained from the
calibration of the model with information of Heap 2
9
Top of
the heap
Bottom of
Concentration (cell/g)
the heap
Iron oxidizing microorganisms
Sulfur oxidizing microorganisms
Figure 6 Profiles of iron and sulfur oxidizing microorganisms. Prediction using parameters obtained from the
calibration of the model with information of Heap 2
CONCLUSION
A state of the art integral bioleaching heap/dump model has been developed, which takes into
account the main phenomena associated to the process, such as mineral-solution reactions, transport
of ionic species and microorganisms, chemical speciation, attachment/detachment and growth of
iron- and sulphur-oxidizing microorganisms, oxygen balances in liquid and gas phases and heat
conservation.
The results presented in this work show that this integrated model can be adjusted satisfactorily to
the experimental data obtained in the operation of industrial bioleaching heaps, such as copper
recovery, acid consumption, iron recovery, and iron concentration in effluent solution. Besides the
model follow satisfactorily the experimental behaviour observed and measured in bioleaching heap
processes, such as the regeneration of ferric ions by iron oxidizing microorganisms, the consumption
of ferric ions by the dissolution of sulphide minerals, the increase of the solution redox potential as a
consequence of the microorganisms activity, the sequential dissolution of the different copper
sulphide minerals, and the evolution in time of the microorganisms concentration profile inside the
heap.
The model is currently used to assess heap/dump bioleaching performance on different industrial
projects and scenarios, and to predict the copper recovery and acid consumption associated to mining
plans of CODELCO’s divisions.
10
ACKNOWLEDGEMENTS
The authors acknowledge BioSigma S.A. for financing this work and allowing its publication.
NOMENCLATURE
αi Conversion of the mineral species i, kg/m3
t Time, days
v Dissolution rate of a mineral grain (kinetic law), kg/m2/day
r Ore density, kg/m3
ri0 Ore particle diameter, m
β Kinetic rate constant, kg/m2/day
T Temperature, K
aFe3+, aFe2+ Activity of free ferric and ferrous iron, mol/L
k A, k B Constants associated to the chalcopyrite’ rate law
A,B Exponents associated to the chalcopyrite’s rate law
Rcr Critical ratio between ferric to ferrous ions, associated to the chalcopyrite’s rate law
aH+ Activity of free protons in the liquid that surrounds ore particles, mol/L
De Effective diffusion of protons inside ore particles, m2/day
G Grade of mineral species of interest in the ore particles
REFERENCES
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sulfide concentrates in conventional and electrochemically controlled systems’. Hydrometallurgy,
Volume 217, pages 16-23.
Bennett, C.R., McBride, D., Cross, M., Gebhardt, J.E. (2012) ‘A comprehensive model for copper
sulphide heap leaching Part 1 Basic formulation and validation through column test simulation’.
Hydrometallurgy, Volume 127-128, pages 150-161.
Bolorunduro, S.A. (1999) ‘Kinetics of leaching of chalcocite in acid ferric sulphate media: chemical
and bacterial leaching’. M.Sc. thesis, University of British Columbia, Canada.
Bouffard, S. (2008) ‘Application of the HeapSim model to the heap bioleaching of the Pueblo Viejo
ore deposit’. Hydrometallurgy, Volume 93, pages 116-123.
Carrasco, M. (1998) ‘Speciation modelling in circuits of copper minerals leaching’. Chemical
engineering thesis, Faculty of Physical Sciences and Mathematics, University of Chile.
Casas, J.M., Lienqueo, M.E., Cubillos, F., Herrera, L. (2000) ‘Kinetic modelling of iron precipitation as
jarosite in leaching solutions using Thiobacillus ferrooxidans bacteria’. XIV Chilean Congress of
Chemical Engineering. 23 to 26 October 2000.
Dixon, D.G. (2000) ‘Analysis of heat conservation during copper sulphide heap leaching’.
Hydrometallurgy, Volume 58, Issue 1, pages 27–41.
11
Dry, M.J., Bryson, A.W. (1988) ‘Prediction of redox potential in concentrated iron sulphate solutions’.
Hydrometallurgy, Volume 21, Issue 1, pages 59- 72.
Franzmann, P.D., Haddad, C.M., Hawkes, R.B., Robertson, W.J., Plumb, J.J. (2005) ‘Effects of
temperature on the rates of iron and sulfur oxidation by selected bioleaching Bacteria and Archaea:
Application of the Ratkowsky equation’. Minerals Engineering, Volume 18, Issue 13-14, pages 1304–
1314.
Leahy, M.J., Schwarz, M.P., Davidson, M.R. (2004) ‘A column bioleaching model for chalcocite: an
investigation of oxygen limitation and bacterial inoculation on leaching’. In BACMIN Proceedings,
pages 41--47, Bendigo, Australia, 8-10 November 2004. AusIMM.
Leahy, M.J., Davidson, M.R., Schwarz, M.P. (2005) ‘A model for heap bioleaching of chalcocite with
heat balance: Bacterial temperature dependence’. Minerals Engineering, Volume 18, Issues 13-14,
pages 1239–1254.
Leahy, M. J., Schwarz, M., Davidson, M. R. (2006) ‘An air sparging CFD model for heap bioleaching
of chalcocite’. Applied Mathematical Modelling, Volume, Issue 11, pages 1428-1444.
Leahy, M.J., Schwarz, M.P. (2009) ‘Modelling jarosite precipitation in isothermal chalcopyrite
bioleaching columns’. Hydrometallurgy, Volume 98, Issues 1-2, pages 181-191.
Madsen, B.W., Groves, R.D., Wadsworth, M.E. (1974) ‘Application of a mixed kinetics model to the
leaching of low grade copper sulfide ores’. SME-AIME Fall Meeting, Acapulco, Mexico, September 22-
25, 1974.
Mathews, J.H., Fink, K.D. (1999) Numerical Methods using MATLAB, 3rd edition, Prentice Hall.
Ogbonna, N., Petersen, J., Dixon, D.G. (2005) ‘HeapSim - Unravelling the mathematics of heap
bioleaching’ In Dry M., Dixon D.G., eds. Computational Analysis in Hydrometallurgy, 35th Annual
Hydrometallurgy Meeting. CIM-MetSoc, Montreal, pages 225-240.
Ogbonna, N., Petersen, J., Laurie, H. (2006). ‘An agglomerate scale model for the heap bioleaching of
chalcocite’. The Journal of The South African Institute of Mining and Metallurgy, 106, pages. 433-442
Petersen, J., Dixon, D.G. (2002) ‘Systematic modelling of heap leach processes for optimisation and
design’. Proceedings of the EPD Congress and Fundamentals of Advanced Materials for Energy Conversion.
TMS, pages 757-771.
Petersen, J., Dixon, D.G. (2006) ‘Competitive bioleaching of pyrite and chalcopyrite’. Hydrometallurgy,
Volume 83, Issues 1-4, pages 40-49.
Robertson, S. (2017) ‘Development of an integrated heap leach solution flow and mineral leaching
model’. Hydrometallurgy, Volume 169, pages 79-88.
Rojas, F.J. (2015) ‘Phenomenological modelling of the fluid dynamics of gaseous phase and the
oxygen balance inside a bioleaching heap’. Mining engineering thesis, Faculty of Physical Sciences
and Mathematics, University of Chile.
Silva, O., Fuentealba, L. (2000) ‘Phenomenological model for the leaching of copper oxide minerals’.
Technical document property of IM2 Company, FONDEF Project, number D97I1045, Chile.
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thermodynamic analysis’. Hydrometallurgy, Volume 48, Issue 3, pages 327–342.
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Vilcáez, J., Suto, K., Inoue, C. (2008) ‘Modeling the auto-thermal performance of a thermophilic
bioleaching heap employing mesophilic and thermophilic microbes’. Hydrometallurgy, Volume 94,
pages 82-92.
13
Speciation and Conditioning of Copper Leach
Solutions
Jesús Casas1, José Luis Campos2, Leonardo Romero3, Patricia Piña4 and Roberto
Bobadilla4
1. Process Consulting, Chile
2. Universidad Adolfo Ibáñez, Chile
3. Universidad Católica del Norte, Chile
4. CodelcoTech, Chile
ABSTRACT
This work presents an hydrogeochemical model of solute speciation applied to raffinates and
pregnant leach solutions (PLS) of copper ore (bio)leaching and chloride-leaching operations. Also, a
conceptual process was defined for conditioning the raffinate solutions in order to control the
concentrations of dissolved sulphate, chloride, nitrate, aluminium and iron. The objective of solution
conditioning is to diminish the amount of dissolved impurities and adjust the leach solution to
improve its compatibility with bioleaching operations in heaps/dumps and maximize the activity of
acidophilic microorganisms during the copper recovery process. Solute speciation in leach solutions
was estimated by solving a multicomponent equilibrium model using the Hydrogeochemical Code
Phreeqc, using the SIT model to calculate the solute activities, with an updated database for main
metal chloride and sulphate metal-complexes. Solution conditioning consisting in nanofiltration and
redox potential reduction using metallic iron scrap were also simulated and solute speciation for
treated solutions were estimated under different total dissolved salts and acidity conditions.
Speciation results on pH, acidity, solute concentrations, and ionic activities for dissolved cupric, ferric
and ferrous iron were compared and discussed for the study of leach solutions. Sulphate complexes
increases with the solution acidity, relevant complexes were: HSO4-, AlSO4+, FeH(SO4)2(aq), Al(SO4)2-
and Fe(SO4)22-. Chloride complexes exhibit low activities in the studied conditions and mostly was
present as free ion (Cl-). Magnesium were distributed as Mg2+, MgCl+ and MgSO4(aq).
1
Application of an Operative Model of Excellence for
the Optimization of Hydrometallurgical Plants
Reinaldo Mendoza and María Veas
RMV Ingehidromet, Chile
ABSTRACT
The profitability of a business associated with achieving its maximum productivity, is the final
objective of all mining operations. According to our experience, many operations tend to deviate
from this objective when certain variables of the metallurgical process is controlled by focusing only
on the value of the variable to be achieved, rather than how these values are achieved.
In order to optimize the profitability of a mining operation, RMV developed an Operational
Excellence Model, based on metallurgical tests of the feasibility studies of mining plants in operation,
and on specific actions to correct operational deviations, that influence negatively the metallurgical
yield of the process, applying the know-how of RMV and its engineers.
The validation and robustness of this operational model is given by the good results obtained of the
applicability of the model in eight opportunities, in mining operations of medium and large scale, in
Chile and abroad.
This study concludes that after the application of this model it is possible to better the metallurgical
operation and obtain an increase of the total copper recovery between 5 and 15 percentage point over
the present recovery before to apply the model. Additionally, it is concluded that the maximum
profitability that is intended by any mining project, will only be reached to the extent that
the metallurgical control or quality of the operation, is close to the initial model, that is, the one
reported mainly by the metallurgical tests, at laboratory, pilot and/or industrial scale, besides having
a control on the deviations of a quality operation.
1
Dynamic Simulation of Operational Variables for
Optimal Design of a Processing Plant Adaptation
Verónica Escobar, Sebastián Galvez and José Guerra
Jacobs, Chile
ABSTRACT
Life-of-mine variations in ore feed characteristics and /or need for an increase in feed-rates, or a novel
processing route, might all require the brownfield adaptation of an existing plants. Because the
existing plant was not designed for the new condition, any adaptation to the novel condition will
have to deal with existing restrictions. Also, the method by which the adaptation takes place has great
impact in the way the process responds, thus planification of the transition is non-trivial.
Under these conditions, steady state analysis used for process calculations can be misleading since
significant phenomena are transient in nature and are not explained through such models.
Operational aspects of the transition to the new process condition can be missed in preliminary
assessment of the new process and important operating costs overlooked. It is here that dynamic
simulations are used to simulate important operational variables and improve steady-state
calculations for plant adaptations as previously described. Variations of important process streams
around their mean steady state values can thus be modeled and peak demands identified for correct
equipment sizing and adaptations. Robustness of the adapted plant for facing variations in feed or
reagent characteristics can also be modelled and identified, designing modifications that mitigate any
adverse effects. Transient models also assist in estimating how soon after the change of technology
will the process resume a steady-state operation if applicable, assisting the scheduling needs of the
project development.
In this work an outline of methodology shall be presented in which dynamical modeling of important
operational variables, even in simplified fashion, is explicitly recommended for assessing future plant
performance of brownfield adapted plants. Examples shall be provided of how such modeling
enriches the understanding of future plant performance including the transition in such a manner as
to permit design improvements that otherwise could be missed.
1
INTRODUCTION
Mining companies are well known to be very sensitive to the price of mineral commodities and over
the past years they have been decreasing worldwide. This cycle has created a new set of challenges
and opportunities for mining competing to secure higher production of the minerals demanded by
the world economy. One of the consequences of this has been to favour those projects that improve
the financial viability of their operation, making brownfield projects more attractive, to the point that
they have been lately outnumbering greenfield projects (Smale, 2013).
The future of most mining companies depends on maintaining and growing their access to mineral
resources and having the capacity of exploiting them at a competitive cost. Often, the strong desire
to increase production puts pressure to expand the resource base of the mine to get maximum value
out of the capital employed. This, plus declining world-class discovery resources, greenfield projects,
makes brownfields projects a high priority activity in many operating mining companies. The
advantage of the brownfield project is Low Cash Cost, and Low Capital Intensity due to savings
through the reuse of significant infrastructure (Pino, 2011).
For the long-term survival of a company it is critical that these projects be well developed and
successfully executed. The primary aim of brownfields projects is to add value through:
 Mine or plant capacity expansion.
 Displacement of lower-margin ore from the mine plan.
 Optimization to changes in mineralogy and improvements in geological understanding.
 Study of ramp up, which has many benefits for the design, start-up and operation.
 Implementation of a new processing strategy.
On the other hand, during the last decade various copper oxide hydro-metallurgical plants have been
reaching the end of their production life, mainly due to the depletion of the oxide mineral and an
increase of the sulphide minerals. Examination of the Life of Mine (LoM) profile will highlight critical
issues including future grade and throughput issues, key technology, innovations and scenarios for
increased production. The brownfields projects should address these key issues.
In this context, brownfield project should plan the adaptations of their plants such as to lessen any
potential adverse impact on production during the implementation and execution phase. The
adaptations can range from a straightforward increase in processing capacity, leaving the process
path relatively unchanged, to radical changes that may involve the implementation of a new process.
The purpose of this paper is to highlight particularities of this latter type of project in which a new
process is introduced, and signal out potential aspects that could constitute relevant challenges for a
successful execution. A methodology for technical studies is to be proposed that help to solve these
issues. This methodology is characterized by a strong use of dynamic process simulation tools, to
assist in the development of the conceptual engineering and pre-feasibility phases of the studies.
CHALLENGE IN ADAPTING EXISTING PLANTS TO NEW PROCESSES

When an existing installation has to be adapted to a new process, a challenge of a different kind
emerges. In this context, the existing facilities play a restrictive role that narrows the universe of
possible designs. Indeed, it will rarely be possible to reconvert a facility equivalent to what a
greenfield project would propose as design, using up-to-date technology and a tailored equipment
2
selection chosen for ideal fit to process. As a result the operation of a processing plant adapted to a
new process most likely will include "obstacles to the operation" that are not easy to identify initially.
As a consequence, changes are introduced in advanced engineering phases, with an adverse impact
in costs and/or overall project schedule.
For the brownfield adaptation to the new leaching process, conceptual studies that only include
issues related to infrastructure and average capacity, is often done. This approach run the risk of
relegating the development of a new operating philosophy, to the more advanced stages of
engineering and missing the opportunity to produce an optimal philosophy for the new process.
Furthermore, continued consideration of the old operating philosophy might not identify a cost
effective implementation of the new process. In this case, operating costs estimates and validations
of the installed capacity by use of steady state calculations can be misleading and possibly induce a
bad business decision. Another challenge is the average life of the equipment plant and should be
considered in the total capital cost.
As a simple example to illustrate the point in question, consider a certain stream flow for a new
process, which presents an oscillating and periodic pattern between a minimum and a maximum
value. This stream indeed can be represented by stationary models using a single average value for
the flow rate. This average value could be within the capacity of existing pumping systems, inducing
to think that there is no need to further invest in adaptations for the pumping systems. Moreover, the
amplitude between maximum and minimum could be dependent on the planned sequence of leach
pad loading. Therefore, if a review of the operating philosophy is not performed at the initial
conceptual studies, this impact would not be considered in the design. The project would specify a
solution for the peak pumping demands, without having even studied ways to avoid the root cause
of peak demands.
In pursuit of advancing a proper understanding of all relevant operational aspects resulting from the
adaptation of an existing plant, this paper proposes a methodology that includes dynamic modeling
of the main operational variables at early stages of plant adaptation studies. For this purpose,
dynamic process modeling and simulation stands out as the ideal tool to predict the behavior profile
of all modeled variables.
Brownfield Project Development

For the development of engineering phase studies of existing plants adaptation to new processes, the
information available must validate the rationality of the process and enable the identification of
appropriate design criteria for an industrial scale implementation. This can require from frequent
field visits to carry out direct plant inspections, up to the use of more modern tools such as 3D.
Capacity increase projects will require particular support from Operational Diagnostic Studies, to
establish the level of revamping that might be required. Plant changes that remove or add surge
capacity (stockpiles, process ponds) must be carefully studied to identify the impact this has on the
global utilization of the processing plant (Escobar, Gálvez & Guerra, 2015). Additional information
such as Design Criteria, mass balances, leaching cycle, kinetics information, flowsheets, P&IDs, etc.,
should be considered.
In particular, tie-in identification and preliminary scheduling of the works required for the
implementation can be performed and establish an estimate of the investment cost to be considered.
Included as part of this comprehensive approach to plant adaptation studies, optimization of the new
process, bottleneck analysis and other tasks that seek to identify and implement improvement
3
opportunities. Having identified a set of feasible implementations of the new process that includes
all required modifications, formal trade-off studies can be undertaken (Pino, 2011). The objective is
to establish a recommendation for those feasible alternatives will maximizes business case.
Brownfield projects that impact operational facilities, it is imperative to minimize non-productive
moments. Planning should proceed with the focus on risk minimization and maximization of
efficiencies and as far as possible, productive facilities should avoid any downtime. In particular, tie-
ins for new equipment should be considered early in the conceptual studies, whereas new routing of
lines and other activities of this nature should be planned to take place during planned maintenance
downtime. The focus should always be to identify ways to avoid operational disruption at the time
of introducing the definitive adaptations.
Brownfield plant modifications also constitute an opportunity to incorporate new technology and to
upgrade the control systems, so as to permit modern data analytics from process data and to
introduce more effective control strategies. Through such changes, it can be possible to enhance
process stability and permit statistical process control techniques to be incorporated so as to improve
performance. Also, improved operational data collection can be used for future operational
improvement projects, to serve as basis for following engineering studies.
To avoid running the risk of not identifying operational aspects which may constitute a risk to the
project if corrective actions are not taken early, this paper proposes the use of dynamic modeling of
main process variables. Modeling not only implies running numerical simulations, but also involves
performing a detailed description of how different variables interact among themselves(Desbiens,
Hodouin and Millot, 1999)
. This in itself improves the understanding of the operational performance of the plant. In the specific
case of a heap leaching plant, the overall profile of copper that is sent to SX (flow and concentration)
can be dependent on both mineralogical characteristics as well as design philosophy used for
planning the leach pad loading. In a plant where two heap leach pads coexist with independent PLS
and raffinate ponds, modelling studies clearly show how the leach pad loading sequence impacts
copper profiles, in particular in scenarios which include alternation of the leach pad loading between
both heaps. Simulation of copper content and overall flow profiles for different loading strategies
produced the necessary information required not only to predict future performance but also to
optimize loading strategies that minimize operational challenges, as well as evaluation design
modifications that improve operability.
It is foreseen that the implementation of dynamic simulation models will result in main benefits:
 Compare different plant design and different ore types and mining strategies.
 Assess operating strategies that affect capacities.
 Assess the plant control to have less operating error and less supervision.
 Increased process stability yielding more consistent metallurgical behaviour.
In order for the change in plant design to proceed, valid simulation models of the process must be
formulated (Kennedy, 2014). Theoretical models are valid over the entire operating range of the
process, provide an understanding of basic mechanisms and are the most reliable route towards
process modelling. They have the disadvantage, however, of utilizing large numbers of parameters
and may therefore be difficult to obtain. Empirical models do not normally provide an understanding
of basic mechanisms and are dangerous when extrapolated outside the limits of the data but,
generally less time consuming and therefore less expensive.
4
Specific example with two independent circuits
Consider a leaching plant that makes use of multiple areas for ore stacking and irrigation, as in Figure
1, which represent a plant designed with only one heap, and later added another. Each area in itself
is associated with its respective raffinate irrigation demand and PLS production capacity.
Figure 1 Simplified diagram of ore stacking in plant with two independent leach heaps
In the scheme previously described a continuous stacking of ore takes place by the operating
philosophy. A particularly rich dynamical case occurs if the full metallurgical cycle requires that all
available area is used for leaching. In this case, the pumping profile of irrigation raffinate and the PLS
flow profile sent to SX, per area, can be strongly dependent on the ore stacking strategy in use.
A first stacking strategy could dictate a continuous loading in each area replacing the depleted ore,
then to do the same in the other area. This strategy maximizes the continuous stacking and minimizes
alternating the transport of ore between the two areas. Another radically different strategy would
seek to alternate with greater frequency between stacking areas, entailing more frequent changes of
the ore transport systems to switch between heap pads, and a shorter duration for each continuous
stacking period, within each area.
In the steady-state model, an average value of raffinate and PLS per area is calculated, proportional
to the irrigated area, the specific irrigation rate, and other parameters. However, it turns out that an
ore stacking strategy must be specified to perform a detailed dynamical model of the system. If a
leach cycle that includes "resting" periods that do not demand raffinate irrigation is considered. In
this case, any strategy that maximizes continuity of stacking area will produce contiguous areas of
stacked ore simultaneously “resting”, which at one point could be located entirely in one area and
therefore imply a peak demand of raffinate. In this example the flow pattern for raffinate and PLS is
then function of multiply variables, making it necessary to model the system to perform detailed
projections for main process streams per area.
Figure 2 PLS and raffinate stream as function of ore stacking strategies
5
Figure 2 shows three profiles of raffinate to be pumped to one of the two areas, for a leach process
similar to what is shown in Figure 1. The profiles are the result of using simplified design criteria and
a metallurgical cycle that includes a prolonged “waiting” period without irrigation. The figure shows
different profiles for one same process that responds to different ore stacking strategies, where the
strategy N°1 maximizes continuity (minimizes alternations of stacking between available areas) but
implies maximum variation between minimum and maximum flow rate value. At the other end the
stacking strategy N°3 presents greater frequency of change between areas, but lower amplitude
between minimum and maximum flow rate. It is important to emphasize that all profiles have the
same average value, so all are consistent with the same average flow rate that would be estimated by
a stationary state model.
Example 2 “An integration of a new leach plant to an existent SX plant”

A new heap leaching plant will send the PLS solution to an existing nearby plant that has additional
capacity in its SX and EW area. In turn the existing plant will send the raffinate solution back to
irrigate the new heaps, corresponding in flow to the sent PLS.
Figure 3 Integration of a new leach plant
The PLS solution from the PLS pond will be sent to the SX plant by a pipeline and two 700 m3/h
pumps. The start-up strategy consisted in generating the initial irrigation solution with acidulated
water. As the PLS reaches the pond, the recirculation to the heap began and continues until a steady
flow of about 700 m3/h is reached. At this point one of the pump started sending the PLS solution to
the SX Plant, which is the minimum flow of the SX Pump System.
Figure 4 Strategy for ramp up
After the dynamic simulation of the ram up of the process, it was observed that the recirculating the
solution to 700 m3/h produced a high concentration of Cu (+ 40 g/L; Figure 5), an undesired situation.
The following options were considered to decrease the Cu concentration:
6
• Variable Frecuency Drive (VDF) Pump to reduce the minimum operation and recirculation flow.
• Include a third pump for reduction of the design flow of each.
These analyses selected the third VDF pump to reduce the concentration of Cu to less than 20 g/L.
Figure 5 Cu concentration during the ramp up
Value from modeling and dynamic processes simulation

In general terms, by performing dynamic process modeling, one is forced to consider operational
aspects of the process in accordance with the projected operational philosophy. During this process
of modeling, a sound understanding of the operation is reached, permitting to identify issues and
discover if particular adaptations are required to permit a fully feasible implementation of the
adapted process, with existing infrastructure.
It is our belief that engineering studies can better understand dynamical phenomenon of plant
performance by modeling works and that by simulating the critical operational variables of a process,
knowledge is created that can be acted upon. In specific, potential operating issues can be brought to
light early and thus identify engineering solutions, and more precise cost estimates can be produced
that fully reflect the real costs of performing a planta adaptation. Moreover, once a new process has
been modeled, usage of simulation can allow the evaluation of multiple simulation runs without
incurring additional modeling costs. This way, a multitude of possible scenarios can be evaluated in
order to identify optimized alternatives, and thus provide greater value from initial engineering
designs and trade off studies. Operational aspects can also be simulated so as to identify how the
adapted facilities will respond once operated in accordance to all potential operating philosophies.
CONCLUSION
In conclusion, brownfield plant adaptations for new process needs requires the development of
conceptual studies, trade off reports and preliminary engineering works to establish feasibility and
provide initial cost estimates that support a positive business case. However, it is strongly
recommended that these studies be complemented with detailed modeling of operational variables
in an early stage of the studies. The process itself of detailed dynamical modeling provides intrinsic
knowledge regarding operability of the proposed process and permits to promptly identify
potentially hindering issues on operational performance that need be fixed for proper plant
performance. Dynamic modeling also produces dynamical profiles for each modeled variable that
can be used in optimization studies and design improvement identification reviews. In extreme cases,
7
modeling can signal out challenges that have to be remedied prior to establishing full viability of the
adaptation project, allowing that design solutions be found in early stages of project development for
issues that could ultimately imply costly late engineering changes or wrong business decisions to be
made.
REFERENCES
Desbiens, A., Hodouin, D. and Millot, M. (1999) “Model-Based Predictive Control; A General
Framework”, 38th Annual Conference of Metallurgist, Quebec, Canada.
Escobar, V., Gálvez, S., y Guerra, J. (2015). “Análisis conceptual de proceso para configuración técnico
– económica óptima en el diseño de plantas de chancado”, VI Congreso Internacional de
Conminución de Minerales Minecrush Chile 2015, Viña del mar, 2015.
Kennedy, M. W.. (2014) Metallurgical Plant Optimization Through the use of Flowsheet Simulation
Modelling. Celebrating the Megascale: Proceedings of the Extraction and Processing Division
Symposium on Pyrometallurgy in Honor of David G.C. Robertson.
Pino, F., (2011), “Advantages and disadvantages of brownfield projects”, Procemin 2011, Santiago,
Chile.
Smale, Don, (2013). “Review and outlook for Copper, Nickel, Lead and Zinc”, Unctad, Multi-Year
Expert Meeting on Commodities and Development.
8
Multizone Process Water Metering using Distributed
Acoustic Sensing (DAS)
Daniel Finfer1, Phil Newman2, Neil Rein3 and Mohammad Amir1
1. Silixa, United Kingdom
2. Anglo American, United Kingdom
3. Anglo American, South Africa
ABSTRACT
Silixa was commissioned by Anglo American to execute the worlds’ first pilot installation for a non-
intrusive, multi-zone, multi-fluid process flow metering system based on distributed acoustic sensing
(DAS) technology. The pilot was executed at eMalaheni Water Reclamation Plant (EWRP), where
Acid Mine Drainage (AMD) is reclaimed from local coal mines for use as both drinking water and
mining process water. As is the case for many process plants of this scale, the desire for water flow
control is challenged by the need for large numbers of reliable, low-Capex flow meters that can be
retrofit non-intrusively on pipes of varying materials with a range of sizes. In this case, the process
metering installation featured liquid and slurry handling lines (made from both steel and HDPE)
ranging from 165mm to 400mm in diameter; all of which were monitored using a single fiber. Further,
the process metering system network was required to be robust against flows featuring high solid
fractions (>30%). It was demonstrated that distributed fiber optic sensing can be used to enable flow
sensing at several locations within the plant simply by instrumenting all of the pipes of interest with
a continuous length of optical fiber without the addition of costly power and communications
systems. It was seen that the sensing layout was straightforward to install, and that the flow rate
output was in good agreement with reference measurements made using conventional sensors. The
successful sensing of these flows indicates good potential for this technology to be used for pervasive
metering in a broad range of plant types.
1
CHAPTER 3
Base Metal, Precious

Metal, non-Metallic
Elements, Saline
Compounds and Rare
Earth Hydrometallurgy
Cyanidation of Silver Telluride (Ag2Te): Effect of
Lead (II) Concentration, Particle Size and Presence of
Pyrite
Adrián González, Fabiola Nava and Alejandro Uribe
CINVESTAV Unidad Saltillo, Mexico
ABSTRACT
The recovery of precious metals from refractory ores has been widely investigated due to depletion
of free milling ores. There are numerous causes and degrees of refractoriness and one of them is the
presence of precious metals tellurides such as calaverite (AuTe2), krennerite ((Au,Ag)Te2), sylvanite
(AgAuTe4), petzite (Ag3AuTe2) and hessite (Ag2Te). In the present study, the cyanidation of silver
telluride (Ag2Te) was investigated with the aim of recovering silver. The effect of lead(II)
concentration (i.e., 50, 100 and 150 mg/L), particle size (i.e., +38/-45 µm, +45/-53 and +53/-63 µm) and
presence of pyrite at two different Ag2Te/FeS2 mass ratios (i.e., 0.59 and 1) on the leaching kinetics
are reported. The addition of lead(II) was the variable with the strongest effect, followed by particle
size and presence of pyrite. Eh-pH diagrams suggest the formation of TeO2, which apparently
inhibits the cyanidation reaction, tellurium species that is not present when lead(II) is added. When
lead(II) is added, the elements present in the solid residue of the cyanidation reaction are tellurium
and lead (probably in the form of oxides or hydroxides), but not silver. The addition of certain
amount of lead(II) is necessary to successfully dissolve the silver from silver telluride (Ag2Te) and
to reduce cyanide consumption at any of the size fractions studied, although in the presence of
pyrite a small reduction of silver recovery is observed.
1
INTRODUCTION
In hydrothermal deposits precious metals may occur as tellurides species, of which the most
common are calaverite (AuTe2), krennerite ((Au,Ag)Te2), sylvanite (AgAuTe4), petzite (Ag3AuTe2)
and hessite (Ag2Te) (Aguayo, Pérez & Encinas, 1996; Henley, Clarke & Sauter, 2001; Zhang et al.,
2010). The presence of precious metals tellurides may render an ore refractory, the extend of this
depending on the particular telluride present and on the mineralogical association (Jackman &
Sarbutt, 1990). Due to the depletion of “free milling” ores and to the more intense geological
exploration, precious metals extraction from refractory ores have attracted increasing attention (La
Brooy, Linge & Walker, 1994).
Cyanidation has been practiced for over 100 years to extract precious metals from their ores due to
the high stability of the gold/silver-cyanide complexes (equation (1)) (Habashi, 1967; Zhang, Fang &
Muhammed, 1997; Senanayake, 2006). However, the solubility of precious metals tellurides in
cyanide solutions has been debated for many years as these dissolve at a slower rate, compared to
native gold, silver and electrum (Cornwall & Hisshion, 1976; Marsden & House, 2006). Therefore,
alternative treatments must be applied to increase the recovery of precious metals (e.g., roasting,
bio-oxidation, fine grinding, oxidation with alkaline calcium hypochlorite, cyanidation in presence
of lead(II), etc.). There is little scientific and technical literature on the subject. On one side, works
employing synthetic calaverite and sylvanite have been carried out showing low gold extractions
(Padmanaban & Lawson, 1991; Lu & Lawson, 1994). On the other side, the increase on cyanidation
rates by ultrafine grinding (Liddell & Dunne, 1988) and cyanidation at high pH (above 12) have
been reported (Jayasekera, Ritchie & Avraamides, 1988; 1991).
4Ag + 8CN - + O2 + 2H2 O = 4Ag(CN)-2 + 4OH - (1)
It is well known that the presence of heavy metal ions such as lead, bismuth, thallium and mercury,
catalyze both gold cyanidation and oxygen reduction (Dai & Jeffrey, 2006; Dai & Breuer, 2013;
Deschenes et al., 2010). The effect of lead nitrate addition on the cyanidation of gold ores has been
studied (Sayiner, 2014) and it is believed that the catalytic activity of lead on anodic dissolution of
gold consists on the formation of gold-lead alloys such as AuPb2, AuPb3 and metallic lead on the
surface of gold. These alloys occupy some of the surface sites on gold and prevents the formation of
polymerized AuCN film and some other passivating species (Deschenes et al., 2010; Sandenbergh &
Miller, 2001).
Precious metals extraction from tellurides have been commercially treated in Kalgoorlie (Western
Australia), Vatukoula (Fiji), Cripple Creek (Colorado), and Kirkland Lake (Ontario) (Zhang et al.,
2010). Nevertheless, there is a large measure of disagreement on the behavior of precious metals
tellurides on cyanidation systems due to the lack of research on the cyanidation of telluride species
other than calaverite and sylvanite.
The aim of the present investigation was to study the cyanidation kinetics of silver telluride
(Ag2Te), since the presence of this species is common in deposits containing tellurium and precious
metals. For this purpose, the effect of lead(II) concentration (i.e., 50, 100 and 150 mg/L), particle size
(i.e., +38/-45, +45/-53 and +53/-63 µm), and the presence of pyrite at two different Ag 2Te/FeS2 mass
ratios (i.e., 0.59 and 1) on the silver extraction by cyanidation are reported. The cyanidation kinetics
2
results are complemented with Eh-pH diagrams and chemical analysis by energy-dispersive
spectrometry (EDS) (EDAX Genesis), to identify the products of the process and the species that
hinders silver dissolution.
METHODOLOGY
Materials and reagents

The Ag2Te used in this study was purchased from Sigma-Aldrich (99.999 %) and ground to obtain
the narrow size fractions +38/-45 µm, +45/-53 µm and +53/-63 µm. The pyrite sample (≥ 95 % purity)
was of natural occurrence and his mineralogical composition was determined by X-ray diffraction
(Philips X-Pert) and was ground to 100 % passing 200 mesh. Reagent grade chemicals (i.e., sodium
cyanide, sodium hydroxide and lead(II) nitrate) and deionized water were used.
Experimental procedure
Cyanidation experiments were conducted in a 100 mL water-jacketed batch reactor magnetically
stirred at approximately 350 rpm, 25 °C, 1250 mg/L CN - and pH 10.9 adjusted with NaOH
(standard cyanidation). The reactor was equipped with pH electrode (Cole-Parmer) and
temperature probe. The general procedure for the cyanidation experiments was as follows: 0.0477 g
of silver telluride (Ag2Te) were placed into the reactor together with 80 mL of deionized water; the
pH was adjusted by adding NaOH, and the CN - concentration was adjusted by adding NaCN.
When the effect of lead(II) concentration and Ag2Te/FeS2 mass ratios on the silver extraction were
studied, they were added before sodium cyanide. To study the effect of particle size and Ag2Te/FeS2
mass ratio, a concentration of 50 mg/L of lead(II) was employed since only in the presence of lead
acceptable silver recoveries (above 98 %) are achieved.
Samples of the solution were withdrawn at predetermined times during the cyanidation period and
silver was analyzed by atomic absorption spectroscopy (Varian SpectrAA220). The solids were
filtered off, air dried and analyzed by EDS to identify the present elements.
The experiments were carried out in triplicate and therefore, the mean value of the measured silver
extraction and error bars defining the 95 % confidence interval of student’s t-distribution are
reported.
To elucidate the predominant species in the cyanide and cyanide-lead(II) systems, Eh-pH diagrams
were constructed using HSC 6.1 Software. Bearing in mind the conditions at which cyanidations
were carried out, the diagrams are useful to determine the possible species that may be present in
the reaction system.
Effect of lead(II) concentration on the extraction of silver

As shown in Fig. 1, when silver telluride was subjected to standard cyanidation in the absence of
lead nitrate, the extraction of silver was 13.16 % after eight hours. In contrast, when 50 mg/L, 100
mg/L or 150 mg/L of lead(II) as lead nitrate was added, the extraction of silver increased to 98.3 %,
100 % and 100%, respectively.
3
Figure 1 Effect of lead(II) concentration on silver telluride (Ag 2Te) cyanidation for a solution containing 1250
mg/L CN- (0.0477 g Ag2Te, 0.08 L, pH 10.9, 25 °C and 350 rpm)
Lead(II) not only has a beneficial effect on dissolving silver from silver telluride, it also influences
cyanide consumption. When 100 mg/L of lead(II) as lead nitrate was added to the cyanidation
process, the cyanide consumption decreased from 1.7 g NaCN/g Ag, for standard cyanidation (e.g.,
no lead present), to 0.9 g NaCN/g Ag.
According to Padmanaban & Lawson (1991), when synthetic calaverite was subjected to
cyanidation, the formation of a product layer mainly consisting of tellurous anhydride (TeO2)
together with a small quantity of elemental tellurium, inhibit gold dissolution. Therefore, the same
solid products could be hindering silver extraction from silver telluride (Ag 2Te).
Redox potential measurements were performed during the cyanidation tests in Fig. 1. The redox
potential measurements were in the range 0.12 – 0.16 V vs SHE. A thermodynamic analysis with the
aid of Purbaix diagrams was carried out to better understand the reason behind the low extraction
of silver by standard cyanidation. Fig. 2 presents the predominance diagrams for the CN - and CN- –
Pb(II) systems (2a and 2b, respectively). In these diagrams the species tellurous anhydride (TeO 2)
and silver telluride (Ag2Te) predominate at pH 10.9. It is worth noting that when lead(II) was
added, the predominance area of the TeO2 is reduced as pH is increased; furthermore, at pH 10.9
and at the measured redox potential (0.12 – 0.16 V vs SHE), the predominant species of tellurium is
Ag2Te and not TeO2. This could be the main reason of the faster silver extraction when lead(II) was
added.
The solid products of the standard cyanidation and when a concentration of 50 mg/L lead(II) was
used, were analyzed by EDS to determine the weight % of the elements in the solid products. In the
case of standard cyanidation, the solid products that were analyzed, correspond to those in which
silver extraction was 13 % after eight hours (see Fig. 1). The results of the EDS analysis are
presented in Table 1.
4
Figure 2 Eh-pH diagram for the Ag2Te-CN and Ag2Te-Pb-CN systems at 25 °C: (a) 1.7X10-3 M Ag2Te; 4.8X10-2
M CN- and (b) 1.7X10-3 M Ag2Te; 4.8X10-2 M CN-; 2.4X10-4 M Pb
Table 1 Chemical composition of the reaction products, obtained by EDS: standard cyanidation
and cyanidation in presence of 50 mg L-1 lead(II)
Element (wt, %) Standard cyanidation Cyanidation / 50 mg/L lead(II)
Ag 60.52 --
Te 38.37 66.34
Pb -- 25.87
O 1.11 7.79
It can be observed in Table 1 that when silver telluride was subjected to standard cyanidation the
mass ratio Ag/Te of the unreacted Ag2Te is 1.57 (for the pure Ag2Te, such ratio is 1.69), and some
oxygen appears on the surface of the products (i.e., 1.11 %). This suggest that elemental tellurium
could be precipitating on the surface of the unreacted Ag 2Te. When lead(II) is added to extract 100
% of silver, the residues of the process mainly consist of tellurium (i.e., 66.34 %) and lead, which
may be present in the form of elemental lead or lead oxide. In the case of silver telluride (Ag 2Te)
standard cyanidation, there was no evidence of a product layer that could inhibit the extraction of
silver by cyanidation. At this temperature (25 °C) and for the reaction time used, the supposed layer
that retards the reaction could be forming and probably consists of elemental tellurium.
Effect of particle size on the extraction of silver

Figure 3 illustrates the effect of particle size on the extraction of silver by cyanidation when a
concentration of 50 mg/L of lead(II) was employed. It is observed in the figure that the particle size
had a significant effect on the rate of silver extraction. Although good recoveries were obtained
when lead(II) was added, the fine size fraction (i.e., +38/-45 µm) would result in faster extraction
rates. Considering that conventional milling processes reduces particle size to -75 µm, very fine
5
grinding would be necessary to extract silver from silver telluride (Ag 2Te) by cyanidation in
presence of lead(II).
Figure 3 Effect of particle size fraction on silver telluride (Ag2Te) cyanidation for a solution containing 1250
mg/L CN- and 50 mg/L Pb(II) (0.0477 g Ag2Te, 0.08L solution, pH 10.9, 25 °C and 350 rpm)
Effect of presence of pyrite on the extraction of silver

Since pyrite is the most common sulfide gangue that accompanies precious metal minerals, it is
important to study the effect of different Ag2Te/FeS2 mass ratios on the extraction of silver from
silver telluride (Ag2Te) by cyanidation. The results obtained are shown in Fig. 4.
Figure 4 Effect of the Ag2Te/FeS2 mass ratio on silver telluride (Ag2Te) cyanidation for a solution containing
1250 mg/L CN- and 50 mg/L Pb(II) (0.0477 g Ag2Te, 0.08L solution, pH 10.9, 25 °C and 350 rpm)
6
The figure 4 shows that for a Ag2Te/FeS2 mass ratio of 1, the extraction of silver was slightly faster,
compared to that obtained for the mass ratio of 0.59 and considering the confidence interval, this is
more noticeable in the first two hours. These two extraction kinetics in presence of pyrite were
faster than in the absence of pyrite in the time range of 0 to 4 hours. At four hours, the silver
extraction reached approximately 96 % and remained constant afterwards. In contrast, in the
absence of pyrite, silver extraction reached 100 % in approximately eight hours. When pyrite was
present, in either of the two mass ratios, the kinetic extraction was accelerated in the first four hours
and then was passivated. Such behavior occurs even though the presence of sulfide minerals does
not report any beneficial effect on precious metals cyanidation kinetics, with the exception of galena
(Deschenes et al., 2000).
CONCLUSIONS
Based on the results obtained, the following conclusions may be put forward:
When silver telluride (Ag2Te) was subjected to standard cyanidation, approximately 13 % of silver
was extracted after eight hours. The addition of lead(II) to the cyanidation system, from 50 mg/L to
150 mg/L, enhanced the extraction to values above 98 % after eight hours.
Particle size had a significant effect on silver extraction, the finer the size the faster the extraction
rate. It is necessary to carried out the process in the presence of lead(II) (e.g., 50 mg/L, 100 mg/L or
150 mg/L), otherwise the silver extraction will be hindered, no matter the size of the silver telluride
used.
When lead(II) addition of 50 mg/L is used, the silver extraction kinetics in presence of pyrite
(Ag2Te/FeS2 mass ratios of 0.59 and 1) was faster compared to that observed in the absence of pyrite,
in the first four hours. Nevertheless, after four hours the silver extraction in either 0.59 or 1
Ag2Te/FeS2 mass ratios were inhibited and did not reach more than 96 %.
An accurate understanding of the kinetics of precious metals dissolution from tellurides is required
to interpret the complex behaviour of leaching reactors, and to the process development for
refractory gold/silver concentrates. Nevertheless, further investigation is needed.
ACKNOWLEDGEMENTS
The authors are grateful to CONACYT (Mexico) for the postgraduate scholarship awarded to
González-Ibarra, and for the research project CB2015/257115.
REFERENCES
Aguayo, S., Pérez, E. & Encinas, M.A. (1996) ‘Recursos y alternativas de tratamientos para los
minerales de teluro de Sonora (México)’, Revista de Metalurgia, vol. 32, no. 1, pp. 33-39.
Cornwall, W.G. & Hisshion, R.J. (1976) ‘Leaching of telluride concentrates for gold, silver and
tellurium – Emperor process’, Transactions of the Society of Mining Engineering of AIME, vol. 260, pp.
108-112.
Dai, X. & Jeffrey, M.I. (2006) ‘The effect of sulfide minerals on the leaching of gold in aerated
cyanide solutions’, Hydrometallurgy, vol. 82, no. 3, pp. 118-125.
7
Dai, X. & Breuer, P.L. (2013) ‘Leaching and electrochemistry of gold, silver and gold-silver alloys in
cyanide solutions: effect of oxidant and lead(II) ions’, Hydrometallurgy, vol. 133, pp. 139-148.
Deschenes, G., Lastra, R., Brown, J.R., Jin, S., May, O. & Ghali, E. (2010) ‘Effect of lead nitrate on
cyanidation of gold ores: progress on the study of mechanisms’, Minerals Engineering, vol. 13, no. 12,
pp. 1263-1279.
Habashi, F. (1967) ‘Kinetics and mechanism of gold and silver dissolution in cyanide solutions’, Montana
College of Minerals Science and Technology.
Henley, K.J., Clarke, N.C. & Sauter, P. (2001) ‘Evaluation of a diagnostic leaching technique for gold
in native gold and gold±silver tellurides’, Minerals Engineering, vol. 4, no. 1, pp. 1-12.
Jackman, I.R. & Sarbutt, K. (1990) ‘The recovery of gold from a telluride concentrate’, Proceedings of
Randol Gold Forum ’90, Randol International Inc., Golden, Colorado, pp. 55-60.
Jayasekera, S., Ritchie, I.M. & Avraamides, J. (1988) ‘Electrochemical aspects of leaching gold
telluride’, Proceedings of the Randol International Gold Conference, Randol International Inc., Golden,
Colorado, pp. 187-189.
Jayasekera, S., Ritchie, I.M. & Avraamides, J. (1991) ‘Prospects for the direct leaching of gold
tellurides – recent developments’, Proceedings of World Gold ’91, The Australasian Institute of Mining
and Metallurgy, Melbourne, pp. 181-183.
La Brooy, S.R., Linge, H.G. & Walker G.S. (1994) ‘Review of gold extraction from ores’, Minerals
Engineering, vol. 7, no. 10, pp 1213-1241.
Liddell, K.S. & Dunne, R.C. (1988) ‘Ultra-fine grinding effect on leach recovery from refractorie gold
ores’, Proceedings of the Randol International Gold Conference, Randol International Inc., Golden,
Colorado, pp. 120-122.
Lu, Z. & Lawson, F. (1994) ‘Metallurgical properties of synthetic sylvanite’, The AusIMM proceedings,
vol. 299, no. 2, pp. 89-93.
Marsden, J. & House, I. (2006) The chemistry of gold extraction, 2nd edn, Society for Mining,
Metallurgy, and Exploration, Inc., Littleton, Colorado, USA.
Padmanaban, V. & Lawson, F. (1991) ‘Metallurgical properties of synthetic calaverite’, The AusIMM
proceedings, vol. 296, no. 1, pp. 31-37.
Sandenbergh, R.F. & Miller, J.D. (2001) ‘Catalysis of the leaching of gold in cyanide solutions by
lead, bismuth and thallium’, Minerals Engineering, vol. 14, no. 11, pp. 1379-1386.
Sayiner, B. (2014) ‘Influence of lead nitrate on cyanide leaching of gold and silver from Turkish gold
ores’, Physicochemical Problems of Mineral Processing, vol. 20, no. 2, pp. 507-514.
Senanayake, G. (2006) ‘The cyanidation of silver metal: review of kinetics and reaction mechanism’,
Hydrometallurgy, vol. 81, no. 2, pp. 75-85.
Zhang, Y., Fang, Z. & Muhammed, M. (1997) ‘On the solution chemistry of cyanidation of gold and
silver bearing sulphide ores. A critical evaluation of the thermodynamic calculations’,
Hydrometallurgy, vol. 46, no. 3, pp. 251-269.
Zhang, J., Zhang, Y., Richmond, W. & Wang, H. (2010) ‘Processing technologies for gold-telluride
ores’, International Journal of Minerals, Metallurgy and Materials, vol. 17, no. 1, pp. 1-10.
8
9
Leaching of Auriferous Minerals with Hypochlorite
Salts and Recovery with Activated Carbon -
Polydopamine Composite
David Meza, Juan Benavides, Ernesto de la Torre and Alicia Guevara
DEMEX, Escuela Politécnica Nacional, Ecuador
ABSTRACT
In Ecuador, there are auriferous minerals with presence of free gold and refractory gold associated
with sulfide-arsenides, which tend to be treated by gravimetric concentration, amalgamation and
cyanidation. Refractory ores, are oxidized by roasting with SO 2 and SO3 generation, causing
environmental damage. It was proposed an aqueous oxidation-leaching of these minerals. For this
reason, the influence of the concentration of sodium hypochlorite (NaClO) or calcium hypochlorite
salts (Ca(ClO)2), and the influence of the concentration of sodium chloride (NaCl), were studied.
The CA-PDA obtained was tested by ion adsorption tests [AuCl4] - (pH = 2, Temperature = 18 °C,
time = 24 hours, 10 mg dm-3). The adsorption behavior was fitted to a Freundlich isotherm. A
mineral that has 15 g/t of gold associated with silicates (QAu) and a mineral with 62 g/t of gold
associated with sulfide-arsenides (CFr) was studied in this process. It was possible to find that the
recovery of gold in solution increases with the concentration of NaClO, Ca(ClO)2 and NaCl. Gold
recoveries were achieved 61.1 % solution in QAu mineral and 17.9 % with CFr mineral, using 30 g/L
NaClO and 150 g/L NaCl. When assessing the temperature in leaching processes, it was found that
this increases the recovery of dissolved gold, so, the recovery of gold in solution increased from
61.6 to 98.8 % with QAu mineral. Leaching in three stages found a 95.7 % of recover the gold in
solution. The pristine activated carbon and CA-PDA samples showed an adsorption capacity
constant for ions [AuCl4]- of 43.3 mg Au∙g-1 CA and 118.9 mg Au∙g-1 CA-PDA
1
INTRODUCTION
Ecuadorian minerals usually contain free gold and gold associated with
sulfides-arsenides that give them refractory characteristics to direct cyanidation (De la Torre and
Guevara, 2005). An indirectly chlorination has been proposed using hypochlorite salts in acid
media to generate chlorine in-situ, that reacts with the free gold of the minerals, and form the auric
chloride species [AuCl4]-, this process is indicated by Equations (1) and (2) (Viñals et al., 1995):
ClO− (aq) + Cl− (aq) + 2HCl(aq) → 2Cl− (aq) + Cl2 (g) + H2 O(l) (1)
3
Au(s) + Cl− (aq) + Cl2 (g) → [AuCl4 ]−
(aq) (2)
2
In refractory gold minerals, the in-situ chlorine solution can’t react with gold in the mineral, because
it is not free by the presence of sulfides-arsenides (Curreli et al., 2005). The formation of
hypochlorous acid (HClO) using hypochlorite salts has been proposed (Jeffrey et al., 2001). The
formation of HClO can be observed in Equation (3) (Snoeyink and Jenkins, 1980).
ClO− (𝑎𝑞) + H + (𝑎𝑞) → HClO(𝑎𝑞) (3)
The process of oxidation of sulfides-arsenides is shown in Equations (4) and (5) (Hasab et al., 2013):
4
2FeS2 (𝑠) + 15HClO(𝑎𝑞) + 7H2 O(𝑎𝑞) → 2Fe(OH)3 (𝑠) + 4SO2− − +

4 (𝑎𝑞) + 15Cl (𝑎𝑞) + 23H (𝑎𝑞) (4)
2FeAsS(𝑠) + 11HClO(𝑎𝑞) + 11H2 O(𝑎𝑞) → 2Fe(OH)3 (𝑠) + 2SO2− 3− − +
4 (𝑎𝑞) + 2AsO4 (𝑎𝑞) + 11Cl (𝑎𝑞) + 27H (𝑎𝑞) (5)
Once the sulfides-arsenides are oxidized, HClO in the presence of other acids, becomes a leaching
agent like chlorine, as indicated by Equation (6) (Behnajady and Moghaddam, 2011):
2Au(𝑠) + 3HClO(𝑎𝑞) + 3H + (𝑎𝑞) + 5Cl− (𝑎𝑞) → 2(AuCl4 )− (𝑎𝑞) + 3H2 O(𝑎𝑞) (6)
In other way, it is known that polydopamine is a non-toxic bio-polymer which is easily obtained
(Yan, Yang, Lin, Ma, Lu and Lee, 2013, Liebscher et al., 2013). This polymer can provide catechol
and amine functional groups which act as active sites, facilitating the formation of coordination
bonds with ions such as [AuCl 4]- (Dreyer, Miller, Freeman, Paul and Bielawski, 2012; Hong et al.,
2014). This project aims to evaluate the influence of salts of sodium hypochlorite and calcium
hypochlorite on the gold dissolution of gold ores. The behavior of two minerals with different
characteristics: one with gold associated with silicates and quartz (QAu), and other one with gold
associated with pyrite and arsenopyrite (CFr), was studied. In addition, the adsorption
performance of [AuCl4]- with activated carbon (AC) was evaluated by impregnation of a non-toxic
and biodegradable polymer such as polydopamine (PDA).
2
METHODOLOGY
Characterization
The behavior of two Ecuadorian minerals was studied: a) mineral that presents gold associated
with silicates (QAu), and b) flotation auriferous concentrates, refractory to cyanidation (CFr).
The elemental chemical composition was determined by analyzing the contents of Au, Ag, Cu, Pb,
Zn, Ca, Mg, Na, K, Al, Co, As, cyanuric Au and the amount of Au amalgams. The samples were
analyzed by the atomic absorption spectrophotometry technique using the Perkin Elmer A. Analyst
300 equipment. To know the mineralogical compositions: qualitative and semi-quantitative of the
mineral CFr, X-ray diffraction analysis was performed using a Bruker D8 Advance diffractometer.
Lixiviation
Using both minerals reduced to d80=30 μm, stirred leaching tests were performed using NaClO
solutions: 10, 20 and 30 g/L; NaCl: 75 and 150 g/L and as regulator of pH
HCl: 100 g/L. (Filcenco-Olteanu et al., 2010). The leaching conditions that showed the highest
recovery of gold in each mineral were considered to perform leaching at controlled temperature
using a thermostatic bath at 50 °C with agitated reactors covered with parafilm plastic (Radulescu
et al., 2008). Based on studies by Hasab et al. (2013), the influence of Ca(ClO)2 was evaluated by a
three-stage process. Leaching was performed using Ca(ClO)2 (200, 100, 50 g/L of Ca(ClO)2 and
NaCl 75g/L). Acid washes were performed at the end of each leaching step with HCl: 40 g/L).
Adsorbing
Solutions of 10 mg dm-3 of ions [AuCl4]- were prepared. In 5 erlenmeyers were placed
0.10 g of CA, which were contacted with 100 cm 3 of ion solution, subjected to constant magnetic
stirring for 15, 30 minutes, 1, 2 and 3 hours. After the time, the solutions were filtered and the
adsorbent was recovered. This procedure is repeated with the CA-PDA composite. The filtered
solution was analyzed by atomic absorption (Soleimani et al., 2008).
Characterization
Table 1 shows that the amounts of cyanuric gold and gold amalgams present values close to the
value of gold content in the mineral in QAu mineral. In CFr mineral these values are far from the
value of the amount of gold present in the mineral, which proves the refractory behavior of the
CFr mineral. The elements such as: Cu, Pb, Zn, Ca, Mg, Na, K, Al and Co, present insignificant
percentages in the two samples. In CFr mineral, the As presents an amount of 13.81%, this element
forms the sulfides-arsenides involved in the refractory characteristics of the CFr mineral.
3
Table 1 Elemental chemical composition of both minerals
Elements Fe Cu Na K As Ag Au Cyanuric gold Gold amalgams

(%) (%) (%) (%) (%) (g/t) (g/t) (g/t) (g/t)
QAu 0.89 0.05 2.58 0.95 <0.01 25.98 15.54 14.54 7.65
CFr 18.18 0.20 <0.01 <0,01 13.81 102.37 62,46 4.06 3.5
In Table 2, it is evident that, QAu mineral presents a low number of sulfides, it contains 1% of
pyrite, and in its greater proportion it presents quartz 75%. In CFr mineral, the greater mineral
percentage are occupied by the sulfides-arsenides with 35% of pyrite and 30% of arsenopyrite.
These minerals are the possible cause of the refractory behavior in CFr mineral.
Table 2 Mineralogical composition of minerals QAu and CFr
Mineral QAu (%) Mineral CFr (%)

Quartz SiO₂ 75 22
Kaolinite Al₂(Si₂O₅)(OH)₄ 12 5
Poligoskita (MgAl)₅(Si,Al)₈O₂₀(OH)₂.8H₂O 5 <1
Muscovite KAl₂(AlSi₃O₁₀)(OH)₈ 5 <1
Pyrite FeS2 1 35
Arsenopyrite FeAsS <1 30
Chalcopyrite CuFeS2 <1 2
Pyrrhotine Fe(1-x)S <1 3
Figure 1 shows the microscopic view of CFr mineral, that shows the sulfides-arsenides present in
the mineral and the gold (o) associated with arsenopyrite (y), pyrite (x) and the silicate gangue (z).
Figure 1 Photograph of polished sections of CFr mineral

A Gold included in silicate gangue (55 and 15 μm)
B Gold included in arsenopyrite (7 μm)
X pyrite, Y arsenopyrite, z ganga and O gold
(Guevara, 2001)
4
Lixiviation
Figure 2 shows that, the best gold recoveries in solution were obtained with 30 g/L of NaClO, they
were: 61.6% in the QAu mineral and 17.9% in CFr mineral. The pH value in the two minerals was
less than 3.5. The difference of the percentages of recovery of gold in solution, is due to the
mineralogical differences previously shown in Table 2.
100 100
Mineral QAu
QAu Mineral Mineral CFr
CFr Mineral Mineral QAu
QAu Mineral Mineral CFr
Au Recorvery in Solution (%)

CFr Mineral
80 80
60 60
40 40
20
A 20
B
0 0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
[NaClO] (g/L) [NaClO] (g/L)
Figure 2 Gold recovery in solution, as a function of NaClO concentration (T = 20 °C, solids % = 16.6,
d80 = 30 μm, pH < 3.5, and time = 24 hours)
A [NaCl] = 75 g/L and [HCl] = 40 g/L; B [NaCl] = 150 g/L and [HCl] = 40 g/L
Leaching process at room temperature of 20 °C and at 50 °C, as shown in Figure 3. The increase in
leaching temperature for the QAu mineral increases the recovery of gold in solution from 61.6 to
98.8%, even though, the increase was obtained from 17.9 to 28.8% in CFr mineral
100
80
Mineral QAu (T=(T=

QAu Mineral 20ºC)
20 °C)
60
Mineral CFr (T=(T=
CFr Mineral 20ºC)
20 °C)
40
Mineral QAu (T=(T=
QAu Mineral 50 ºC)
50 °C)
20
Mineral CFr (T=(T=
CFr Mineral 50ºC)
50 °C)
0
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (hours)
Figure 3 Gold recovery in solution, as a function of time, using NaClO as a leaching agent
(Solids %= 16.6, d80= 30 μm, t= 24 hours, [NaClO] = 30 g/L; [NaCl] = 150 g/L)
Considering the tests performed by Hasab (2013), 3-stage leaching was used in both. The
three-stage leaching tests, using Ca(ClO)2 in QAu mineral reached 84.2% gold recovery in solution,
5
as shown in figure 4A. With the CFr mineral, was obtained 95.8% of recovery gold in solution
(figure 4B).
100 100 Stage 3
Stage 1 Stage 2 Stage 3 Stage 1 Stage 2
80
A 80
B

Acid wash
[HCl]=40 g/L
60 60
Acid wash
[HCl]=40 g/L
40 Etapa 2: 40
Acid wash [Ca(ClO)2]=100
[HCl]=40 g/L g/L; [NaCl]=75
Acid wash
g/L [HCl]=40 g/L
20 Etapa 3: 20
[Ca(ClO)2]=50
g/L; [NaCl]=75
g/L
0
0
0 2 4 6 8 10 12 14 16 18 20 22 24
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (hours) Time (hours)
Figure 4 Gold recovery in solution, as a function of time, using Ca(ClO)2 as a leaching agent (3 stages)
A Three stages leaching QAu mineral (T = 20 °C, solids %= 16.6, d80 = 30 μm, pH = 4.0 and time= 24 hours)
B Three stages leaching with CFr mineral (T = 20 °C, solids %= 16.6, d80 = 30 μm, pH = 4.0 and time= 24 hours)
The acid washes with 40 g/L HCl increases recovery at each stage. The iron hydroxide (Fe(OH)3),
formed in Equations (4) and (5), which usually interferes with the dissolution of gold in acid
leaching (Equation 7), was dissolved by washing the tailings with HCl, and under the working
conditions, the soluble complex ferric chloride (FeCl+
2 ), was formed (Havlík, 2008).
Fe(OH)3 (𝑠) + 3HCl(𝑎𝑞) → FeCl+ −

2 (𝑎𝑞) + Cl (𝑎𝑞) + 3H2 O(𝑎𝑞) (7)
The oxidation process of the mineral CFr is shown in Table 3, where the mineralogical analysis
performed at the tailings of each leaching stage indicates the reduction of pyrite and arsenopyrite.
Table 3 Mineralogical composition of tailings obtained by 3-stage leaching in the refractory

mineral
Mineral CFr Tailings Leaching Tailings Leaching Tailings Leaching

Stage 1 Stage 2 Stage 3
(%) (%) (%) (%)
Quartz SiO₂ 22 14 13 9
Kaolinite Al₂(Si₂O₅)(OH)₄ 5 4 4 4
Halite NaCl 0 0 12 2
Gypsum CaSO4 2H2O 0 38 37 76
Pyrite FeS2 35 25 16 2
Arsenopyrite FeAsS 30 15 14 3
Chalcopyrite CuFeS2 2 2 2 2
Pyrrhotine Fe(1-x)S 3 0 0 0
6
Comparison with gold recovery reference methods
In Figure 5, a comparison of the best results obtained for the two minerals studied with the direct
cyanidation method is presented. In QAu mineral, the leaching technique with [NaClO]=30 g/L,
NaCl] = 150 g/L, and at 50 °C, is more efficient than cyanidation, achieving a gold recovery in
solution of 98.8%. In a 3-stage leach using CFr mineral, 95.8% of the total recovery of gold in
solution was achieved.
100
Stage 1 Stage 2 Stage 3
NaClO leaching at 50 °C
80 Lixiviación con NaClO a 50
(QAu mineral)
ºC (mineral QAu)
3-stage leaching with
60 Lixiviación en 3 mineral)
Ca(ClO)2 (CFr etapas con
Ca(ClO)2 (mineral CFr)
Acid Wash Direct cyanidation
[HCl]=40 g/L Cianuración directa (QAu)
(QAu mineral)
40
Direct cyanidation
Cianuración directa (mineral
20 Acid wash (CFr mineral)
CFr)
[HCl]=40 g/L
Roastingyand
Tostación direct
Cianuración
0 directa (mineral(CFr
cyanidation CFr)
mineral)
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (hours)
Figure 5 Comparison of the different Au leaching methods with minerals QAu and CFr
(solid% = 16.66, d80= 30 μm and time = 24 hours)
Adsorbing
Table 4 shows that there is an improvement in the adsorption for the composite with a degree of
impregnation of PDA of 2.8%. These results were analyzed using the Freundlich model where Kf is
the adsorption capacity constant and is related to the adsorbent affinity for the adsorbate, and n is
the adsorption intensity constant (Hong et al., 2014). Compared to the virgin CA, the composite
CA-2.8% PDA has an adsorption capacity constant of 118.9 mg Au g-1 CA-2.8% PDA, which is 174%
higher than corresponding to the virgin carbon (43.3 mg Au g-1 CA).
Table 4 Parameters of the Freundlich adsorption isotherm for the virgin activated carbon and the
CA-PDA composite at different percentages of impregnation
Sample Freundlich model

[AuCl4]-
kf (mg g-1) n
Virgin Carbon 43.3 0.6
CA-2.8%PDA 118.9 0.5
*Ion [AuCl4]- adsorption tests (Contact time = 24 hours, pH = 2.0, temperature = 18 °C and ORP = 900 mV);
7
This increase in affinity for ions [AuCl4]- is attributed to the electrostatic interaction with the amino
functional groups and to the chelation ability of the catechol groups of the PDA in the composite.
The possible mechanism for ions [AuCl4]- adsorption on polydopamine is presented in figure 6.
Figure 6 Possible mechanism for ions [AuCl4]- adsorption on polydopamine (Hong et al., 2014)
CONCLUSION
The concentrations of the hypochlorite salts affect the gold recovery in solution of the minerals,
because as the concentrations of hypochlorite salts increased, the recoveries of dissolved gold
increased. The concentration of NaCl is not influential in the gold dilution process.
Using NaClO, the temperature is a determining factor when increasing the recoveries of gold in
solution. At room temperature, the recovery of dissolved gold was 61.6% using [NaClO]= 30 g/L;
[NaCl = 150 g/L with the mineral with QAu, while a temperature of 50 °C and under the same
conditions achieved a recovery of 98.8%.
When increasing the temperature from 20 to 50 °C, in the leaching tests with [NaClO]= 30 g/L;
[NaCl]= 150 g/L using the CFr mineral, the recovery of gold in solution only increased from
17.8 to 28.8%, this occurred due to the presence of sulfides-arsenides that don’t allow the total
liberation of the gold with these chemical agents.
The three-stage leaching applied to the minerals QAu and CFr achieves a good gold recovery in
solution between 80 and 95%, however, the best recovery for the QAu mineral (98.8%), is obtained
with the test at 50 °C using sodium hypochlorite.
The CA-PDA composite has better adsorbent properties at impregnation values of 2.8 and 4.9%, at
higher values a matrix saturation occurs.
The adsorption capacity constants for [AuCl4]- of (CA) and (CA-PDA) were 43.3 mg Au g-1 CA and
118,9 mg Au g-1 CA-PDA respectively, indicating a higher affinity of the ions by the composite.
8
REFERENCES
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journal of mineral processing, 82(4), 178-186.
Behnajady, B., & Moghaddam, J. (2011). Chloride leaching of lead and silver from refractory zinc
plant residue. Research Journal of Chemistry and Environment, 15(2), 473-480.
Curreli, L., Ghiani, M., Surracco, M., & Orrù, G. (2005). Beneficiation of a gold bearing enargite ore by
flotation and As leaching with Na-hypochlorite. Minerals Engineering. 18(8), 849-854.
De la Torre, E., & Guevara, A. (2005). Recuperación de oro a partir de minerales refractarios
polisulfurados. Quito, Ecuador. Escuela Politécnica Nacional.
Dreyer, D., Miller, D., Freeman, B., Paul, D., & Bielawski, Ch. (2012). Elucidating the Structure of
Poly(dopamine), Langmuir, 28(15), 6428-6435.
Filcenco-Olteanu, A., Dobre, T., Panturu, E., Radulescu, R., y Groza, N. (2010). Recovery of Gold from
Alluvial Sand by Wet Chlorination. Revista de Chimie, 61(2), 223–226
Guevara, A. (2001). Étude minéralogique des minerais équatoriens dór réfractaires et des produits de leurs
traitements minéralurgiques et métallurgiques. (Proyecto previo a la obtención de diplomado en geología).
Université Catholique de Louvain
Hasab, M., Rashchi, F., & Raygan, S. (2013). Kinetic studies for gold leaching of a refractory sulfide
concentrate by chloride-hypochlorite solution. Iranian Journal of Materials Science and Engineering, 11(2),
37–47. http://ijmse.iust.ac.ir/files/site1/user_files_4qu804/eng/tavakoli-A-10-127-05d0e392.pdf
(Junio, 2016).
Hasab, M., Rashchi, F., & Raygan, S. (2014). Chloride-hypochlorite leaching and hydrochloric acid
washing in multi-stages for extraction of gold from a refractory concentrate. Hydrometallurgy, 142(1), 56-59.
Havlík, T. (2008). Hidrometalurgy: Principles and Applications. Cambridge, England.
Hong, G., Shen, L., Wang, M., Yang, Y., Wang, X., Zhu, M., & Hsiao, B. (2014). Nanofibrous
polydopamine complex membranes for adsorption of Lanthanum (III) ions, Chemical Engineering
Journal, 244(1), 307-316.
Jeffrey, M., Breuer, P., & Choo, W. (2001). A kinetic study that compares the leaching of gold in the
cyanide, thiosulfate, and chloride systems. Metallurgical and materials transactions B, 32(6), 976-986.
Liebscher, J., Mrówczynski, R., Scheidt, H., Filip, C., Hadade, D., Turcu, R., Bende, A., & Beck, S.
(2013), The Structure of Polydopamine – a Never Ending Story?, Langmuir, 29(33), 10539-10548.
Radulescu, R., Filcenco-Olteanu, A., Panţuru, E., & Grigoraş, L. (2008). New Hydrometallurgical
Process for Gold Recovery. Chem Bull Politehnica Universitãtii (Timişoara), 53(67), 135–139.
Snoeyink, V., & Jenkins, D. (1980). Water Chemistry. (2da. Ed.). Michigan, Estados Unidos: Wiley.
Soleimani, M., & Kaghazchi, T. (2008). Adsorption of gold ions from industrial waste water using
activated carbon derived from hard shell of apricot stones – An agricultural waste, Bioresource
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Viñals, J., Núñez, C., & Herreros, O. (1995). Kinetics of The Aqueous Chlorination of Gold in Suspended
Particles. Hydrometallurgy, 38(2), 125–147
Yan, J., Yang, L., Lin, M., Ma, J., Lu, X., & Lee. (2013). Polydopamine Spheres as Active Templates
for Convenient Synthesis of Various Nanostructures, Small, 9(4), 596-603.
9
An effective New Leaching Aid Successfully Tested
with Copper Ores
Jack Bender
BASF Corporation, USA
ABSTRACT
Solvent extraction compatibility testing of a large set of potential leaching aids was used to identify
the pool of compounds for testing. Small-scale bench columns were used to select two compounds
for the larger scale columns. The ore was a mostly copper oxide ore that had a P100 of 2” with a P80
of 1.5” and a smallest fraction of -10 mesh. Approximately 90 kg of the agglomerated ore was leached
for 60-120 days in batches of 16 columns, at which point roughly 75% of the total copper was leached.
The lead leaching aid candidate achieved a 15-20% increase in copper recovery over columns without
leaching aids with an overall standard deviation of less than 1% for the data between columns. The
low standard deviation in the results was due to the meticulous control of acid concentration,
lixiviant flow, and distribution of lixiviant. In addition to the oxide ore, a customer mixed sulfide ore
has been leached with similar results. In addition to the column testing, the leaching aids were
subjected to bacteriological compatibility testing to ensure no adverse effect to the existing
microorganisms in the ore. Biocompatibility was determined for various sulphur and iron oxidizing
bacteria. Results of the testing showed little if any negative effect on the microorganisms. Surface-
active surfactant type leaching aids tend to have a negative effect on solvent extraction and can have
a negative effect on the electrowinning system. Leaching aid solvent extraction compatibility was
accomplished by dosing leaching solutions with the leaching aids and then performing
extraction/stripping kinetics, selectivity, phase disengagement, loading and organic solubility
testing. The leaching aids have also been tested in electrowinning systems with copper having been
plated from the solutions. In conclusion, the increase of copper leach recovery and the low toxicity of
these compounds to SX-EW will be discussed.
1
INTRODUCTION
The initial details of the leaching aid work were presented at Copper 2016 (Bender et al., 2016). The
article included the initial testing results, biocompatibility results, toxicity details and the initial
solvent extraction compatibility work. At the time, the results for the leaching aids were slightly
better than the results for the control columns. Further work defined more optimal chemistry and
dosage for the original oxide ore. In addition, work was conducted on a mixed sulphide copper ore
from a customer. The results of the later trials were dramatically improved from the initial results.
The solvent extraction compatibility is of great importance to customers (Kordosky and Virnig, 2007).
Leaching aids are not removed from the PLS before SX or EW processes. In general, these compounds
are meant to lower surface tension in the aqueous which can cause an increase in coalescence and
phase separation times. The increase in contact time between the PLS and the solvent extraction
organic can lead to increased entrainment losses, poor transfer kinetics, hydrolytic degradation of the
extractant, and/or nitration of the extractant if conditions are suitable. Poor transfer kinetics can be a
result of the interfacial activity of the leaching aid. If the chemical compound is attracted to the
organic-aqueous interface it can inhibit the transfer of copper and ultimately this can affect the net
transfer of copper to the electrolyte. While much of the lab phase work is completed at this stage,
there is still an investigation into conditions of interest. Particularly the effect of chloride and nitrate
ions on the lixiviant. The results of this ongoing work will be presented in future articles.
EXPERIMENTAL
Column Testing
To reduce the variables in the leaching tests, the ore was precisely classified by SGS in Tucson, AZ.
The ore was a mostly copper oxide ore that had a P80 of 1.5” and a smallest fraction of -10 mesh. The
distribution of the column charge can be found in Table 1. The copper concentration in the ore was
0.42% with 91.2% of the copper as acid soluble copper. Analysis of the ore was also verified by SGS
in Tucson. Approximately 90 kg of the agglomerated ore was leached for 60 days in batches of 16
columns, at which point roughly 75% of the total copper was leached (total copper on column was
approximately 380 g). Agglomeration was accomplished by mixing the various fractions in a cement
mixer with 1.75 kg of water and 1.52 kg of sulfuric acid. The acid was calculated as 25% of the total
acid consumption by ore. The agglomerated material was then transferred to columns for the
leaching trials.
Sixteen PVC columns of 2 m high and 20 cm of diameter were used to hold the 90 kg of ore. A
distribution felt was used to evenly dispense the lixiviant solution onto the ore. Four of the columns
were constructed of clear PVC so that the system could be visibly inspected. Each column had its
own high precision pump and lixiviant reservoir. Solution was collected from the bottom of the
column into buckets which eventually were put into analytical balances so that the amount of
solution could be easily tracked. The leach rate was 8 mL/min of 10 g/L sulfuric acid at 21 °C.
Samples were collected daily for the first 30 days of the 60 day leaching trials. For each column, a
sample was analysed for pH, free acid, copper concentration by atomic absorption (AA), surface
tension, and oxidation potential (ORP). The lixiviant samples were also analysed each day to ensure
that there was no contamination or change in concentration of chemical species. The solution feed
2
rates were measured every day and if any adjustments were needed, the appropriate changes were
made.
Figure 1 Ore classification, agglomeration, and column testing for leaching aid experiments
Table 1 Distribution particles sizes of copper ore in leach tests (Crush Size P80 of 37.5 mm (1.5
inch)
Particle Size Sample Wt

mm inch (kg) (%)
37.5 1½ 18.0 20.0
25.0 1 32.0 35.5
19.0 ¾ 9.3 10.3
12.5 ½ 7.7 8.6
6.3 ¼ 7.4 8.2
1.7 N°12 8.1 9.0
minus 7.6 8.4
3
Chemical Compatibility
Lab circuits were set up with individual surge tanks. Each surge tank was filled with 500 mL of 10%
v/v LIX984N that has been contacted once with O:A 1:1 QC electrolyte (160 g/L sulfuric acid and 35
g/L copper). Flow rates were 30 mL/min of organic and 30 mL/min of aqueous. Mixer speed was kept
at 1750 rpm. Circuit operation was performed at room temperature, which was approximately 21 ºC.
The feed solution was a mine site PLS. The lab circuits were run with continuous mixing. Visual
observation during and at the end of the run showed no increase in emulsion or crud. The starting
organic and the three organics after continuous circuit testing were put through a standard kinetics
test. Phase disengagement testing (PDT) was performed as per the BASF technical service process.
Leaching aid concentrations for the PDT were tested in great excess to determine onset of critical
micelle concentration.
Chemical Compatibility
There has not been a significant effect on phase disengagement when using the leaching aid in the
appropriate dosage, which is approximately 25 ppm. At doses up to 4 times the operating dosage,
the PDT are within the error of the experimental method. At extremely high concentrations, 10 times
dosage, there is an effect on the aqueous continuous phase disengagement, although it is still not a
dramatic effect. Since the volumes of lixiviant are so large in leaching systems, it is extremely difficult
to add multiple quantities of the desired dosage.
Figure 2 Phase disengagement testing for an overdose of leaching aid
Chemical compatibility was first tested using a batch test method in jacketed beakers as per BASF
QC testing procedures. The testing was performed with up to 50 ppm leaching aid concentration,
which would be twice the normal operating concentration. There was no negative effect on extraction
kinetics, strip kinetics or phase disengagement time.
4
Table 2 Solvent extraction compatibility for a batch test using leaching aids versus a batch test
control
Barren Phase separation

Reaction Conditions Assay
Organic E30 E300 S30 S300 O, A (s)
Copper (g/L) 1.42 4.72 4.75 1.64 1.63 75, 95
Blank
% equilibrium 98.30% 99.04%
Copper (g/L) 1.43 4.69 4.73 1.64 1.63 80, 85
20 ppm leaching aid
Copper (g/L) 1.42 4.69 4.72 1.65 1.63 75, 95
50 ppm leaching aid
A continuous circuit was operated in order to determine if there was an effect on the kinetics of
extraction or stripping when operating with a low concentration of leaching aid. Results can be found
in Table 3. While the test operated at slightly lower than the 25 ppm eventually determined to be the
most optimal leaching aid concentration, the 15 ppm concentration of leaching aid had no effect on
extraction kinetics, strip kinetics or phase disengagement time. Test conditions were using a
1Ex1Ex1S configuration, 10 v/v% LIX 984N, mine PLS and synthetic LE were used in the continuous
circuit.
Table 3 Solvent extraction compatibility for a continuous circuit operation using leaching aids
versus a continuous circuit control
Barren Phase separation

Reaction Conditions Assay
Organic E30 E300 S30 S300 O, A (s)
Copper (g/L) 1.45 4.69 4.77 1.67 1.64 60, 85
Fresh Organic
8 Hrs (w/o leaching Copper (g/L) 1.53 4.75 4.81 1,68 1.66 55, 90
aid) % equilibrium 98.75% 99.37%
40 Hrs (w/o leaching Copper (g/L) 1.53 40.73 4.78 1.67 1.64 40, 90
80 Hrs (w/o leaching Copper (g/L) 1.56 4.80 4.87 1.70 1.63 35, 90
Copper Leaching
Leaching of copper secondary sulfide and oxide ores is relatively straightforward. Whether leaching
a run of mine (ROM) or an agglomerated ore, a lixiviant is used to convert the copper minerals into
copper sulfate in solution. The process of converting copper oxide to copper sulfate can be considered
quite fast and does not need any secondary processes. For the conversion of secondary sulfides, it is
necessary to oxidize the copper, which is assisted by biological species. However, this also can be
considered a relatively fast process.
Over time, the lixiviant will come into contact with copper minerals through wetting of the surfaces
of the rock. For the wetting of the ore to be complete, the lixiviant has to have a surface tension low
enough that the aqueous can permeate completely. In addition, as the copper mineral is consumed
5
the copper sulfate in solution must have a surface tension low enough to allow the exchange of
aqueous solution between the bulk aqueous and the aqueous in the particles. It is not just important
for the lixiviant to reach the copper mineral, it is essential to transfer the solubilized copper sulfate to
the bulk PLS.
Each set of column trials consisted of 16 columns containing approximately 90 kg of ore as described
previously. Four columns were set aside as blanks and have no leaching aid added. For the leaching
aids, test conditions were run in quadruplicate. In Trials 5 and 6, there was approximately 381 g of
total copper in each column at 91.2% leachable copper, or ~347.5 g/column.
The column trials were run so that the lixiviant is in a closed loop circulation. In some cases, solvent
extraction was included to remove copper; however, this did not change the results and complicated
the operation of the leaching columns. In the case of the results in Figures 3-5, the lixiviant was
recycled into the columns (Figure 1). An attempt was made to determine if leaching aid was
consumed during the trial; however, no consumption was noticed in the 60-120 day trials.
Figures 3-5 illustrate the leaching of ore in two different ways. The first graph of each figure shows
the data from the control columns (each data point the sum of quadruplicate testing) versus the
columns with leaching aid (quadruplicate testing for each point) with respect to the copper leached
from the ore. Due to the care with which the ore was processed and the columns leached, the standard
deviation of the leaching results between columns was very low. In fact, the error bars are not
substantially large then the data points. The second graph in each figure shows the efficiency of the
leaching aid, and is plotted as the percent of copper leached in excess of the control for the same data
as in the first graph.
Results in Figure 3 are for Trial number 5. The goal of this trial was to determine if application of the
leaching aid, added after agglomeration, impacts leaching in a closed cycle trial. A wide range of
dosages were used in order to determine if the leaching aid concentration was essential to the
leaching rate. Solvent extraction was performed until copper in raffinate was an appropriate level.
The copper leached using the leaching aid was approximately 72% of the leachable copper for all
three sets of conditions while the copper leached from the blank was approximately 56%.
The results of this leaching data were achieved in 30 days. Dosage did not seem to affect the results
for these sets of conditions.
Figure 3 Graphs for the leaching of copper from ore containing 347.5 g leachable copper/column and the plot
of the percent of copper leached in excess of the control
6
Results in Figure 4 are for Trial number 6. The goal of this trial was to determine if application of the
leaching aid, added during agglomeration, impacts leaching in a closed cycle trial. To extract copper
from PLS, all the solutions for each set of conditions were collected into one drum per quadruplicate
testing after weighing each sample collection container individually. Solvent extraction was
performed until copper in raffinate was an appropriate level. The copper leached using the leaching
aid was approximately 73-80% of the leachable copper while the copper leached from the blank was
approximately 69%. While the results of the leaching were similar to Trial 5 after 30 days, the trial
was allowed to continue for a total of 60 days.
Figure 4 Graphs for the leaching of copper from ore containing 347.5 g leachable copper/column and the plot
of the percent of copper leached in excess of the control
A customer trial was performed for the following set of data. The customer has a mixed
primary/secondary sulphide ore. For the same 90 kg column charge, there was approximately 63
grams of acid leachable copper. The ore was processed in the same manner as the oxide ore. The leach
time was extended to 120 days due to the nature of the leaching process. All other leaching conditions
were kept the same as previous trails. It was noted that there was an initial shock of the bacteria, as
was seen in the biocompatibility data (Bender et al., 2016). This shock is short lived, 2 weeks, and
then results similar to the oxide trials were seen. Approximately 20% more copper was leached with
the leaching aid. At 120 days, approximately 60% of the copper was leached with the leaching aid as
opposed to 49% leached in the control.
7
Figure 5 Graphs for the leaching of copper from ore containing 63 g leachable copper/column and the plot of
the percent of copper leached in excess of the control
Overall the leaching of oxide and sulfide ores was dramatically increased with the addition of the
leaching aid. While the copper was leached faster, it is not possible in a relatively short range leaching
lab trial to determine the extent of copper leaching. Thus, it is not possible to claim the amount of
additional copper that will eventually be leached from the ore. Certainly, the rate at which copper is
leached will benefit the mine site regardless of the overall copper leached.
CONCLUSION
The leaching aid resulted in between a 15 to 20% increase in copper recovery over the columns
without leaching aids with an overall low standard deviation for the data. The low standard
deviation in the results was due to the meticulous control of acid concentration, lixiviant flow, and
distribution of lixiviant. In addition to the column testing, the leaching aids were subjected to
chemical compatibility testing to ensure that there are no negative effects on downstream processes.
Based on the results of the current column testing, BASF is moving forward with customer trials.
REFERENCES
Bender, J., Hight, L., Emmerich, N., Brewer, R. (2016) Leaching Aids for Dump and Heap Leach; SX
Compatibility, Biocompatibility, and Recycle of Lixiviant. Copper 2016.
Kordosky, G. and Virnig, M. (2007). Copper Leaching Aids – Compatibility with the copper SX
process. Copper, 2007.
8
Development of an Active Carbon: Polydopamine
Composite to Increase the Adsorption Capability of
Ions [AuCl4]¯ and Cu2+
Juan Benavides and Ernesto de la Torre
ABSTRACT
This work reported a method for the development of an activated carbon–polydopamine (AC-PDA)
composite. The effects of polidopamina (PDA) impregnation time (1-24 h), pH (7,5-11,5), ethanol
concentration (10-50 % w/w) and dopamine concentration (0,5-8 mg cm-3) were studied to determine
the best conditions of the impregnation process at lab scale. The AC-PDA obtained was tested by ion
adsorption tests [AuCl4]- (pH 2, T 18 °C, t 24 h, 10 mg dm-3) and Cu2+ (pH 5, T 18 °C, t 24 h,
10 mg dm-3). The adsorption behavior was fitted to a Freundlich isotherm. The pristine activated
carbon and AC-PDA samples showed an adsorption capacity constant for ions [AuCl 4]- of
43,3 mg Au∙g-1 AC and 118,9 mg Au∙g-1 AC-PDA, while for ions Cu2+ 1,1 mg Cu∙g-1 AC y
9,7 mg Cu∙g-1 AC-PDA. This increase in ions [AuCl4]- and Cu2+ affinity is attributed to the electrostatic
interaction with amino functional groups and the chelation ability of catecholic groups of the PDA
on the activated carbon. The composite was characterized with gravimetric analysis (GA), iodine
number, point of zero charge measurement (PZC), scanning electron microscope (MEB),
thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR), which reveal
a successful grafting of PDA onto activated carbon surface.
1
INTRODUCTION
Activated carbon (AC) is a material with diverse applications due to its surface properties and low
cost. It is considered an ecological and renewable product, widely used in water treatment to remove
organic and inorganic contaminants due to its large specific area, adsorption capacity and surface
reactivity (Guo et al., 2015). The adsorption capacity depends on some factors, such as: specific
surface, pore structure and size, functional groups and adsorbate affinity. The AC can be made from
raw materials such as wood, charcoal, petroleum coke, sawdust, coconut shell and palm kernel
(Park and Jang, 2002). The activation process determines the porous structure, surface chemistry and
physical properties. Therefore, different activation methods on the same raw material can produce
totally different characteristics in activated carbon (Guo et al., 2015, Li, Quinlivan and Knappe, 2002).
The chemical properties of activated carbon are determined to a high degree by the presence of hetero
atoms such as oxygen, nitrogen, hydrogen, sulfur and phosphorus (Maldonado, Morales, Pérez and
Carrasco, 2011). Generally, the carbon after the activation process has mostly oxygenated functional
groups, such as hydroxyl, carboxyl, phenol, lactone, and acid anhydrides (Li et al., 2002). The surface
modification of the AC by impregnation or chemical reaction is carried out to develop active sites or
functional groups, which change the adsorption and selectivity of a certain adsorbate present in a
liquid or gaseous phase (Laginhas, Valente and Titirici, 2016; Guo et al., 2015).
The amino functional groups as well as the hydroxyl functional groups have significant roles in the
field of heavy metal adsorption. The main reason is that the nitrogen atom belonging to the amino
functional group and oxygen belonging to the hydroxyl may be linked to a proton or a metal ion
respectively, following an electron exchange. Because the electronegativity of oxygen is greater than
that of nitrogen, it will be easier to donate a pair of electrons from the nitrogen atom than from the
oxygen in the process of forming a metal complex (Laginhas et al., 2016; Rashidi and Yusup, 2016).
Dopamine (DA) can adhere on many substrates because of its structure. It has functional groups such
as catechol and amino. The catechol group is susceptible to be oxidized to generate a
dopaminequinone structure as shown in Figure 1. This functional group is responsible for the
adhesion whereas in its oxidized form causes the crosslinking of the DA polymer. After the DA is
oxidized a nucleophilic reaction having the final product is 5,6-dihydroxyindole (DHI) (Ye, Zhou and
Liu, 2011; Hong et al., 2012). This new molecule forms covalent bonds with similar molecules, in
addition, of physical interactions with the molecule of DA. Macromolecules such as DHI-DHI dimer,
trimeric conjugate DA-DHI-DHI and trimer (DA)2/DHI together give rise to polydopamine (PDA)
(Hong et al., 2012).
2
Figure 1 Dopamine polymerization process: A) Oxidative polymerization with formation of covalent bonds
and B) Physical self-assembly between dopamine and 5,6-dihydroxindole (DHI)
(Hong, Na, Choi, Song, Kim y Lee, 2012)
PDA is a non-toxic bio-polymer that is easily obtained. The versatility of its functional groups gives
it the unique ability to adhere to almost any surface through hydrogen bonds, π-π aromatic
interactions and electrostatic interactions (Yan, Yang, Lin, Ma, Lu and Lee, 2013; Liebscher et al. 2013).
This polymer is able to provide catechol and amine functional groups which act as active sites,
facilitating the formation of coordination bonds with transition metal ions such as copper (II),
lanthanum (III), mercury (II) and [AuCl4]- as shown in Figure 2 (Dreyer, Miller, Freeman, Paul and
Bielawski, 2012; Hong et al., 2014). It is here that the interest of this work is focused since the yield of
the adsorption of organic and inorganic compounds of the AC can be improved by the impregnation
of a non-toxic and biodegradable polymer such as polydopamine.
3
METHODOLOGY
Conditioning of activated carbon

The activated carbon of palm kernel was subjected to a pre-cleaning treatment. 500 g AC were
washed 3 times with distilled water to remove fine material and any remaining reagents from the
manufacturing process. After washing, the sample was dried for 48 h at 110 °C to ensure removal of
the remaining water in the porous matrix (Yu et al., 2014).
DA polymerization
A 10 mM TRIS buffer solution was prepared, 200 mg DA was added in 100 cm3 of the buffer solution
and subjected to magnetic stirring for a time of 5 h until a PDA precipitate formed. The PDA was
separated from the solution with Whatman grade 2 filter paper with 8 μm pore size, washed with
distilled water and dried at 80 °C for 12 h (Ju et al., 2011). To estimate the size of the particles
constituting the PDA, an optical microscopy analysis was performed with an Olympus SZX16 device.
In addition, the decomposition temperature was determined by TGA analysis.
Impregnation of DA and polymerization in activated carbon

Samples of 4 g of pre-treated AC were immersed in a solution containing 2 mg cm-3 DA
(Zhang et al., 2014; Lee et al., 2007). This was done in a buffer solution for which 364 mg of TRIS was
dissolved in 100 cm3 of distilled water and the pH was adjusted to 8 using 5 % HCl. After the solution
was prepared, 400 mg of DA was added. Subsequently, the system was subjected to magnetic stirring
for a time of 3 to 24 h (Hong et al., 2014, Yu et al., 2014). The obtained AC-PDA composite was washed
3 times with distilled water and dried at 110 °C for 24 h.
To evaluate the effect of pH on the impregnation process, TRIS buffer solutions were prepared at
pH 7, 8, 9, 10 and 11.5. These tests were carried out under magnetic stirring conditions for a period
of 24 h (Yang et al., 2015, Yan, et al., 2013, Ball, Frari, Toniazzo and Ruch, 2012, Zhi and Liu, 2016).
To control the impregnation through the polymerization rate, the impregnation process was carried
out in media containing ethanol from 49.0 to 24.5 % (Yue et al., 2013, Yan et al., 2013, Hydari et al.,
2012, Ju, Lee, Lee, Park and Lee, 2011; Liu et al., 2014). At the concentrations of 0.5, 1, 2, 4, 6 and
8 mg cm-3 of DA, impregnation media were prepared to determine the influence of their concentration
on the process (Liu, Ai and Lu, 2014). The AC-PDA composites obtained from all these tests were
characterized by volatile content (ASTM-D3175), ash and fixed carbon (ASTM-D3174), iodine index
(NTE INEN Standard, 1988: 95) and gravimetric analysis.
Adsorption tests of ions [AuCl4]¯ y Cu+2

One liter of solution was prepared with a concentration of 10 mg dm -3 ions [AuCl4]¯
(Zhang et al., 2014). This solution was performed based on the characteristics of a Cl 2-HClO-HCl
leaching test (Hasab, Rashchi and Raygan, 2014). A mixture of 670 cm 3 of 21 % HCl, 194.8 cm3 of
distilled water, 125.2 cm3 of NaClO and 15 g of NaCl was made. To this solution was added 10 cm3
of a gold standard solution of 1000 mg dm-3. The pH of the solution was adjusted to 2, and the ORP
to 900 mV to ensure the stable presence of ions [AuCl4]¯ (Hasab et al., 2014).
4
A mass corresponding to 0.01; 0.10; 1 and 10 g of the AC were placed in four erlenmeyers;, which
were contacted with 100 cm3 of solution containing 10 mg dm-3 of [AuCl4]¯ ions under magnetic
stirring for 24 h. After the time, the adsorbent was filtered and recovered. The solution was analyzed
by atomic absorption with an A. Analyst 300 device to determine the gold concentration (Soleimani
and Kaghazchi, 2008). This procedure is repeated for the AC-PDA composite.
1 liter of 10 mg dm-3 Cu2+ solution was prepared by weighing 4 mg of CuSO4 and dissolving in 1 liter
with distilled water in a volumetric flask (Yu et al., 2014; Zhang et al. 2014). Subsequently, the
procedure described for adsorption isotherms of [AuCl4]¯ was repeated.
A preliminary study was carried out to evaluate the potential reuse of the AC-PDA composite. In the
case of desorption of [AuCl4]¯ , 1 g of adsorbent was contacted with a solution of 3 M HCl at room
temperature, pH 2 for 24 h magnetic stirring (Zhang, 2014; Soleimani et al., 2008). To evaluate the
adsorbent reuse capacity, consecutive adsorption-desorption cycles were repeated four times (Hong
et al., 2014; Dong, Zhang, Wang, Liu and Jin, 2014). In the case of Cu2+, desorption assays were
performed homologously and the HCL concentration was reduced to 0.1 M.

The PDA synthesis showed a total change in coloration of the polymerization medium characteristic
of dopamine oxidation after 5 h, a result consistent with previous studies (Ju et al., 2011; Zhang et al.,
2014). A dark brown suspension was obtained as the final product. Analysis by optical microscopy
determined that PDA aggregates formed have a diameter ranging from
8 to 50 μm. The TGA analysis performed in an inert atmosphere (N 2, 20 cm 3 min-1) shows that the
decomposition of the PDA starts at 220 °C and ends at 800 °C. In addition, a remnant of 37.2 % is
present in relation to the total weight, this suggests that the polydopamine can be carbonized under
an inert atmosphere. The results of the percentage of PDA impregnation on activated carbon as a
function of time are shown in Figure 2. The tests were carried out at the best polymerization
conditions reported by Yu et al., (2014).
10
8
Impregnation PDA (%)
0
0 10 20 30 40 50
Time(h)
Figure 2 Percentage of PDA impregnation on activated carbon as a function of time (pH 8.0 and concentration
DA 2.0 mg cm-3)
The percentage of impregnation as a function of time presents a maximum (2.8 %) at 12 h after the
process was started, after which there is no significant increase. The resulting impregnation yield is
5
only 31.9 %, this is due to the formation of PDA aggregates large enough to block AC pores and
prevent the entry of smaller PDA macromolecules (Ball et al., 2012). It is important to note that
68.1 % of the DA monomer is in the waste solution. Figure 3 shows the effect of pH on PDA
impregnation and its relation with iodine number. The pH acts as the initiator of the polymerization
process, but this becomes even more relevant because of the surface reactivity of the AC (Lee et al.,
2007; Li et al., 2002).
10 750
Iodine Index (mg I2/g AC)

8
740
6
730
4
720
2
0 710
7 9 11 13 0 1 2 3 4 5
A) pH B) Impregnation PDA (%)
Figure 4 Effect of pH on PDA impregnation (DA concentration 2.0 mg cm-3): A) Percentage of impregnation as
a function of pH; B) Effect of PDA impregnation on the iodine index
Figure 3 (A) presents the results obtained when evaluating the effect of the pH of the impregnation
medium. An increase in the impregnation percentage up to 4.2 % is observed, which is explained by
the zero-loading point (PZC) presented at pH 11 for the kernel of the palm kernel. Figure 3 (B) shows
the effect of increasing the PDA impregnation generated by the pH variation on the adsorption
capacity measured through the iodine index. Clearly a decrease in the adsorption capacity is
observed. The PDA forms deposits in the macropores and acts as a barrier that prevents the passage
to the mesopores and finally to the micropores (Maldonado, 2011).
The rate of PDA polymerization on the AC generates a highly heterogeneous material, but can be
controlled by the addition of ethanol (Yan et al., 2013). Figure 4 shows the effect of the presence of
ethanol in the impregnation medium for this system. Some changes in the process of impregnation
of PDA allowed to increase the performance of the process. It can be seen how the presence of ethanol
in the impregnation medium has favorable results in the deposition of PDA on the surface of the AC
6
10

6
0
10 20 30 40 50 60
Ethanol Concentration (% w/w)
.
Figure 4 Effect of ethanol concentration on the impregnation of PDA in activated carbon (pH 8.9 and
concentration DA 2.0 mg cm-3)
Figure 5 corresponds to the tests performed to increase the impregnation and improve the mass
transfer into the activated carbon of the PDA. In this case the deposition of PDA on the surface of the
coal increases until reaching a maximum value when the dopamine concentration is 6 mg cm -3. The
results of these tests showed evidence of the presence of PDA in the carbon structure, volatile content
increases progressively as PDA impregnation increases. The content of volatiles increases from 3.7 to
8.6 % for the AC and the CA-PDA composite, respectively. This is because the polymer decomposes
completely at 800 °C, temperature lower than that of the test (950 °C) (Park et al., 2002; Hydari et al.,
2012).
A preliminary study was performed with a recycle of the waste solution as the buffer solution and
the results obtained did not indicate any significant impact on the percentage of PDA impregnation.
For this, it was necessary to perform an aeration process to assure the presence of dissolved oxygen
in the recycle (Li et al., 2015; Nir and Reches, 2015). Finally, as recirculation of the buffer solution was
considered, it was decided to reduce the temperature of the solution to 8 °C while maintaining an
aeration for 30 min. Thus, it was intended to maintain or slightly exceed the concentration of the
dissolved oxygen in the solution which may vary from 7 to 8 mg dm -3 (Labella et al., 2015).
7
10

6
0
0 2 4 6 8 10
Dopamine Concentration (mg/mL)
Figure 5 Effect of dopamine concentration on the impregnation of PDA (pH 8,9; ethanol concentration 16,3 %)
Adsorption tests of ions [AuCl4]¯ and Cu2+

The pH at which the tests were carried out allowed the surface of the adsorbent to have a positive
charge around the introduced nitrogen atoms. For this reason, an electrostatic interaction between
the [AuCl4] - ions and the surface of the composite AC - PDA (Yu et al., 2014; Zhang et al., 2014). For
higher values of PDA impregnation, a decrease in the adsorption occurs which is due to the reduction
of the specific surface of the activated carbon by the presence of the PDA. These results were analyzed
using the Freundlich model to which the data were adjusted. The equilibrium parameters were
determined for the virgin activated carbon and the AC-PDA composite that presented the best
adsorbent characteristics. The Freundlich isotherm is based on adsorption on a heterogeneous surface
with uniform energy.
Cu2+ adsorption tests were carried out at a pH of 5 to avoid precipitation in the form of copper
(Cu(OH) 2) and electrostatic repulsion by the PDA (Yu et al., 2014; Zhang Et al., 2014). As shown in
Table 1, there is an increase in adsorption by the AC with impregnation of 4.9 % PDA. The increase
is since the catechol groups of the PDA have a strong tendency to form complexes or coordination
bonds with copper ions in aqueous solution (Yu et al., 2014; Rall and Kalm, 1994).
The adsorption-desorption cycles of [AuCl4]¯ have a recovery of 86.3; 83.4 and 71.6 % by a solution of
3 M HCl. This shows a composite reuse capacity of 3 cycles. Hydrochloric acid, being a strong
oxidizing agent and due to the concentration used, degrades the polymer and degenerates the surface
of the AC (Hong et al., 2014, Del Frari, Bour, Ball Toniazzo and Ruch, 2012). In addition, a certain
amount of residual gold can be present which occupies the active sites in the surface of the coal which
diminishes its capacity of adsorption. For the adsorption of Cu2+ ions, recoveries of 93.3 were
obtained; 90.2 and 78.1% using 0.1 M HCl. This result is consistent with the results reported in the
literature for PDA degeneration and reuse (Yu et al., 2014; Zhang, 2014).
8
Table 1 Parameters of the Freundlich adsorption isotherm for the virgin activated carbon and the
CA-PDA composite at different percentages of impregnation
Sample Freundlich model
[AuCl4]- Cu2+
𝐾𝑓 (mg g-1) 𝑛 𝑅2 𝐾𝑓 (mg g-1) 𝑛 𝑅2
Virgin Carbon 43,3 0,6 0,82 1,1 0,6 0,91
AC-2,8%PDA 118,9 0,5 0,92 2,5 0,8 0,93
AC-4,9%PDA 33,9 0,8 0,97 9,7 0,7 0,98
AC-5,6%PDA 5,8 0,9 0,88 0,4 0,4 0,94
* Ion adsorption tests: [AuCl4] - (time: 24 h, pH 2.0, T 18 ° C, ORP 900 mV); Cu2+ (24 h, pH 5.0, T 18 ° C)
The AC-PDA composite with the best adsorbent properties was characterized morphologically by
MEB. Figure 6 presents the AC-PDA composite at different magnifications (800X and 1200X).
Figure 6 (A) shows spherical PDA formations with diameters ranging from 20 to 0.5 μm on the
internal surface of the AC, which demonstrates the success of the impregnation process. In
Figure 6 (B) it can be seen how the PDA forms deposits of spherical geometry on the surface of
activated carbon.
Figure 6 Scanning electron microscopy of the composite AC-PDA (A 800 X, B 1200 X)
An overlapping sheet structure corresponding to the characteristic morphology of the palm kernel
can be observed. In addition, a TGA analysis was performed to estimate the relative composition of
the AC-PDA composite. A percentage of impregnation 2.8 %, calculated below the overall percentage
9
of impregnation calculated by gravimetric analysis, was calculated from the decomposition
temperature ranges of the PDA, this can be justified by a non-uniformity of the deposition of PDA in
the internal structure of activated carbon (Yu et al., 2014).
CONCLUSION
The surface of granular kernel cell AC was successfully functionalized with PDA. The AC-PDA
composite presented higher adsorption capacity of [AuCl4]¯ and Cu2+ ions compared to virgin AC
due to the introduction of nitrogen heteroatoms (N-H or -N=) and catechol functional groups
belonging to the PDA.
The conditions that define the best PDA impregnation process on AC are: pH 8.9; 16.3 % ethanol;
1 mg cm-3 of DA, 30 min of aeration at 8 °C and 24 h of shaking.
The impregnation pH plays an important role in the impregnation process since the chemical
interaction between the PDA and the surface of the AC depends on this parameter. The AC of palm
kernel, used in this research has a PZC of 11. However, in other matrices based on activated carbon
the value will be different, so it must be determined in each case.
The AC-PDA composite presents better adsorbent properties at impregnation values of 2.8 and
4.9 %, at higher values a matrix saturation occurs.
The AC-PDA composite can be reused for 3 cycles of adsorption-desorption of [AuCl4]¯ or Cu2+ ions
until the original characteristics of the virgin activated carbon matrix are recovered, due to
degradation of the polymer.
The approximate cost of the AC-PDA composite is 43 USD / kg and its prospects of industrial
application are oriented to the pre-concentration or separation processes of gold and copper in the
hydrometallurgical industry of refractory minerals, copper extraction and environmental
remediation.
The AC-PDA composite can be used as a versatile platform for secondary reactions due to the
presence of its new active sites (N-H or -N=), this allows it to be used as a base material to generate
technologies such as catalysts and activated carbons biocides.
REFERENCES
Del Frari, D., Bour, J., Ball, V., Toniazzo, V., & Ruch, D. (2012). Degradation of polydopamine coatings
by sodium hypochlorite: A process depending on the substrate and the film synthesis method,
Polymer Degradation and Stability, 97(1), 1844-1840.
http://dx.doi.org/10.1016/j.polymdegradstab.2012.05.002.
Dong, Z., Zhang, F., Wang, D., Liu, X., & Jin, J. (2014). Polydopamine-mediated surface
functionalization of graphene oxide for heavy metal ions removal, Journal of Solid State Chemistry,
224(1), 88-93. http://dx.doi.org/10.1016/j.jssc.2014.06.030.
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13
Silver Leaching from Jarosite by Thiourea in Acid
Media: effect of Copper and Sulfur on the Stability of
the Thiourea-Silver System
Dandy Calla, Fabiola Nava and Juan Fuentes
CINVESTAV Saltillo, Mexico
ABSTRACT
The jarosite residue has been produced during many years in the hydrometallurgical zinc plants to
remove iron and sulfate from the zinc liquor. The jarosite is a stable species that may contain some
elements in its structure, e.g., silver, that would be interesting to recover. As jarosite is refractory to
the standard cyanidation method for silver recovery, some pretreatment for decomposition in
alkaline or acid medium at elevated temperature is required to recover the silver contained. The
thiourea leaching in acid media is proposed as an alternative method to cyanidation, for the recovery
of silver from jarosite residues.
The stability of thiourea was evaluated in synthetic solutions by titration with iodate. It was
demonstrated that the presence of copper and sulfur has a detrimental effect on the thiourea stability
and consequently on the silver leaching. The release of copper from the jarosite to the solution by the
thiourea leaching increases the redox potential of the solution causing the thiourea oxidation and
thus hindering the silver leaching
The thiourea leaching tests of an industrial Mexican jarosite showed that the silver contained in the
jarosite can be completely leached (10,000 ppm thiourea, pH = 1, 90°C and 2 h) if the thiourea
concentration in the system is sufficient. During the leaching, copper is also released to the solution;
it increases the redox potential and can cause the thiourea oxidation. When the jarosite/solution ratio
is decreased from 100 g/L to 5 g/L, the silver leaching increases from 76% to 100%. This fact can be
associated with the thiourea concentration in solution, that increases from 4% to 71% due to the
diminution of the copper released into the solution.
1
INTRODUCTION
Jarosites
The jarosites (MFe3(SO4)2(OH)6, where M=Na+, K+, Ag+, etc.) are part of the isostructural jarosite-
alunite group, and they are commonly found in the oxidized parts of sulfide-bearing ore deposits, in
acid sulfate soils with acid mine drainage (Bigham et al. 1996, Bigham & Nordstrom 2000, Welch et
al. 2007) and mixed with clays (Dutrizac & Jambor 2000).
The synthetic jarosites are produced in industrial processes or at laboratory level. Due to properties
and advantages of their formation, the sodium and ammonium jarosites are the species used in the
zinc industry (Figure 1) because they form a compound that allows easy separation of the iron from
the leaching solution and reduces the loss of divalent base metals.
Figure 1 Jarosite precipitation incorporated to a hydrometallurgical zinc processing (Dutrizac & Jambor 2000).
The important factors affecting the stability of jarosite are pH and temperature (Das et al. 1996); in
acid media, the jarosite can be decomposed at 90°C and pH 2 (Eq. 1), liberating some cations of its
lattice, e.g., silver (Calla-Choque, Nava-Alonso & Fuentes-Aceituno 2016).
MFe3(SO4)2(OH)6 + 6H+ = M+ + 3Fe3+ + 2SO42- + 6H2O (1)
Thiourea leaching
Thiourea (TU, CS(NH2)2) is an alternative reagent for the leaching of gold and silver in acid
conditions; this process must be carried out in the presence of oxidants like ferric ions, hydrogen
peroxide, or others (Eq. 2). The first step of the partial oxidation of thiourea to formamidine disulfide
(FDS, (NH2)2CSSC(NH2)22+) is reversible (Eq. 3, Preisler & Berger 1947). FDS is a good oxidant for gold
and silver; however, if the increase on the solution’s potential is sufficiently high, it will cause the
degradation of thiourea to FDS, and the consecutive oxidation of FDS to several intermediate species
leading to the final formation of elemental sulfur (Marsden & House 2006).
Ag + 2CS(NH2)2 + Fe3+ ↔ Ag(CS(NH2)2)2+ + Fe2+ (2)
2CS(NH2)2 ↔ (NH2)2CSSC(NH ) 2 22+ + 2e - (3)
2
Ferric and cupric ions act as oxidizing agents for thiourea and both produce FDS, but cupric ions
have a stronger impact on the stability of thiourea because besides the thiourea oxidation the cuprous
ions resulting from the thiourea oxidation can form complexes with the thiourea (Eq. 4), consuming
the available thiourea.
2Cu2+ + 2(n+1) CS(NH2)2 → 2[Cu(CS(NH2)2)n]+ + (NH2)2CSSC(NH2)22+ (n=1-4) (4)
This work presents a study on the thiourea chemical stability in the presence of cupric ions and
elemental sulfur using synthetic solutions at room temperature to contribute to the understanding of
the acid thiourea system. In addition, industrial jarosite decomposition-leaching tests were
performed at different jarosite/solution ratios in an attempt to limit the presence of copper and to
improve silver recovery as well as the stability of thiourea in solution.
METHODOLOGY
This work is divided in two sections: the study of the copper and sulfur effect on the thiourea stability
in synthetic thiourea-silver solutions, and the decomposition-leaching of silver from industrial
jarosite.
The effect of cupric ions and sulfur on the stability of thiourea, in the thiourea-silver system, was
evaluated by the titration technique for the quantification of the thiourea in solution. The percentage
of thiourea oxidized was calculated by a first titration using 0.05 M potassium iodate as titrant, 6 ml
of 6 M sulfuric acid, 1 ml of 2% starch and 4 ml of sample. In addition, a second titration was
performed by adding zinc powder that will reduce the FDS into thiourea again; this second titration
permits the quantification of the irreversible thiourea oxidation: the thiourea that was oxidized to
form not FDS but further oxidation products. The irreversible oxidation of thiourea was determined
by the difference between the concentration of the initial thiourea (first titration) and the
concentration of thiourea in the presence of zinc (second titration). For the evaluation of the thiourea
stability in presence of copper, solutions with 10,000 ppm thiourea and 16 ppm silver were prepared
with different copper concentrations, as shown in Table 1. Additional experiments were done to
evaluate the effect of sulfur on the thiourea stability; these tests were performed by adding 0.05 g of
sulfur in 100 ml of each one of the solutions presented in Table 1. Before each titration, the
concentration of silver and copper, pH and potential of each solution were measured. The sulfur
produced was validated by X-ray diffraction.
Table 1 Composition of the synthetic solutions used to evaluate the effect of copper on the stability
of thiourea and silver in the thiourea-silver system. All solutions were prepared with 10,000 ppm
thiourea and 16 ppm silver. The pH was not controlled.
System Copper concentration (ppm)

TU-Ag(I)-Cu(II) 300 700 4,129 8,280
The decomposition-leaching tests of industrial jarosite were performed at pH 1, 90°C and 10,000 ppm
thiourea. Two jarosite/solution ratios were used in order to evaluate its effect on the silver recovery
and on the thiourea stability in acid media. The first ratio was 100 g of industrial jarosite without
modification of particle size in 1 L of solution; it is important to note that this jarosite is of fine nature
3
(d80 = 24 μm). The second jarosite/solution ratio was 5 g of industrial jarosite with a particle size fixed
at +25 μm/-38 μm in 1 L of solution; in both cases the same industrial jarosite was used. The
mineralogical species of the jarosite were identified by X-ray diffraction (Philips, X-Pert PW3040) as
natrojarosite and franklinite as the main species. The silver content (158 g/t) was obtained by fire
assay, the metals in solution were analyzed by atomic absorption spectrometer (Varian
SpectraAA220) and the particle size distribution was determined by laser diffraction analysis
(Coulter LS-100Q).
Effect of sulfur and cupric ions on the stability of the TU-Ag system
Cupric ions can be released into the solution while the jarosite is decomposed; therefore, it is
important to evaluate the effect of this oxidant species on the stability of thiourea-silver (thiourea
degradation). Elemental sulfur can be formed by oxidation of the FDS (Eq. 5) from thiourea; for this
reason, the effect of sulfur on the thiourea stability was also evaluated. The first two copper
concentrations of the prepared solutions (300 and 700 ppm, Table 1) were selected considering the
values obtained in preliminary decomposition tests of the industrial jarosite (not shown in this work);
the high copper levels were evaluated in order to explore the effect of the redox potential on thiourea
degradation. Tables 2 and 3 show the results of the thiourea stability for the solutions prepared with
cupric ions (Table 2), and with cupric ions and elemental sulfur (Table 3); the pH and Eh values
measured before titration with and without zinc are also presented in these tables.
[H2NHNCSSC(NH2)2]+ → H+ + CN(NH2) + S + CS(NH2)2 (5)
Results presented in Tables 2 and 3 show the thiourea stability in the systems TU-Ag (I)-Cu (II) and
TU-S-Ag (I)-Cu (II) respectively. It is possible to observe, in both systems, that an increase in the
concentration of the cupric ions increases the redox potential of the solution. It is important to
mention that the Eh values in tests A4, A5, B4 and B5 are greater than 0.42 V vs. SHE; this potential
value is the redox potential of the oxidation of thiourea to formamidine disulfide (Figure 2). In these
four tests (A4, A5, B4 and B5) when the cupric ions were added to the system a white solid was
formed; according to Dupuis (1987) and as it was confirmed by X-ray diffraction, this solid product
(2CuSO4(CS(NH2)2·nH2O) is related to the irreversible oxidation of thiourea.
Figure 2 Distribution diagram for TU-H2O species at 25°C and pH 2.
4
This fact indicates that one proportion of the thiourea is oxidized irreversibly, and another is in the
form of FDS, which can be reduced again to thiourea in the presence of metallic zinc, i.e., in the A5
test, the presence of copper causes the oxidation of 96.86% of the thiourea present in the solution; of
this percentage, 76.31% is irreversibly oxidized and 20.55% is oxidized to form FDS. It is important
to note that in these tests (A4 and A5), part of the silver is precipitated from an initial concentration
of 16 ppm to 2.5 ppm when sulfur is not present, and to around 0.4 ppm when it is present in the
solution. This behavior indicates that sulfur does not have a significant effect on the oxidation of
thiourea, but it does have a significant effect on the stability of silver in solution. A precipitation
above 97% (0.5-0.3 ppm) of silver is shown when sulfur is present in the system.
Table 2 Stability of TU and Ag in the presence of cupric ions for synthetic solutions presented in
Table 1. Initial concentration of thiourea 10,000 ppm and 16 ppm silver. The pH was not controlled.
System TU-Ag(I)-Cu(II)
Thiourea direct titration Thiourea titration with zinc
Before titration Thiourea Before titration Irreversible
Initial Cu 2+ Ag Cu Eh oxidation Ag Cu Eh thiourea
pH (%) pH oxidation (%)
Test Ppm ppm ppm V ppm ppm V
A1 0 16.0 0.0 2.29 0.26 0 0 0 6.44 0.19 3.97
A2 300 16.0 257 2.19 0.39 14.67 0 4.7 6.57 0.15 12.10
A3 701 16.0 520 2.14 0.40 40.50 0 4.0 6.68 0.17 12.59
A4 4,129 2.5 1,068 2.11 0.58 96.15 0 4.4 6.14 0.14 76.08
A5 8,258 2.5 4,185 2.09 0.59 96.86 0 4.7 5.92 0.14 76.31
Table 3 Stability of TU and Ag in the presence of cupric ions and sulfur with an initial
concentration of thiourea 10,000 ppm, 16 ppm silver and 0.05 g of sulfur/100 ml solution. The pH
was not controlled.
System TU-S-Ag(I)-Cu(II)
Thiourea direct titration Thiourea titration with zinc
Before titration Thiourea Before titration Irreversible
Initial Cu Ag
2+Cu Eh oxidation Ag Cu Eh thiourea
pH (%) pH oxidation (%)
Test Ppm ppm ppm V ppm ppm V
B1 0 16 0 2.24 0.27 0 0 0 6.43 0.21 3.40
B2 300 16 255 2.20 0.38 20.66 0 3.9 6.80 0.16 8.30
B3 701 16 638 2.00 0.4 40.70 0 4.4 6.81 0.09 12.96
B4 4,129 0.5 1,079 2.12 0.57 96.63 0 4.0 6.13 0.13 81.74
B5 8,258 0.3 4,358 2.26 0.59 97.43 0 4.2 5.85 0.14 80.31
For low cupric concentrations (300 and 700 ppm), thiourea oxidation is similar when sulfur is present
or not in the solution (Tables 2 and 3, respectively). A small amount of the thiourea is oxidized in
both cases i.e., 14.67 and 40.5% of the thiourea is oxidized when sulfur is not present in the solution
5
(A2 and A3), while, if sulfur is present, 20.66 and 40.7% of the thiourea is oxidized for the same copper
concentrations (B2 and B3). The silver in solution in both cases remains constant.
The results presented in this section show that the presence of cupric ions increases the potential of
the system. Cupric ions play an important role because at high concentrations it can increase the
potential of the system to more than 0.5 V vs. SHE, where thiourea is oxidized and affects the stability
of silver in solution; when sulfur is present in combination with cupric ions they both have a
detrimental effect on the stability of silver in solution (from 16 ppm to 0.3 ppm).
Silver leaching from industrial jarosite by thiourea

The jarosite decomposition-leaching tests were performed at pH 1, 90°C and a thiourea concentration
of 10,000 mg/L. Two jarosite/solution ratios were used to evaluate its effect on the silver recovery and
on stability of the thiourea in acid media. The first ratio was 100 g of industrial jarosite without
modification of particle size in 1 L of solution; it is important to remember that this industrial jarosite
presents fine particle size (d80 = 24μm). The second ratio was with 5 g of the industrial jarosite, with
a fixed particle size (+25 μm/-38 μm) in 1 L of solution.
The kinetics of silver leaching in both cases is very fast (Fig. 3) attaining a recovery of 100% of the
silver in the first 20 min when the ratio jarosite/solution is 5 g/L, and 76% when the ratio is 100 g/L.
These tests show that a highest jarosite/solution ratio (100 g/L), the silver recovery shows an
inhibition phenomenon, which may be related to the oxidative decomposition of thiourea. It is
important to note that when the solution reaches the temperature of 90°C with jarosite (t = 0), only
43% of thiourea is present in solution, as shown in Table 4, and this concentration decreases to 2.85%
at 90 min of the test. This oxidative decomposition of thiourea is responsible for the inhibition on the
silver recovery, as can be corroborated with the Eh values shown in Table 4, where the redox potential
varies from 0.42 to 0.57 V vs. SHE. The increase in the oxidizing ability of the system promotes the
oxidation of thiourea; the increase of the redox potential is associated with the continuous release of
the cupric ions as presented in Table 2. As it can be observed from the results of these tests, the
contribution of the cupric ions plays an important role in the oxidative degradation of the thiourea.
When the jarosite/solution ratio is 5 g/L, the inhibition phenomenon in the silver leaching shown in
the previous section is reduced due to the decrease in the copper concentration, that diminishes from
680 to 157.8 mg/L when the ratio is reduced from 100 g/L to 5 g/L respectively (Table 4). In both cases
the copper concentrations represent 100% of the copper present in the industrial jarosite, but the
reduced copper concentration promotes a greater stability of the thiourea because the system
potential does not increase to a value greater than 0.43 V vs. SHE; this potential contributes to the
stability of thiourea which is present in 71.4% at the end of the test.
6
100
80
Silver recovery (%)

60
40
100 g/L
20
5 g/L
0 20 40 60 80
Time (min)
Figure 3 Decomposition-leaching of silver from jarosite at 90°C and pH 1.
Table 4 Copper in solution and percentage of thiourea in the decomposition-leaching from jarosite
at 90°C and pH 1.
Leaching with 100 g/L Leaching with 5 g/L

Time Cu Eh Thiourea in Cu Eh Thiourea in
(min) ppm V solution (%) ppm V solution (%)
0 291 0.42 43 45 0.40 NM*
10 434 0.52 15.13 110 0.43 NM*
20 537 0.55 5.42 150 0.43 NM*
30 588 0.56 2.82 157 0.42 NM*
60 657 0.56 2.28 157 0.42 NM*
90 680 0.57 2.85 157 0.43 71.40
NM*= No Measured
Finally, it can be said that the control of the copper concentration in solution is of great importance
in this type of systems, where the acid media favors the release of these cations when they are present
in the mineral. The detrimental effect of cupric ions on the thiourea, and consequently, the silver
stability, is due to their high oxidizing ability.
CONCLUSIONS
The presence of cupric ions in high concentrations has the capacity to increase the potential of the
system to more than 0.5 V vs. SHE, where thiourea is mostly oxidized and contributes to the
instability of silver in solution. When cupric ions in combination with sulfur are present in the system,
they have an increased detrimental effect on the silver stability in solution (from 16 ppm to 0.4 ppm).
Control of copper by diminution of the jarosite/solution ratio from 100 g/L to 5 g/L eliminates the
phenomenon of inhibition on the recovery of silver, which occurs when the thiourea is almost
completely oxidized. This reduction of the copper present in the system promotes a greater stability
7
of thiourea because the reduction on the potential of the solution, from 0.57 to 0.43 V vs. SHE; this
reduction on the solution potential increases the thiourea stability from 2.85% to 71.40%, respectively.
ACKNOWLEDGEMENTS
The authors are grateful to CONACYT Mexico for the Dandy Calla-Choque postgraduate
scholarship, as well as the project CB2015 / 257115.
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Dupuis, C. (1987) ‘Study of the stability of thiourea and the recovery of gold by direct electrolysis
applied to the treatment of auriferous chalcopyrite concentrates’, Faculty of Science and Engineering.
Laval University, Master of Science: 29-125.
Dutrizac, J. E. and J. L. Jambor (2000) ‘Jarosites and their application in hydrometallurgy’, Reviews in
Mineralogy and Geochemistry, 40: 405-452.
Marsden, J. O. and C. I. House (2006) ‘The chemistry of gold extraction’, Society for Mining, Metallurgy,
and Exploration, Inc. (SME), Colorado.
Preisler, P. W. and L. Berger (1947) ‘Oxidation-reduction potentials of thiol-dithio systems: Thiourea-
formamidine disulfide’, Journal of the American Chemical Society, 69(2): 322-325.
Welch, S. A., A. G. Christy, D. Kirste, S. G. Beavis and F. Beavis (2007) ‘Jarosite dissolution I-Trace
cation flux in acid sulfate soils’, Chemical Geology, 245(3-4): 183-197.
8
Oxygen Mass Transfer in the Albion ProcessTM: from
the Laboratory to the Plant
Paul Voigt, Mike Hourn and Daniel Mallah
Glencore Technology, Australia
ABSTRACT
The successful commissioning and ramp up of the Albion ProcessTM at the GPM Gold Project relied
on the successful scaling up of the process from batch and continuous pilot plant campaigns (Voigt,
2016) Critical information about reaction kinetics and residence time, grind size and pulp density
were determined at the laboratory scale and successfully applied to the commercial scale. A
limitation of small scale testwork, is that some parameters cannot be measured reliably and scaling
up is a function of the physical size of the equipment which isn’t possible to test with laboratory
scale equipment. Oxygen mass transfer rate is one such parameter since this is a complex
interaction of many factors including slurry temperature, solution and slurry chemistry, slurry
viscosity, agitator type, dimensions and power, oxygen bubble residence time, oxygen purity, tank
geometry and oxygen injection technique. Oxygen generation represents an important operating
cost for the Albion ProcessTM. Pivotal to the Albion ProcessTM operating economically at
atmospheric pressure is the capability to efficiently transfer oxygen while utilising as much oxygen
injected to the process as possible. To respond to this Glencore Technology developed the
HyperSpargeTM supersonic gas injector. This paper compares the HyperSpargeTM against other
sparging techniques to quantify the benefits of oxygen injection via a supersonic gas jet on scale up
of the oxygen mass transfer system. The paper then examines plant survey data from the GPM
Gold Project to demonstrate the very high oxygen utilisation that can be achieved with a correctly
designed oxygen mass transfer system.
1
INTRODUCTION
One of the main challenges in chemical reactor design is the scale-up of processes from the
laboratory to industrial scale. One particular challenge are those processes which cannot be
faithfully simulated with an experiment at the laboratory due to the physical dimensions and
complexity of the real system. One example of this is the design of oxygen mass transfer systems in
atmospheric oxidative leaching such as the Albion ProcessTM. Some of the problems with the small
size of equipment are the specific agitator power input is artificially high, the bubble residence time
in the vessel is artificially low, the oxygen partial pressure at the base of the vessel is artificially low
and the way oxygen is injected into the process may not be the same as the industrial process. Some
of the problems of the complexity of the system is the dynamic nature of the process including the
presence of solids, recycle streams and minor elements plus the variances within the reality of a
process plant such as disruptions or variance of feed quality.
It is critical that for such processes the fundamentals are understood so that key data can be
collected from appropriately designed experiments at the laboratory scale for input into a proven
design approach to render the industrial scale process effective and fit-for-purpose.
To maximise oxygen mass transfer efficiency, operational availability, simplicity and safety,
Glencore Technology (GT) developed the HyperSparge TM supersonic gas injector. Originally for
injecting oxygen to the Albion ProcessTM, the HyperSpargeTM has found application in other
processes using air, oxygen, sulphur dioxide and gas mixtures. Over 400 HyperSparge TM units are
installed globally in duties from in-line slurry conditioning, fermentation, waste-water treatment,
CIL/CIP processes and oxidative leaching.
This paper compares the HyperSpargeTM to other gas injection techniques such as ring spargers and
converging nozzles. The key data are identified for scale-up from the laboratory to industrial scale.
Survey data are examined from the GPM Gold plant in Armenia where the oxygen mass transfer
system was successfully designed and comments are made about the operational advantages of the
HyperSpargeTM compared to other systems such as sintered spargers.
OXYGEN MASS TRANSFER

The Albion ProcessTM is an atmospheric oxidative leaching process developed by GT in 1994 and is
described extensively in the literature (Hourn & Turner, 2010; Hourn & Turner, 2012; Hourn et al.,
2014; Voigt et al., 2015; Senshenko et al., 2016). Oxidation of pyrite is one of the key reactions in the
Albion ProcessTM chemistry as shown in Equation 1.
FeS2 + 15/4O2 + ½ H2O = ½ Fe2(SO4)3 + ½ H2SO4 [1]
The first step of the oxidation mechanism is the dissolution of oxygen in the liquid phase since
electron transfer occurs in part through the action of the ferric and ferrous ion couple and the action
of dissolved oxygen reacting directly with pyrite. Hence the rate at which oxygen is transferred is
critical to the process efficiency and can be simplified for a reactor as shown in Equation 2
(Middleton & Smith, 2004).
O2 Transfer Rate = kLa.V.(Csat – C) [2]
2
Where kL is the liquid film transfer co-efficient (m.s-1), a is the specific gas surface area (m -1), V is
reactor volume (m3), Csat is the oxygen solubility at saturation (g.m-3) and C is the steady state
oxygen level (g.m-3). The terms kL and a are normally combined to represent the oxygen mass
transfer co-efficient which is the parameter to be maximised.
For practical purposes the kLa needs to be maximised by determination of a relationship with
power input through the sparger and the agitator and then selection of equipment that satisfies the
oxygen transfer rate requirements of the system. Middleton (1992) simplified the equation relating
kLa to power input is shown in Equation 3.
kLa = K . (Us)a . (Pg/V)b [3]
Where K is a coalescence constant, Us is superficial gas velocity (m.s-1) and Pg is absorbed power
(W). A correction is also applied for temperature since increasing temperature will reduce slurry
viscosity and surface tension increasing the mass transfer interfacial area. The coefficients a and b
are empirical constants that are system specific and are determined through testwork.
There are many theoretical correlations between kLa and energy input reported in the literature and
the majority tend to be based on data in biochemical reactors meaning the extension to oxidative
leaching can be problematic with limited applicability because the agitation intensity, system
chemistry, operating temperature and oxygen injection methods are very different (Van’t Reit, 1979;
Vasconcelos et al., 1998; Oguz et al., 1987; Moo-Young & Blanch, 1981). Most of these correlations
are also derived at very small scale, with laboratory vessels of 10 litres or less in size.
The best way to achieve successful industrial scale up is to determine the a and b empirical
constants for equation 3 for a given system through specific experiments that reflect the actual
system conditions. Once determined for a specific system, Equation 3 is then used along with other
reactor design equations and experience to calculate the tank geometry and power input required
from the agitator and gas injector to achieve the required k La. GT has developed an experimental
procedure to determine the a and b empirical constants for a given system which will result in a
successful scale up with minimal error. An example of using this method to compare the
experimental and calculated kLa for a copper leach system is shown in Figure 1.
Figure 1 Experimental and calculated kLa for a system using GT experimental methodology
3
INJECTION OF OXYGEN
Importance of oxygen injection method

The method in which oxygen is injected has a large bearing on the efficiency of the oxygen mass
transfer. Referring to Equation 2, the liquid film co-efficient (kL) is proportional to the oxygen
diffusion coefficient and inversely proportional to the liquid film thickness. The consequence for
oxygen injector selection is that high pressure gas injection maximises shear and significantly
erodes the liquid film thickness resulting in increasing kL. Referring to Equation 3, the surface area
(a) is proportional to power absorbed into the system relative to system volume and superficial gas
velocity. Surface area is also inversely proportional to bubble size. The consequence for oxygen
injector selection is to maximise shear and minimise bubble size but also to select an agitator that
provides sufficient complimentary power input.
Options for oxygen injection

There are many gas injectors available on the market. The converging nozzle type and ring spargers
(essentially open pipes) and among the most common from an operational perspective. Sintered
spargers find application in flotation machines and chemical reaction systems and are well suited to
the laboratory but are plagued with operational issues at the industrial scale, particularly in
processes with chemical reactions due to the fast accumulation of reaction products and the
continual need to clean them.
GT performed a number of experiments comparing the performance of an open pipe sparger, a
converging nozzle type sparger and a newly developed supersonic sparger by GT, the
HyperSpargeTM.
Open pipes and sparge rings do not transfer a significant amount of energy into the leach vessel,
with all the energy required for oxygen mass transfer provided by the impeller. For these spargers,
the gas is compressed to just above the hydrostatic head level in the slurry tank and the pressure
drop across the tip of the injection point is low, resulting in low gas speeds.
Convergent nozzles, such as the CPT Slamjet and Minnovex gas spargers, were developed for
flotation column aeration duties, and have found some use in slurry oxidation systems. These
nozzles converge to a narrow opening, and the gas is compressed to several atmospheres above the
hydrostatic head level in the slurry tank. The pressure drop across the tip of the injection point is 3
– 5 atmospheres, resulting in higher gas speeds at the point of injection. This results in more energy
being put into the gas from the sparging system, and so less energy is required at the impeller.
Testwork carried out by GT has found that for oxygen mass transfer purposes, energy input to the
system via the gas sparging system is more efficient than energy input via the impeller, as long as
the majority of the energy released from the gas pressure drop across the sparger is converted to
kinetic energy and not lost as heat. As such GT developed a supersonic gas injector, the
HyperSpargeTM, to further improve the efficiency of the gas injection system. The HyperSpargeTM
used a converging-diverging nozzle to maximise energy recovery from the gas pressure drop by
accelerating the gas to supersonic velocities.
4
Efficiency of oxygen injection methods
Energy is put into the gas sparging system by pressurising the gas prior to the sparger, to store
energy in the gas stream. The theoretical energy input to compress the gas is defined in Equation 4.
W = (n/(n-1))mRT[(P2/P1)(n-1)/n – 1 [4]
Where n is isothermal efficiency, W is work (J), P 1 is outlet pressure (N.m-2) and P2 is inlet pressure
(N.m-2), T is temperature (K), R is the ideal gas constant (8.314472 J.K -1.mol-1) and m is moles.
The pressure energy is then recovered as work into the system, ideally the efficiency of this
conversion is maximised. High speed gas injection maximises turbulence at the injection point,
which reduces the liquid film boundary layer around the gas bubble, increasing the liquid film
diffusion rate, and so increasing the kL value. The higher kinetic energy of the gas will translate to a
higher interfacial area, which also assists mass transfer.
In a conventional pipe or ring sparger, the nozzle diameter is relatively large, resulting in a low
velocity gas flow, which remains constant along the length of the nozzle. In this configuration,
higher gas flows can lead to larger bubble sizes and consequently smaller interfacial areas (a). As a
general rule, the size of the bubble generated from a conventional sparger will be close to the size of
the orifice.
The formation of fine bubbles requires a specific type of nozzle to be fitted to the end of the sparger.
Nozzles can normally be described as convergent (narrowing down from a wide diameter to a
smaller diameter in the direction of the flow) or divergent (expanding from a smaller diameter to a
larger one in the direction of the flow).
Convergent nozzles accelerate subsonic gases, with the dynamic pressure decreasing from the
nozzle opening to the narrowest point as the gas is accelerated. Once the ratio of the gas pressure at
the nozzle throat to the feed pressure reaches a critical value, the flow will reach sonic velocity. This
forms a shock wave in the nozzle throat. The nozzle is then said to be choked, and the gas flow is at
Mach 1. Gas flow cannot be accelerated beyond Mach 1 in the throat of the nozzle.
Increasing the nozzle feed pressure further will not increase the velocity of the gas at the throat of
the nozzle, and so any additional pressure energy is then stored in the gas in the form of heat.
Divergent nozzles decelerate subsonic gases; the gas expands in the nozzle and slows down.
However, when the gas enters the divergent section at Mach 1, the divergent nozzle will accelerate
the gas, as the stored heat energy is converted to velocity. Combination convergent-divergent
nozzles, such as those used in the HyperSpargeTM can, therefore, accelerate gases that have choked
in the convergent section to supersonic speeds. These nozzles develop thrust by converting the
stored heat that builds up in the gas in the throat into velocity when in the divergent section of the
nozzle.
When gas is accelerated to velocities above the speed of sound in the divergent section of the
nozzle, the local pressure drops further, and does not recover to ambient pressure until the gas
passes through the resulting shock wave as illustrated in Figure 2.
5
Figure 2 Collapsing bubbles crossing the shock wave of a supersonic nozzle (Kawamura et al., 2004)
The low pressure that is generated in the divergent section of the nozzle leads to collapse of the gas
bubble into a fine mist, and results in a dramatic increase in the gas surface area. This is shown in
the figure above, where the gas bubble leaves the throat of the nozzle at a size that is fairly similar
to the size of the throat diameter, and then collapses to a fine mist of micro-bubbles in the low
pressure zone in the divergent section. This collapse is triggered by the gas crossing the shock wave
that is set up once the gas is choked in the throat of the nozzle. This shock wave can extend
anywhere from the nozzle throat to the end of the nozzle and beyond, depending on the pressure
applied to the nozzle.
A convergent-divergent nozzle has two important roles. The design of the nozzle determines the
exit velocity for a given pressure and temperature. And because of flow choking in the throat of the
nozzle, the nozzle design also sets the mass flow rate through the nozzle. Therefore, the nozzle
design determines the thrust of the gas injection system. By changing the shape of the nozzle and
the flow conditions upstream and downstream, you can control both the amount of gas that passes
through the nozzle and the thrust generated by the nozzle. A convergent-divergent nozzle is
represented below.
Figure 3 Cross section of a convergent-divergent nozzle (NASA, 2015)
EXPERIMENTAL
A number of experiments were performed to compare the nozzle types evaluating on the variables
of thrust and oxygen mass transfer co-efficient (kLa). Experiments were performed in a jacketed,
1750 litre tank fitted with four baffles and a lid to minimise evaporative loss. The process solution
employed was a copper leach solution at pH 1, with 15 g/l -1 copper. High purity gaseous oxygen
and nitrogen was used. The nozzles employed for the experiments were:
 10mm open pipe
 Converging high pressure sparger, 4mm exit diameter
6
 Converging-diverging HyperSpargeTM nozzle, Mach 3 (MV), 1mm throat and 5mm exit
diameter
 Converging-diverging HyperSpargeTM nozzle, Mach 1 (MT), 1mm throat and 1.7mm exit
diameter
Thrust
Thrust is a direct measure of the efficiency of conversion of pressure energy in the incoming gas
stream into momentum. The higher the thrust measured, the more efficient the nozzle will be in
converting pressure energy into mass transfer without loss to heat dissipation. The nozzles were
positioned perpendicular and centred to a balance surface. The gas plume impinged the balance’s
surface and the mass imparted recorded. For an identical energy input in the sparging gas (ie fixed
flow and delivery pressure), each nozzle generated a different degree of thrust. The data are shown
in Figure 4.
Figure 4 Developed thrust measured at 200kPa
The results above show that at low oxygen flow all of the profiled nozzles exhibited similar thrust
values; less than 3 grams (g) of thrust recorded by the scale. However, at higher flows, the nozzles
have a very different behaviour. The open pipe sparger did not develop any thrust at all across the
entire range of gas flowrates, and so did not exert any force on the balance. The convergent nozzle
showed an almost linear response, with thrust increasing with flowrate, up to a maximum of 5 g at
13 lpm of gas flow.
Both GT HyperSpargeTM supersonic nozzles generated significantly more thrust than the open pipe
or convergent nozzle. In general, the nozzle designed to produce maximum thrust outperformed
the high velocity nozzle across all flow rates, achieving a thrust of 18 g at a gas flowrate of 13 lpm.
This compared well to the maximum theoretical thrust for a nozzle discharging 13 lpm of gas flow
of 21 g. This meant that 85 % of the pressure energy in the gas stream was converted to momentum
7
for the HyperSpargeTM MT nozzle profile. Both supersonic nozzles also displayed a considerable
steepening of the thrust curve at gas flowrates above 11 lpm, close to the point where the nozzles
were choked, indicating superior thrust as the gas speeds exiting the convergent-divergent nozzles
approached supersonic speeds.
Oxygen mass transfer co-efficient (kLa)

For temperatures up to 50oC oxygen mass transfer co-efficient was determined using the Dynamic
Gassing Out Method (Taguchi and Humphrey, 1966). Above 50oC the combined sulphite method
was used (Puskeiler, 2005). Experiments were conducted with and without solids in the reactor. The
results are shown in Figure 5.
The GT MV and MT nozzle designs resulted in a consistently higher k La value across the entire
range of gas flow rates tested relative to the open pipe and the convergent nozzle. As the gas flow
rate approached choked flow in the GT HyperSparge TM MV and MT nozzles, the difference in kLa
was more pronounced, and was up to 300 % of the value observed for the conventional open pipe
and 50% compared to a converged nozzle.
Figure 5 kLa at different supply pressure
The GT HyperSpargeTM MV and MT nozzles showed similar behaviours because both are
convergent-divergent type nozzles. Of the two HyperSpargeTM nozzles, the MT nozzle provided the
highest kLa, gas utilisation and thrust values, typically by 25 % relative to the MV nozzle at a set gas
flow rate. The higher thrust generated in the MT nozzle at the expense of velocity explains this
difference.
8
SCALE UP TO INDUSTRIAL SCALE
Through the scientific process, GT established that supersonic gas injection was technically a
superior way to inject gas into a slurry requiring oxygen. The next step was to develop the
converging-diverging nozzle into a product that can be used at the industrial scale.
The HyperSpargeTM
The HyperSpargeTM was developed by GT as a complete gas injection solution. At the heart of the
device is a converging-diverging nozzle fabricated from a specially selected wear-resistant ceramic
which accelerates gases to supersonic velocities for injection into solutions and slurries. The nozzle
is designed to minimise pressure energy loss. A schematic of the HyperSparge TM and close up of the
nozzle is shown in Figure 6.
Figure 6 HyperSpargeTM supersonic gas injector and nozzle
Apart from the advantages of superior oxygen mass transfer, the HyperSparge TM is safe and easy to
use. The HyperSpargeTM can operate over a range of pressures which can be adjusted to regulate
flow. The nozzles can be easily interchanged with the threaded nozzle holder allowing the use of
different nozzle diameters and hence flow operating envelopes. One attractive feature is that the
sparger can be inserted and removed from a vessel while it is full of slurry spillage free without
using any additional removal device plus with a throat diameter of typically 7 mm, the sparger
does not become blocked and self-cleans by the action of the gas flow. This means less operational
downtime and process interruption.
9
Oxygen Mass Transfer System Design
During the GPM Gold Albion ProcessTM plant development, key oxygen mass transfer experiments
were conducted to determine the kLa under conditions as close as practicable for temperature and
slurry conditions. The data was used by GT to then correctly size the gas injectors, agitators and
select ideal tank dimensions. The design criteria for the GPM Gold Plant is shown in Table 1.
Table 1 GPM Gold Albion ProcessTM Plant Design Criteria
Parameter Units Nominal Design
Throughput tph 13.1 14.5
S2- concentration % 17.6 20.0
S2- oxidation % 76 76
Oxygen Utilisation % 90 80
Required kLa m.s-1 0.12 0.14
CIL Gold recovery % 92 90
The economics of the industrial process rely on the efficiency of oxygen transfer to the system to
maximise transfer rate (achieving design residence time) and maximise transfer efficiency
(utilisation of the oxygen that is injected.
A survey was completed to collect plant data and assess the transfer rate and transfer efficiency.
Since an industrial plant was the subject of the survey, the plant couldn’t be taken off-line to
replicate laboratory experiments. Instead, the oxidation extent and oxygen consumption from the
operating plant were compared against the design. The conditions of the survey were a throughput
rate of 14.0 tph concentrate and a sulphide concentration of 17.0%.The survey data for oxidation
extent and gold recovery are shown in Figure 7.
10
Figure 7 Sulphide Oxidation survey of GPM Gold Albion ProcessTM Plant.
Figure 7 shows that at the design throughput the sulphide oxidation is achieved along with
corresponding gold recovery.
The oxygen utilisation was determined by comparing the oxygen injection to the process during the
survey period against the modelled values. The results are shown in Figure 8.
Figure 8 Oxygen utilisation at the GPM Gold Albion ProcessTM Plant
11
Figure 8 shows that the cumulative oxygen utilisation is in excess of the design value of 90%
achieving 93%. This observation is consistent with other multi-tank Albion ProcessTM plants where
it appears oxygen that is dissolved in the first few tanks of the leaching train is utilised later in the
process.
Both Figures 7 and 8 illustrate that the oxygen mass transfer system was correctly and successfully
designed.
CONCLUSIONS
Oxygen injection using convergent-divergent nozzles generate superior thrust and oxygen mass
transfer compared to other gas injection techniques. Power delivered to the system is more efficient
through gas injection rather than mechanical agitation. The HyperSparge TM is a development of the
convergent-divergent nozzle and offers additional advantages over other sparging technologies
contributing to a safer work environment, maximising process run-time and optimising energy
input through the agitator. GT successfully scaled up the oxygen mass transfer system from the
laboratory to the industrial scale at the GPM Gold Albion Process TM plant which achieves greater
than design performance in terms of oxygen mass transfer and oxygen utilisation.
REFERENCES
Hourn, M., & Turner, D.W. (2010). Albion Process for treatment of refractory ores, Proceedings of
ALTA Conference 2010, Perth, Australia.
Hourn, M., & Turner, D.W. (2012). Commercialisation of the Albion Process, Proceedings of ALTA
Conference 2012, Perth, Australia.
Hourn, M., Voigt, P., & Turner, D.W. (2014). Development of the Albion Process plant to treat
refractory concentrates from the GPM Gold Project, Proceedings of Hydroprocess Conference, Vina del
Mar, Chile.
Kawamura, T., Fujiwara A., Takahashi, T., Kato, H., Matsumoto, Y. & Kodama, Y. (2004). The effect
of the bubble size, dispersion and skin friction reduction. Proceedings of On smart control of
turbulence, Tokyo, Japan.
Middleton, J.C. (1992). Gas-liquid dispersion and mixing. In N. Harnby, M.F. Edwards, A.W.
Nienow (Ed.), Mixing in the Process Industries (pp. 322–363).
Middleton, J.C. & Smith, J.M. (1992). Gas-liquid mixing in turbulent systems. In E.L. Paul, V.
Atiemo-Obeng, S.M. Wiley (Ed.), Handbook of industrial mixing: Science and practice (pp. 585–638).
Moo-Young, M. & Blanch, H.W. (1987). Design of biochemical reactors: Mass transfer criteria for
simple and complex systems, Adv. Biochem. Eng., 19, 1–69.
NASA (2015). Nozzle design – converging/diverging (CD) nozzle,
https://www.grc.nasa.gov/www/k-12/airplane/nozzled.html, retrieved January 2017.
Oguz, H., Brehm, A. & Deckwer, W.D. (1987). Gas/liquid mass transfer in sparged agitated slurries,
Chemical Engineering Science, 42, 1815–1822.
Puskeiler, R. & Weuster-Botz, D. (2005). Combined sulfite method for the measurement of the
oxygen transfer coefficient kLa in bioreactors, Journal of Biotechnology, 120(4), 430–438.
12
Senshenko, A.Y., Aksenov A.V., Vasiliev A.A., & Seredkin, Y.G. (2016). Technology for processing
of refractory gold-containing concentrates based on ultrafine grinding and atmospheric oxidation,
Proceedings of IMPC Conference, Montreal, Canada.
Taguchi, H. & Humphrey, A.E. (1966). Dynamic measurement of volumetric O2 transfer coefficient
in fermentation systems, Journal of Fermentation Technology, 44, 881–889.
Van’t Riet, K. (1979). Review of measuring methods and nonviscous gas-liquid mass transfer in
stirred vessels, Ind Eng Chem Process Des Dev, 18, 357–364.
Vasconcelos, J.M.T., Alves, S.S., Nienow, A.W. & Bujalski, W. (1998). Scale-up of mixed gassed
multi-turbine agitate vessels, Canadian Journal of Chemical Engineering, 76, 398–403.
Voigt, P., Hourn, M., Mallah, D. & Turner, D.W. (2015). Commissioning and ramp up of the Albion
Process at the GPM Gold Project, Proceedings of World Gold Conference, Johannesburg, South Africa.
Voigt, P., Hourn, M. & Mallah, D. (2016). Treatment of low grade materials, Proceedings of MINEX
Conference, Moscow, Russian Federation.
13
Advanced Control System to Maximize Copper
Recovery in Heap Leaching Operations
Francisco Troncoso1, Jorge Menacho1, Cristian Domínguez1, Víctor Cabezas1, Patricio
Camacho1 and Adrián Freitte2
1. De Re Metallica Ingeniería, Chile
2. Emerson, Chile
ABSTRACT
A novel advanced control system (SCA DRM system) aimed to optimize heap leaching operations is
described in this paper. The SCA DRM system is part of the autonomous Smart leaching solution
owned by Emerson, which also includes wireless field instrumentation and wireless communications
as well as a regulatory control system drived by expert strategies to ensure uniform irrigation of the
available flowrates throughout the heaps.
The SCA DRM system acts as a metallurgical brain of the overall automatic control system and it
incorporates three optimizing control strategies based upon a decision tree and a phenomenological
dynamic model. The first strategy, named the hydraulic strategy, controls the overall flowrates to
keep hydraulic stability throughout the circuit, whereas the second strategy keeps the copper
concentration in the pregnant leach solution (PLS) within a controlled band by handling individual
heap influent and effluent flowrates. The third strategy, also called the metallurgical strategy, selects
the best operating conditions that dynamically optimize the copper recovery and acid consumption
or alternatively, reduce the leaching cycle extent to enlarge the capacity of the existing facilities. Each
irrigated unit at any time can be either under wetting condition or under permanent irrigating state.
The permanent state can be a continuous or on/off irrigating condition.
Comprehensive FAT and CAT tests were carried out to fully verify the correct interaction between
the DeltaV distributed control system of the Smart leaching solution and the SCA DRM system,
operating either under normal condition or under on-demand condition.
Leach cycle dynamic simulations show improvements of 2 to 4 percent points in copper recovery and
2 to 4 kg/t of less acid consumption when the heap operation is optimized by using the SCA DRM
system incorporated into the Smart leaching solution, as compared to the same heap leach performance
without the SCA DRM system.
1
INTRODUCTION
An integral solution on instrumentation and automatic control for heap leaching operations has been
recently developed by the Emerson Center of Excellence. This incorporates a novel Advanced control
system called SCA DRM system, aimed to optimize throughput, efficiency and productivity of the
leach operation thus passing from the former Regulatory control system (Smart Leaching version 1.0)
to an advanced and optimizing control system (Smart Leaching version 2.0).
Field equipment and instruments communicated through Wireless technology as well as special
controllers and application stations, are also part of this integral solution (Barrientos, 2016). The
DeltaV distributed control system, the Expert regulatory control system and the Advanced SCA DRM
control system are all host in the application station.
De Re Metallica Ingeniería SpA is an engineering consulting firm centered in metallurgical process
innovation and industrial services and it has been invited by Emerson to incorporate their Advanced
hydrometallurgical control system into the Smart leaching solution. The novel SCA DRM system
supplies optimal irrigation strategies based in the mining and metallurgical characteristics of the ores
under processing and also considering the historical application calendar effectively applied to each
irrigating unit.
The new version 2.0 of the Smart leaching solution is currently under industrial evaluation in a specific
large copper operation in the North of Chile (Beta Site).
ADVANCED CONTROL SYSTEM (SCA DRM)

The advanced control system developed by DRM contains a hydrometallurgical Expert control system
and a phenomenological and dynamic Bio-hydrometallurgical model. Both together are permanently
evaluating and defining the optimal irrigation conditions at each controlled leach pad along the
whole irrigating cycle. An OPC communication module is also part of the system and it allows
communication with the Regulatory irrigation control system host in the DeltaV platform and
additionaly, with the field instrumentation using the Wireless Hart protocol. Figure 1 illustrates the
main components of the SCA DRM system and the Smart leaching solution 2.0.
Figure 1 Main components of the SCA DRM system and the Smart leaching solution 2.0
The advanced control system is oriented to satisfy three specific control tasks under dynamic
conditions along the whole leach cycle. The first task is to reach the hydraulic stability across the
2
overall leach circuit. The second task is related to produce a PLS stream with appropriate copper
levels as required by the SX plant and the third task is oriented to get optimal metallurgical results.
The last task considers the chemical and physical characteristics of the stacked ores, the metallurgical
characteristics of individual type of ore and also the existing and previously applied conditions to
each irrigating unit along the time.
The above-described control strategies are codified into a decision tree thus settling the metallurgical
Expert control system as part of the SCA DRM system.
Accordingly, the decision tree is a comprehensive set of metallurgical rules based on fundamentals
and especially on the operational know how of the leaching practice. The Bio-hydrometallurgical model
simulate leaching scenarios and provides quantitative information to take optimal decisions, either
related to the irrigation plan to be applied on each controlled unit and also the optimal manipulation
of effluents.
The Bio-hydrometallurgical model is a dynamic and phenomenological type model with highly
predictive characteristics. It is based on transport phenomena and leaching kinetics. Operational and
process variables are carefully included thus giving close estimation of the real response of individual
pads and the response of the overall leaching plant. The Bio-hydrometallurgical model is a generic
model which can be easily adapted to other leaching practices like the Acid leaching and the Chloro
leaching modes applied either to heap leaching or to dump leaching of sulphide and oxidated ores.
The Smart leaching solution will be tested on industrial scale in the “Beta test” to be performed in a
large Chilean leaching plant. The instrumentation and control system will be set in 1 strip out of 44,
that is, in about 2.3% of the total irrigation area.
The metallurgical control loop will be the only strategy to be considered in this application as the
other control strategies require instrumentation and control in the overall leaching plant. Each of the
eight modules constituting the test strip will be instrumented and controlled.
The irrigation plan is the main result of the metallurgical control strategy. This plan is applied to each
irrigation unit in the form of a pulse calendar applied on daily basis.
Two different states at each irrigating unit are identified, namely, (i) The initial wetting step and (ii)
The continuous irrigation step after the wetting step. This is illustrated in Figure 2 below.
3
Figure 2 Block diagram according to the metallurgical control loop
The irrigating plan when the initial wetting step is applied depends mainly on physical quality of the
ore stacked on each module because permeability is strongly dependent on the physical quality of
the ore.
The irrigation plan after the wetting step is a function of the copper grade, solubility ratio,
mineralogy, composition of the gangue material, size distribution and plasticity index, among others,
but also it depends on the actual hydro metallurgical response along the time monitored through (i)
Actual grades, (ii) Actual leaching ratio and (iii) Actual recovery of copper at each irrigating unit.
The dynamic behavior of the blocks is represented by means of the Bio hydrometallurgical model
(Troncoso, Cabezas & Menacho, 2014). This is initially calibrated according to the real behavior of the
different ores shown at industrial scale along an appropriate time. The last one is mainly chosen
according to the extension of the leaching cycle.
SCA DRM Functionalities

The SCA DRM system can operate mainly under two functionality modes: (i) Normal condition and
(ii) On demand condition.
4
SCA Normal Condition
Under normal condition (NC) calculation of the irrigation plan, namely, the application rates and
pulse calendar is performed once a day (day ‘’i’’) and it is employed to estimate conditions to be
applied in the next day (day ‘’i+1’’).
The dynamic operational conditions and actual hydrometallurgical response are considered when
performing the calculations. Values of the monitored and discrete variables are averaged along the
time from the instant when calculations are performed and the 24 hours before. This strategy is
illustrated in Figure 3.
Figure 3 Calculation strategy of the SCA operating under normal condition
SCA On Demand Condition

The SCA automatically adopts the on demand (ODC) condition when an alarm is received from the
DeltaV system and immediately an alternative irrigation plan is calculated (application rates and
pulse calendar) to be applied from the instant when the alarm sounds and it is kept the rest of the
day unless new on demand events happen.
Each alarm means recalculate the irrigation plan at each controlled unit. This is performed
considering the initial irrigation plan set on each unit for normal condition and the new not planned
scenary at the plant. This strategy is illustrated in Figure 4 below.
Figure 4 SCA strategy when operating on demand mode
5
SCA DRM Architecture
Current version of the SCA DRM system includes an executable computer application having the
previous described control strategies, a data base (SQL Server Express) to keep and exchange data
and also an OPC server (Matrikon OPC GDA, ‘’OPC Server for General Database Access’’) to permit
connectivity with the DeltaV system (OPC Mirror), by using an OPC communication protocol
(‘’Object Linking and Embedding for Process Control’’).
The SCA DRM system is programed in WPF (‘’Windows Presentation Foundation’’) and C#.Net (‘’C
Sharp.Net’’) using Microsoft Visual Studio® (2013 Professional version) and it is executed on a
Microsoft Windows Server® platform (2008 R2 Standard 64 bit). Changes in programing can be easily
performed to provide updated applications if required.
The user interacts with the SCA DRM system by means of a graphical interface (GUI window form
type) to save and read data, as well as to read the optimizing recommendations.
The SCA DRM system is virtualized from the hardware viewpoint by means of the Oracle VM
VirtualBox in a dedicated server (Application Station), provided with monitor, keyboard and mouse.
An external hard disk allows the back up of the virtual machine.
The above-described architecture is illustrated in Figure 5.
Figure 5 Architecture of the SCA DRM application
METHODOLOGY
Integration of the SCA DRM with the DeltaV Distributed Control System and the
Industrial Leaching Heap
As mentioned before, the advanced control SCA DRM system is part of the integral Emerson Smart
leaching solution for the automation and optimizing control of heap leaching plants.
6
This solution considers equipment and instruments connected by means of Wireless technology
(Wireless Hart protocol) to monitor and control the heap leaching operation, provided with an
application station where the regulatory and advanced control systems are host.
The instrumentation considered on each of the 8 blocks of the assigned strip for the Beta Test is as
follows:
 Flowrate, pressure and temperature instruments are installed in the irrigation pipe feeding
the controlled strip.
 Flowrate and pressure instruments at the entrance of each block on the controlled strip.
 Control valves to regulate the entrance pressure for the on/off operation) properly installed
in the irrigation pipe feeding each controlled block.
 Monitoring devices to measure the phreatic level and temperature inside the test strip
installed in specific drilling holes.
The Emerson DeltaV distributed control system drives monitoring all the field instruments and also
the control of the actuators linked to the pressure regulating valves installed on the test strip.
The hydrometallurgical control is performed by the SCA DRM system. This gives optimizing
recommendations consistent with the daily irrigation plan in each of the 8 controlled blocks in the
testing strip. These irrigation plans are sent to the DeltaV system through OPC communication and
it is then executed by activation of the actuators in the control valves. In the same way, all monitored
data collected by the field instrumentation and transmitted to the DeltaV system, is then sent to the
SCA DRM also through OPC communication.
The test strip is part of the whole industrial heap where a mixed copper ore is leached for over 3
hundred days. The leaching cycle is a two-stage mode, first an intermedia solution is applied for a
period and then rafinatte solution coming from the SX plant is applied up to the end of the cycle.
Figures 6 and 7 show the general arrangement of equipments and instruments over the test strip
above-described as well as the general integration of the participant into the system.
7
Figure 6 Instrumentation in the test strip
Figure 7 Integration SCA DRM – DeltaV – Industrial test strip
8
RESULTS
CAT Tests
Comprehensive FAT and CAT tests were developed by DRM and EMERSON professionals directed
toward checking the correct behavior of the SCA DRM system and its interaction with the DeltaV
distributed control system.
Data coming from the field instrumentation considered in the normal operation of the test strip was
simulated by the DeltaV system. This data was wireless sent to the SCA DRM system through OPC
communication and the SCA DRM system estimated the daily irrigation plan and sent it back to the
DeltaV system also by the OPC wireless communication system in order to actuate on the control
valves installed on each of the 8 blocks of the test strip. The whole procedure was successfully applied
over a simulated leach cycle.
Performance of the integral control system operated under alarm condition was then simulated.
Alarms on demand were simulated by the DeltaV system and then sent them to the SCA DRM system
through OPC wireless communication. Procedures to operate on demand mode were activated in the
SCA DRM system and updated irrigation plans were calculated and sent them back to the DeltaV
system through the OPC wireless communication. Finally the DeltaV system closed the control loops
by means of the actuators on the individual control valves located at the entrance of the 8 blocks of
the test strip.
The irrigation plans recommended by the SCA DRM system, either under normal or on demand
condition, were correctly calculated and correctly executed by the DeltaV system. It is worthwhile to
note that the irrigation pulses represent synchronized opening and closing of the control valves on
each controlled block and consequently it requires the unequivocal execution performed by the
DeltaV system.
It is also important to note that simulations under controlled condition allow estimating about 2 to 4
additional percent points in copper recovery when the Smart leach solution is applied.
The window showing the SCA DRM system recommendations is shown in Figure 8.
Figure 8 Window showing the recommended irrigation plan given by the SCA DRM system
9
Validation Tests
A practical validation of the autonomous Smart Leach solution owned by Emerson is starting within
a program called “The Beta test” with all instrumentation and control system as described above in
this paper. Two similar industrial strips will be compared, that is, the controlled test strip and the not
controlled reference strip.
CONCLUSIONS
During the FAT and CAT tests the interaction between the SCA and Delta V systems by means of
OPC Wireless communication protocols demonstrated to be an open and robust solution to drive
interplay between different computer applications set on different platforms.
In the same way, the irrigation plans recommended by the SCA DRM system were unequivocally
executed by the Delta V through the actuators of the control valves.
Simulated results over the leaching period show significant increase in the copper extraction
preliminary estimated in the range of 2 to 4 additional percent points when the Smart leach system 2.0
is applied.
The following conclusions arise from the validation through the FAT and CAT tests:
 The existing SCA DRM system is completely operative when integrated to the Emerson Smart
leaching system aimed to monitor and control heap leaching plants under optimizing
conditions.
 A high performance standard and robustness of the field instrument measuring system as
well as the optimizing control system is secured when the Wireless Hart protocol is
employed.
 Higher metallurgical performance is expected when the Smart Leach system is applied,
namely, irrigation uniformity índices over 85%, 2 to 4 kg/t of less acid consumption and also
increase in about 2 to 4 additional percent point in the copper recovery can be reached.
 The increase in the kinetic response can be employed to reduce extension of the leaching cycle
in the range of 10% to 20%.
REFERENCES
H. Barrientos, “Smart Wireless Solutions: Process Control and Variables Monitoring in a Leach Pad
Operation”, HydroProcess 2016 – 8th International Seminar on Process Hydrometallurgy, 2016.
F. Troncoso, V. Cabezas and J. Menacho, “Bioleach: New Production Planning Simulator”,
HydroProcess 2014 – 6th International Seminar on Process Hydrometallurgy, 2014.
10
Oxidation Plant Optimization at Empresa Nacional
de Minería
Manuel Carmona, Luis Collao, Miguel González and Gleny Espinoza
ENAMI, Chile
ABSTRACT
At present there is a decrease of oxidized mineral resources, this added to the low in the price of
copper, obliged the industry to perform a complete revision of its costs and improvements in the
processes, reviewing the operational control and the variables that allow an optimization in the
recuperation.
The most complex variable that is handled in the ENAMI processes is the mineralogical diversity,
which contains the mineral ores that the mining producers give in the purchasing powers. This
causes disturbances in the process circuits, where the rest of the variables (pH, sulfation,
concentrations, extractant, degree of release, cycle time, current density, etc.) must interact in such a
way that copper recovery is The highest possible.
In order to deal with this scenario, Plant Management has generated, within the framework of
ENAMI's strategic plan, a metallurgical optimization plan which aims to optimize the metallurgical
parameters of its processes.
The present work shows an analysis of the variables of leaching, chemical and mineralogical studies
and leaching tests which mission is to maximize metallurgical recovery.
The metallurgical optimization was carried out with the geometalurgical evaluation of the minerals
received, classifying them in mines according to their monthly delivery, carrying out the
representative samples according to this classification, their chemical and mineralogical analyzes,
laboratory, pilot and its industrial validation.
The operational control of each variable of the operation and the action plan for the modified
variables to maximize the recovery.
1
Development of a Geometallurigcal Model for the
Oxides of Mantoverde, Chile
Ximena Madariaga1, Javier Pizarro2, Romke Kuyvenhoven2 and Orlando Rojas3
1. Mantos Copper, Chile
2. Empírica Consultores, Chile
3. Geoestima, Chile
ABSTRACT
Mantos Copper has embarked on the development of a geometallurgical leach model for its oxides
at the Mantoverde operation, as part of its strategy to improve orebody knowledge and operational
performance. Mantoverde is located in the region III in Northern Chile. Copper oxide ore is
processed through a LX-SX-EW process, with a production rate of 52.000 tons of fine copper per
year.
The main objective of the geometallurgical model is to populate the Mantoverde block model with
metallurgical parameters for Cu extraction, acid consumption and the potential generation of fine
material, in order to predict the metallurgical behaviour of the ore. As such, the model can
contribute to the optimization of the mine plan, specifically in those areas that will be exploited
during the next five years.
The data used for this model originate from a total of 4,972 drill cores, equivalent to 880,829 meters.
With respect to metallurgical data, data were used from a total of 237 iso-pH bottle roll tests.
Additionally, a total of 217 samples that were analyzed by QemSCAN were included in the study.
The result of this study is a geometallurgical model of the complete orebody that is based on the
data from drill cores and the surface mapping, considering structures, lithology, gangue
mineralogy and mineralized zones. The copper extraction and acid consumption can now be
estimated as a function of the geometallurgical unit to be processed in the plant.
1
CHAPTER 4
Leaching and
Bioleaching of Sulfide
Concentrates and
Minerals
Compatibility and Enhancement of Bioleaching of
Primary Copper Sulfide Ore in the Presence of
Chloride
Patricia Piña, Yasna Gallardo and Roberto Bobadilla-
CodelcoTech, Chile.
ABSTRACT
Industrial hydrometallurgical processes using copper oxides and mixed oxide/sulfide usually exhibit
high concentrations of several ions in their raffinates that hinder the transition to the treatment of
copper sulfides, where the optimized biohydrometallurgical copper extraction process can be
strongly affected by such ionic impurities. In the case of chloride ion, the presence of Atacamite
(Cu2Cl(OH)3) and the use of brackish/saline water, are some of the causes to reach toxic
concentrations for mining microorganisms. Up to date, despite several chloride-tolerant
(halotolerant) acidophilic microorganisms have been found, most of them have slow ferrous iron
oxidation kinetics in presence of chloride ion, or showed low cupric ion resistance. In this context,
BioSigma achieved to isolate the autotrophic bacterial strain Leptospirillum sp. RGM 2261, named
Likallfu, capable of oxidizing Fe(II) under aerobic conditions in the presence of chloride ion
concentrations up to 7g/L, which implies a resistance 3.5 times higher with respect to the collection
strain Leptospirillum ferrooxidans ATCC 29047. Low grade (0.35% Cu) primary copper sulfide ore (36%
Chalcopyrite, 24% Chalcocite, 2% Covellite, 37% Bornite, 1% Tennantite) column bioleaching assays
with strain Likallfu under mesophilic conditions in the presence of chloride ion (5 g/L) showed a 53%
increment in copper recovery compared to controls without inoculation and inoculated with L.
ferrooxidans ATCC 29047, showing the remarkable benefits of strain Likallfu to transform
hydrometallurgical operations with the presence of chloride ion into optimized
biohydrometallurgical copper extraction processes.
1
INTRODUCTION
During 2015 18.7 million tons of copper were produced in the world, of which about 80% comes from
pyrometallurgical grinding-flotation-smelting processes, with high consumption of water and
energy. However, due to the sustained low copper grades undergone by the deposits, the application
of pyrometallurgical technologies in many cases is becoming non-economically viable. Due to its
lower investment and operating costs, the use of hydrometallurgy and in particular of
biohydrometallurgy or bioleaching, makes technically and economically feasible the extraction of
copper from resources that are not exploitable through the pyrometallurgical process. Although
conventional hydrometallurgical technologies are very efficient in recovering copper from oxides,
bioleaching allows the achievement of not always profitable efficiencies from copper sulfides.
Considering that more than 90% of the world's resources and reserves of copper are in the form of
primary sulfides, it is imperative to develop competitive bioleaching technologies for the recovery of
copper from this type of minerals. In this regard, current bioleaching technologies are based on the
recirculation of industrial refining solutions through mineral heaps or dumps, promoting the
development of native microorganisms capable of generate and recycle the leaching agents such as
sulfuric acid and ferric ion (Fe (III)). However, most of the bioleaching processes currently in
operation show that the development of native microbial flora is slow (Tupikina et al., 2014) and on
the other hand that solutions in recirculation reach a high ionic charge that inhibits said microbial
activity, phenomena that significantly reduce the recovery kinetics of copper and in many cases limit
its final extraction, which translates into processes that are not economically profitable (Davis-Belmar
et al., 2014).
On the other hand, the development of life in environments of high ionic strength has originated
through several evolutionary processes. Halotolerant microorganisms are characterized by tolerating
salt concentrations above 0.2 M. These microorganisms include bacteria and archaea that are not
common among acidophilic microorganisms, so there is a lack of bioleaching processes in the
presence of solutions with high ionic strength.
An important element that interferes with the functioning of acidophilic microorganisms in general
is the increase in chloride ion concentration in the bioleaching processes. Chloride is an abundant ion
in mining processes, and particularly in those with water shortages, where it is associated with the
recirculation of solutions in the presence of oxidized copper species such as atacamite. To date,
although some acidophilic halotolerant microorganisms have been found, they do not present rapid
kinetics of iron (II) oxidation, so that they have a very limited utility for biomining processes. In this
respect, it has been reported that the specific presence of chloride ion inhibits the iron (II) oxidation
by biomining microorganisms (Gahan et al., 2010) and that the adaptation of this type of cultures to
higher concentrations of chloride ion is highly restricted (Shiers et al., 2005).
In this study we aim to demonstrate the potential of the bioleaching technology developed by
BioSigma to efficiently recover copper from primary sulfide ore in presence of chloride ion using
microorganisms able to tolerate this toxic ion.
2
METHODOLOGY
Strains and growth conditions: The microorganisms used in this study were Leptospirillum sp. RGM
2261, named Likallfu (microbial strain tolerant to chloride ion, isolated in this study and deposited
for patenting purposes) and Leptospirillum ferrooxidans ATCC 29047 (collection strain sensitive to
chloride ion) both grown in KMD medium (990 mg/L (NH4)2SO4,145 mg/L NaH2PO4·H2O, 52 mg/L
KH2PO4, 100 mg/L MgSO4·7H2O, and 21 mg/L CaCl2), supplemented with 9 g/L iron Fe(II) and 5g/L
chloride ion as NaCl for the case of Likallfu. All cultures were incubated at 30 °C with initial pH 1.6.
Minimum inhibitory concentration (MIC): Minimum inhibitory concentration (MIC) assays were
performed in six-well plates with 5 mL of KMD culture medium inoculated with 1x10 7 cells / mL and
incubated with shaking at 20 or 30 ° C and initial pH 1.6. Concentrations of 0 to 10 g/L of chloride ion
(added as NaCl or KCl), or Al (III) (added as Al 2 (SO4)3 • 18H2O) were assayed and evaluated for
growth by optical counting and iron oxidizing activity for Leptospirillum sp. RGM 2261 strain Likallfu
and Leptospirillum ferrooxidans ATCC 29047.
Microbiological characterization: Identification and quantification of genus of microorganisms in
bioleaching column tests were carried out after DNA extraction by specific quantitative PCR (qPCR)
in the initial inoculation and the final ores.
Chemical characterization: Solutions as well as ores samples were subjected to chemical analysis
during the treatment, including determinations of cupric ion and total iron by atomic absorption
spectrometry (AAnalyst 400, Perkin Elmer), and ferrous iron (Fe(II)) by the o-phenantroline method
(Kolthoff & Sandell, 1963).
Bioleaching assays: Columns 25 cm high with 500 g of low grade (0.35% Cu) primary copper sulfide
ore (36% Chalcopyrite, 24% Chalcocite, 12% Covellite, 37% Bornite, 1% Tennantite; -4#+10# Tyler)
for bioleaching assays were acid conditioned and irrigated in closed circuit with acid water at pH 1.4,
and then irrigated with a solution with 5g/L chloride as NaCl. The microorganisms were added in a
single inoculation through irrigation in a concentration of 1x107 microorganism /g of ore. Assays were
incubated at 30 °C.

As previously stated, halotolerant microorganisms are not common among acidophilic
microorganisms, and chloride ion is perhaps one of the most inhibitory compounds for microbial
iron-oxidizing activity. Therefore, the first step was to test the advantages of the isolated strain
Likallfu compared to a collection strain from the same microbial genus. Based on MIC assays,
Leptospirillum sp. RGM 2261 strain Likallfu showed a 3.5 times higher resistance to chloride ions
(added as sodium chloride) at 30 ° C compared to Leptospirillum ferriphilum ATCC 29047 collection
strain.
Column bioleaching assays with primary copper sulfide ore showed that the condition with
inoculation of strain Likallfu started with ferric production very early (day 6), reaching ORP values
over 600 mV, despite the presence of chloride ion. On the other hand, sensible strain L. ferrooxidans
ATCC 29047 did not show significant iron oxidation activity keeping an ORP below 500 mV through
the entire assay (Figure 1). This confirms the ability of strain Likallfu to oxidize ferrous ion in the
presence of chloride not only in liquid culture but also during the bioleaching process, something
that has not been reported for other Leptospirilli.
3
With respect to copper recovery, strain Likallfu presented a clear advantage being able to recover
53% more copper in the presence of chloride ion compared to the collection strain (23% copper
recovery with strain Likallfu vs. 15% copper recovery for strain ATCC 29047 at day 35). This is more
notorious when comparing the copper recovery with the control without inoculation, where only
strain Likallfu shows a significant difference being 64% more efficient (Figure 2). The collection strain
ATCC 29047 showed only an increment of 1% (7% more efficient) been not significantly different
from the control with no inoculation.
Based on the previous results, the use of strain Likallfu shows remarkable benefits to transform
hydrometallurgical operations with the presence of chloride ion into enhanced
biohydrometallurgical copper extraction processes.
Table 1 Comparison of liquid culture Minimum Inhibitory Concentration (MIC) values for strains
used in this study
Al(III) Chloride (KCl) Chloride (NaCl)

Bacterial strain [g/L]
20 °C 30 °C 20 °C 30 °C 20 °C 30 °C
Leptospirillum sp. RGM 2261 strain Likallfu 5 10 8 8 7 7
Leptospirillum ferrooxidans ATCC 29047 n.d.* n.d. n.d. n.d. n.d. 2
*n.d.: not determined.
700
650
ORP(Ag/AgCl) [mV]
600
550
500
450
400
350
300
0 10 20 30 40
Time [days]
Figure 1 Oxidation-Reduction Potential (ORP, Ag/AgCl) in bioleaching assays on columns of primary sulfide
ore (36% Chalcopyrite, 24% Chalcocite, 12% Covellite, 37% Bornite, 1% Tennantite) with 5 g chloride / L ion,
incubation at 30 ° C and addition of Leptospirillum sp. RGM 2261 strain Likallfu (■); Leptospirillum ferrooxidans
ATCC 29047 (▲); Control without inoculation (♦).
4
30%
25%
% Copper Recovery
20%
15%
10%
5%
0%
0 10 20 30 40
Time[days]
Figure 2 Cu (II) recovery in bioleaching assays on columns of primary sulfide ore (36% Chalcopyrite, 24%
Chalcocite, 12% Covellite, 37% Bornite, 1% Tennantite) with 5 g chloride / L ion, incubation at 30 ° C and
addition of Leptospirillum sp. RGM 2261 strain Likallfu (■); Leptospirillum ferrooxidans ATCC 29047 (▲); Control
without inoculation (♦).
The use of strain Likallfu in heap or dump bioleaching operations opens the possibility of improving
the bioleaching process in a fresh water scarcity scenario and/or the use of sea water, avoiding sea
water pretreatment, and taking advantage of the leaching properties of chloride ion.
CONCLUSIONS
The new isolated bacteria Leptospirillum sp. RGM 2261 strain Likallfu significantly enhances the
bioleaching of primary sulfide ore, being able to recover 53% more copper in the presence of chloride
ion compared to the collection strain ATCC 29047.
ACKNOWLEDGEMENTS
REFERENCES
Davis-Belmar, C., Cautivo, D., Demergasso, C. and Rautenbach, G. (2014). Bioleaching of copper
secondary sulfide ore in the presence of chloride by means of inoculation with chloride-tolerant
microbial culture. Hydrometallurgy, 150, pp.308-312.
5
Gahan, C., Sundkvist, J., Dopson, M. and Sandström, Å. (2010). Effect of chloride on ferrous iron
oxidation by a Leptospirillum ferriphilum -dominated chemostat culture. Biotechnology and
Bioengineering, p.n/a-n/a.
Kolthoff, I. and Sandell, E. (1963). Quantitative inorganic analysis. 1st ed. Belgrado.
Shiers, D., Blight, K. and Ralph, D. (2005). Sodium sulphate and sodium chloride effects on batch
culture of iron oxidising bacteria. Hydrometallurgy, 80(1-2), pp.75-82.
Tupikina, O., Minnaar, S., Rautenbach, G., Dew, D. and Harrison, S. (2014). Effect of inoculum size
on the rates of whole ore colonisation of mesophilic, moderate thermophilic and thermophilic
acidophiles. Hydrometallurgy, 149, pp.244-251.
6
Bioleaching of Enargite: Copper Recovery with
Microorganisms from Arsenic-containing Ores
Patricio Martínez and Roberto Bobadilla
CodelcoTech, Chile
ABSTRACT
Enargite (Cu3AsS4) is a primary copper sulfide mineral found associated with other minerals such
as chalcopyrite and bornite, among others. In Chile, enargite can be found in several mining sites,
especially in the north region (Atacama and Antofagasta). A major drawback is that enargite
contains arsenic, and that it cannot be efficiently separated by froth flotation from other copper
sulfides, generating the so called complex copper concentrates, which are very restricted to be
treated by smelting facilities due to toxic arsenic emissions. Currently, toasting has been the pre-
treatment alternative to reduce its arsenic content. On the other hand, there are no industrial
hydrometallurgical processes to leach enargite, and few studies of bioleaching of this primary
copper sulfide are available. In this work we evaluated the use of BioSigma-SBP® technology to
bioleach copper from primary mixed sulfide ore (2% Cu) with high enargite content (70% of the
copper present), including control conditions without addition of microorganisms to compare with
native micro flora. Lab-scale bioleaching assays in column replicates were operated in closed-circuit
at ambient temperature for up to 84 days, analyzing the microbial, mineralogical and chemical
parameters at the ore and the PLS. The results showed a 51% copper recovery from BioSigma-SBP®
treated ore, compared to 30% with the non-inoculated control. Moreover, the arsenic recovery was
more than 4 times higher in the BioSigma-SBP® compared to the control. This result was confirmed
by QEMSCAN mineralogical analysis of the treated ore which showed that 37% of the enargite was
bioleached at day 84. Finally, the microbial analysis of the treated ore surface shows that
Leptospirillum, Acidithiobacillus and Ferroplasma microbial genera tolerated the arsenic released.
These results show that bioleaching is a feasible technology to recover copper from high arsenic-
containing ores.
1
INTRODUCTION
The most abundant arsenic sulfide minerals on our planet are realgar (As4S4), orepiment (As2S3),
enargite (Cu3AsS4), tennantite (Cu12As4S13) and arsenopyrite (FeAsS). For unknown geological
reasons, enargite is the primary copper arsenic sulfide mineral found mostly in the deposits of the
Andean range. The presence of this type of minerals, mainly in the copper mining operations in the
north of Chile, has been increasing through the evolution of the exploitation of the deposits due to
deeper mining, as well as in new mining operations, becoming an environmental problem due to
the detrimental effects of arsenic in the environment and on human health (Mandal and Suzuki,
2002). The previous together with the every time more stringent limits to arsenic emissions from
smelting processes among other downstream operation restrictions, are making the copper
extraction from enargite a complex task.
Considerable research has been devoted to hydrometallurgical alternatives for enargite processing
including acid and alkaline leaching. In particular, the observation that the presence of iron-
oxidizing microbial activity accelerates enargite oxidation and leaching under acidic conditions
(Lattanzi et al., 2008) has somehow changed the perception of the narrow spectrum of bioleaching
processes, showing that bioleaching can be extended to arsenic bearing ores. The background data
has demonstrated that bioleaching is an extremely efficient process in industrial heaps for
secondary copper sulfides such as chalcocite (Cu2S) and covellite (CuS) (Montealegre, 1993). More
recently, our company has demonstrated the feasibility of industrial–scale bioleaching of low-grade
primary sulfide ores at run-of-mine (ROM) size, including bornite (Cu5FeS4) and chalcopyrite
(CuFeS2) (Parada and Bobadilla-Fazzini, 2014). With respect to enargite bioleaching, few studies are
available, being the majority performed with enargite concentrates (Corkhill et al., 2008; Escobar et
al., 2000; Escobar et al., 1997; Sasaki et al., 2010a) and the minority with enargite-containing ores
(Lee et al., 2011), and mainly focused on high temperature (thermophilic) treatments (70 °C). The
present work aims to demonstrate the feasibility of the use of ambient temperature (mesophilic)
bioleaching as an efficient process for the recovery of copper from arsenic-containing ores and
particularly from ores with high content of enargite.
2
METHODOLOGY
Mineral sample: The mineral sample came from the Antofagasta region in the north of Chile. The
sample was sieved in one fraction of -4# +10# (Tyler) using a vibrating sieve system (AS300, Retsch),
and sub-sampled with rotary cutter equipment (DR-20C, Labtech). Chemical analysis showed that
the fraction contained 2.08% CuT (0.02% soluble) and 0.35% As. QEMSCAN – Bulk Mineralogical
Analysis indicated that copper sulfides were distributed as 70% enargite, 16% chalcopyrite, 6%
bornite and 8% chalcocite.
Strains and growth conditions: The consortium used in this study (BioSigma-SBP®) was isolated
by BioSigma S.A. and grown in KMD medium as previously described (Bobadilla Fazzini et al.,
2011), supplemented with iron and/or sulfur (Fe(II), 15-5 g/L; S°, 1-0,2 g/L.
Microbiological characterization: Identification and quantification of microorganisms in column
tests was carried out after DNA extraction by Next Generation DNA Sequencing as previously
described (Caporaso et al., 2010) in effluent solutions and processed ore samples.
Chemical characterization: Solutions as well as mineral samples were subjected to chemical
analysis before, during and after treatment, including determinations of Cu(II), total arsenic and
total iron by atomic absorption spectrometry (AAnalyst 400, Perkin Elmer), and Fe(II) by the o-
phenantroline method (Kolthoff & Sandell, 1963).
Mineralogical characterization:
Polished sections of the original ore as well as processed ore samples were analyzed at different
times by bulk mineralogical analysis (BMA) with QEMSCAN Express® equipment (FEI, USA).
Bioleaching assays: bioleaching assays were done as previously described (Bobadilla-Fazzini et al.,
2016). Briefly, samples of approximately 500 g were agglomerated and packed in 6 cm diameter
acrylic columns and subject to diluted sulfuric acid for 24 h, and later fed with diluted sulfuric acid
solution pH 1.4 in closed circuit. No trace nutrients reduced inorganic sulfur compounds nor iron
was included in the feeding solution at any time. A single initial inoculation of the acidophilic
consortium to the solution was done to reach an initial density of 5,00E+07 cel/g ore just after the
beginning of the close circuit feeding. All columns were incubated at 30 °C under non-sterile
conditions. The pregnant leaching solution (PLS) obtained in closed circuit was periodically
sampled and evaporation was compensated with pure water before each sampling time.
3
Bioleaching is a technology used for the extraction of base metals from ores using microorganisms.
This process can be used to recover copper, zinc, nickel and cobalt, just to mention some. As a
technology in development for its industrial application, several aspects have not been deeply
studied as is the cases of arsenic-containing ores. Former studies have indicated on one hand the
inability of microorganisms to regenerate ferric iron from the enargite surface (Corkhill et al., 2008),
while others showed that enargite dissolution rates for the ferric biological leaching doubled the
ones obtained from chemical ferric leaching, attributing these major difference to biological ferric
ion regeneration and also to the removal of elemental sulfur from the leached mineral surface by
bacterial oxidation to sulfate (Escobar et al., 1997). These contradictory results show that more
research is required in order to clearly assess the potential of bioleaching for enargite. Based on this,
here we develop column bioleaching assays of ore with 70% of the copper sulfide content as
enargite under ambient conditions with mesophilic inoculation. Bioleaching assays were performed
in 30 cm high columns with or without BioSigma-SBP® microbial consortium inoculation.
Metallurgical results (see Figure 1) indicate that the bioleaching with the mesophilic BioSigma-
SBP® consortium reaches a faster and higher copper extraction with a maximum of 51% in 84 days
in contrast to the non-inoculated columns that reached only 30% in 84 days. This was additionally
supported by the arsenic extraction from both conditions, since the inoculated one reached 16% of
arsenic extraction while the non-inoculated condition showed only 3% at the end of the assay (84
days). A previous study performed at 70 °C has shown that high arsenic precipitation as ferric
arsenate is an important drawback for thermophilic enargite bioleaching (Escobar et al., 2000),
something that was not observed in this study being an advantage of bioleaching under mesophilic
conditions (30 °C).
Figure 1 Copper and arsenic extraction kinetics from high enargite-bearing ore during bioleaching assays at 30
°C. (▲) SI: non-inoculated condition, (●) BioSigma-SBP®: inoculated condition.
As can be seen in Figure 1, a major enhancement on copper recovery from high enargite containing
ore is observed in the inoculated case compared to the non-inoculated condition. This observation
allows us to conclude that an arsenic-containing ore and particularly a high enargite ore is
amenable to ambient temperature bioleaching through the use of BioSigma-SBP® technology. This
result is comparable to the copper dissolution (52%) obtained before from enargite concentrate with
thermophilic Sulfolobus BC performed at 70 °C in shake-flasks (Escobar et al., 2000), and more than
4
twenty times higher than the one previously observed for pure enargite with mesophilic bacteria
(2.4% with At. ferrooxidans inoculation) in the presence of the galvanic effect exerted by addition of
activated carbon at 25 °C (Sasaki et al., 2010).
As a consequence of the iron-oxidizing microbial activity of both, inoculated and native
microorganisms, the oxidation-reduction potential increased as a function of time until stabilization
from day 30 on (Figure 2). The oxidation-reduction potential profiles observed under both
conditions allows us to conclude that the iron-oxidizing microbial activity was much less affected in
the BioSigma-SBP® inoculated case under the presence of dissolved arsenic from the ore allowing
an efficient copper recovery, compared to the non-inoculated condition.
Figure 2 Oxidation-reduction potential (Eh (Ag/AgCl)) in the effluent solution from high enargite-bearing ore
during bioleaching assays at 30 °C. (▲) SI: non-inoculated condition, (●) BioSigma-SBP®: inoculated condition.
Microbial analysis of the processed ore samples at different times with or without BioSigma-SBP®
inoculation is shown on Figure 3. As expected, a higher concentration of Leptospirillum species was
observed with inoculation, but also a higher microbial diversity was early formed over the ore
surface compared to the non-inoculated ore.
Figure 3 Ore microbiological dynamics determined by next generation sequencing from high enargite-bearing
ore during bioleaching assays at 30 °C. Left: inoculated condition; Right: non-inoculated condition.
5
An interesting aspect of the ore surface microbial dynamics was the identification of species of the
genus Acidiphilium only in the inoculated condition. This heterotrophic bacterial genus has been
previously linked to the enhancement of the leaching rate of primary copper sulfides when mixed
with other mesophilic leaching microbes, and has been associated to the bioleaching of the
refractory copper sulfide chalcopyrite (Peng et al., 2008). The final ore surface microbial
composition was very similar under all conditions, indicating that the system tends to a similar
microbial equilibrium, and that inoculation transiently affects the ore microbial dynamics.
Nevertheless, microbial inoculation affected the total number of cells attached, being one order of
magnitude higher in the inoculated case at all times.
The results of the mineralogical analysis by QEMSCAN-BMA allowed the detection of an enargite
content of 0.30% in weight. This value is considerably lower than expected from the copper grade
(2.08%), and is explained by the presence of 2% in weight of unclassified copper species;
attributable to enargite and other copper sulfide mineral species with minor surface alterations.
Nonetheless, the mineralogical analysis showed a very high removal efficiency for most copper
sulfides and unclassified mineralogical copper species. In the particular case of enargite,
QEMSCAN-BMA analysis indicated 0.19% in weight for the treated ore at 84 days, implying a
measured 36.9% of bioleaching efficiency as indicated in Table 1. No further QEMSCAN-BMA data
for the non-inoculated sample was gathered considering the lower copper recovery and arsenic
extraction, being endorsed to copper species different from enargite.
6
Table 1 BioSigma-SBP® removal efficiency determined by QEMSCAN-BMA for high-enargite
containing ore.
Mineral species %Removal on treated ore under BioSigma-SBP®
Bornite 25.5%
Chalcopyrite 97.9%
Chalcocite 100.0%
Enargite 36.9%
Covellite 15.1%
Unclassified Cu 65.6%
CONCLUSIONS
Based on the results showed, we conclude that bioleaching is a viable technology to
hydrometallurgically extract copper from high arsenic-containing ores, showing a 51% copper
recovery from high enargite-bearing ore by means of BioSigma-SBP® technology.
ACKNOWLEDGEMENTS
REFERENCES
Bobadilla-Fazzini, R.A., Piña, P., Gautier, V., Brunel, K., and Parada, P. (2016). Mesophilic
inoculation enhances primary and secondary copper sulfide bioleaching altering the microbial &
mineralogical ore dynamics. Hydrometallurgy.
Bobadilla Fazzini, R. a, Levican, G., and Parada, P. (2011). Acidithiobacillus thiooxidans secretome
containing a newly described lipoprotein Licanantase enhances chalcopyrite bioleaching rate. Appl.
Microbiol. Biotechnol. 89, 771–780.
Caporaso, J.G., Kuczynski, J., Stombaugh, J., Bittinger, K., Bushman, F.D., Costello, E.K., Fierer, N.,
Peña, A.G., Goodrich, J.K., Gordon, J.I., et al. (2010). QIIME allows analysis of high-throughput
community sequencing data. Nat. Methods 7, 335–336.
Corkhill, C.L., Wincott, P.L., Lloyd, J.R., and Vaughan, D.J. (2008). The oxidative dissolution of
arsenopyrite (FeAsS) and enargite (Cu3AsS4) by Leptospirillum ferrooxidans. Geochim.
Cosmochim. Acta 72, 5616–5633.
Escobar, B., Huenupi, E., and Wiertz, J. V (1997). Chemical and biological leaching of enargite.
Biotechnology 19, 719–722.
7
Escobar, B., Huenupi, E., Godoy, I. & Wiertz, J., V. (2000). Arsenic precipitation in the bioleaching of
enargite by Sulfolobus BC at 70 °C. Biotechnol. Lett. 22, 205–209.
Kolthoff, J.M., Sandell, E.B. (1963). Textbook of Quantitative Inorganic Chemistry. MacMillan
Publishing Co., New York.
Lattanzi, P., Da Peloa, S., Musua, E., Atzeib, D:, Elsenerb, B., Fantauzzib, M., Rossib, A. (2008).
Enargite oxidation: A review. Earth-Science Rev. 86, 62–88.
Lee, J., Acar, S., Doerr, D.L., and Brierley, J.A. (2011). Comparative bioleaching and mineralogy of
composited sulfide ores containing enargite, covellite and chalcocite by mesophilic and
thermophilic microorganisms. Hydrometallurgy 105, 213–221.
Mandal, B.K., and Suzuki, K.T. (2002). Arsenic round the world: A review. Talanta 58, 201–235.
Montealegre, R. (1993). The Sociedad Minera Pudahuel bacterial thin-layer leaching process at Lo
Aguirre. 11, 231–235.
Parada, P., and Bobadilla-Fazzini, R. (2014). BIOLEACHING OF MINERALS BY ACIDOPHILE
MICROORGANISMS. Encycl. Ind. Biotechnol. 1–12.
Peng, J., Zhang, R., Zhang, Q., Zhang, L., and Zhou, H. (2008). Screening and characterization of
Acidiphilium sp. PJH and its role in bioleaching. Trans. Nonferrous Met. Soc. China 18, 1443–1449.
Sasaki, K., Takatsugi, K., and Hirajima, T. (2010). Several approaches to enhance the bioleaching of
enargite. In XXV International Mineral Processing Congress 2010, IMPC 2010, pp. 487–497.
8
Pre-Treatment with Sodium Chloride and Sulfuric
Acid of a Bornitic Concentrate and Later Leaching In
Chloride Solution
Fabiana Bahamonde, Matías, Gómez and Patricio Navarro
Universidad de Santiago de Chile
ABSTRACT
A study was made to determine the effect of performing a pre-treatment with a mixture of chloride
sodium and sulfuric acid on a concentrate composed mainly of bornite, for copper extraction yield
improvement. The variables to be evaluated are amount of NaCl to be employed and the
conditioning time. Long standing time and high dosage of sodium chloride, increases copper
recuperation. For dosage of 60 Kg NaCl per ton of concentrate, copper extraction reached about 38.2
percent, versus the sample without pre-treatment that only reached 19.7 percent, leaching was
made at 25°C, for 48 hours with a concentration of chloride ion of 60 grams per liter. However for
this high dosage, standing time has not an important effect, because doubling this parameter from
15 to 30 days, only improves the global recuperation in around one percent. Results of scanning
electron microscopy and X ray diffraction, show that at higher standing time and dosage of sodium
chloride, a greater transformation to non-stoichiometric compounds of Cu-Fe-S and sulfates occurs,
probably due to the production of gaseous hydrochloric acid, which helps sulfuric acid to reach the
center of bornite particles. Besides, this analysis doesn´t show the formation of passive sulfur layer.
This improves copper extraction.
1
INTRODUCTION
Most global reserves of copper are found as sulphide phases, around 80% of the copper coming
from deposits is obtained from Cu-Fe-S ores1. Pyrometallurgical processes have been used for the
treatment of copper concentrates, that is, fusion-conversion and electro-refining. However, this
route has proved to be unfriendly to the environment, due to SO2 emissions (gas) and fine
particulate matter suspended during combustion, in addition to having high costs2. For this reason,
research and developments in the search for hydrometallurgical alternatives have been intensified
over the past few years3.
Several studies have been carried out in order to determine the kinetics of leaching of the bornite.
The ferric sulfate/chloride leaching showed to be a complex process, so there is no unanimity in the
reactions involved4–6. Oxidation of the bornite with ferric ion can be divided into two stages. At
first, a rapid removal of copper leads to the formation of a non-stoichiometric bornite, of
formula Cu5−x FeS4 , which would reach a Cu3 FeS4 ideal formula. The formation of chalcopyrite and
other phases has also been reported. In the second stage, this product is further oxidized to Cu2+ ,
Fe2+ y S 0 , occurring this reaction only at elevated temperatures.
Recently the effect of pre-treating a mineral or concentrate with sodium chloride and concentrated
sulfuric acid has been studied, in order to increase copper dissolution in leaching7–10. Particularly,
the pre-treatment applied to a chalcopyrite ore/concentrate showed excellent results after leaching
at 70 ° C in chloride medium, with recoveries close to 100% after 48 hours of process. The addition
of NaCl and sulfuric acid would promote the formation of more soluble polysulfides in aqueous
medium. Also, in the presence of chloride ions, the elemental sulfur layer becomes more porous,
facilitating the diffusion of the reactants to the center of the particle. Such porosity is also favored
by the formation of HCl and sodium sulphates7.
METHODOLOGY
Ore concentrate
A bornitic concentrate was used, with a granulometric distribution of 80% under 72 µm. The
mineralogical species were determined by X-ray diffraction (XRD). Bornite, was the main source of
copper (66.69%), accompanied by a 19.80% of chalcopyrite (CuFeS2 ), a 5.20% of a copper hydroxide-
silicate (Cu5 (SiO3 )4 (OH)2 ) and 7.18% of magnesium calcium silicate (CaMgSi.). Chemical analysis
was performed through atomic absorption spectroscopy (AAS), resulting in 54.46% of Cu.
Pre-treatment and leaching

A concentrate without pre-treatment was leached during 94 hours, with a solution of 60 grams per
liter of chloride ion, this, to evaluate the effect of adding sodium chloride and sulfuric acid before
the leaching.
The experimental conditions considered in the pre-treatment, are presented in Table 1. The amount
of sulfuric acid corresponds to a fraction of the stoichiometric consumption of the copper
concentrate. Samples were left in a shaker-incubator at 25°C, adding water periodically to avoid
drying.
2
Table 1 Experimental conditions for NaCl- H2SO4 pre-treatment
Experimental variables Levels
NaCl dosage [kg/t] 15, 30 y 60
𝐇𝟐 𝐒𝐎𝟒 dosage [%] 30
Humidity [%] 10
Repose time [days] 15 y 30
The samples were washed with distilled water to eliminate residual acidity and then vacuum
filtered and dried at 50°C. Finally, they were observed by SEM microscopy and powder XRD. The
resulting solutions were analyzed through AAS to determine the amount of Cu and Fe solubilized
in water.
RESULTS AND DISCUSSIONS
Leaching of the sample without pre-treatment

A sample of concentrate was leached in a solution with 60 g/L of Cl ion solution, during 94 hours at
25°C. Figure 1 shows that copper is extracted preferably from the bornite, with a minimal
dissolution of iron, occurring this mainly during the first three hours and reaching a maximum of
3.47%. After 94 hours of process, the dissolved mol ratio Cu/Fe reaches a value of 40.24.
3
Figure 1 Kinetics of dissolution of bornite without pre-treatment with 60 g/L of Cl-
Effect of NaCl-H2SO4 pre-treatment

Figure 2 shows the effect of pre-treating the concentrate for 30 days with a mixture of NaCl-H2SO4.
The previous conditioning of the concentrate exhibit a positive effect in copper dissolution, when
leaching in a solution with 60 g/L of chloride ion.
During the first hour of process, the tests show a large increase in the rate of copper extraction
compared to the sample without pre-treatment, this is attributed directly to the dissolution of
soluble species formed during pre-treatment.
It is observed, that increasing NaCl dosage, generates an increase in the amount of soluble copper
species formed during the pre-treatment stage, but once that this species are dissolved, there is no
improvement in the leaching rate.
For dosage of 60 kg of NaCl per ton of concentrate, copper extraction reached a 38.2% compared to
the sample without pre-treatment that only reached a 19.7% after 48 hours of leaching.
4
Figure 2: Effect of NaCl dosage.
Repose time
The effect of conditioning time for samples pre-treated with 30 kg NaCl/ ton is presented in Figure
3. It can be noticed, that doubling the repose time from 15 to 30 days, generates an increase in the
formation of higher solubility species in the concentrate, possibly sulphates, an effect that results in
an increase of 9.74% of copper dissolution in the first hour of leaching.
Figure 3 Effect of reposing time
In experiments performed with 60 kg NaCl / ton the effect of the repose time was minimal,
increasing a 3.13% of copper dissolution in the first hour, and improving recovery by around one
percent after 48 hours of leaching , suggesting a limit on the amount of copper that can be
solubilized from the bornite during pre-treatment.
5
Characterization of samples
Pre-treated samples with 60 kg NaCl / ton for 15 and 30 days were submitted to XRD-SEM analysis,
as well as the rubbles of their leaching. The results of that analysis are summarized in Figure 4.
Bornite
concentrate
NaCl − H2 SO4 Rubble of

leaching
Pre-treatment
15 days of 30 days of
repose repose
Cu5 FeS4 Cu9 Fe9 S16 Cu9 Fe9 S16

CuFeS2 CuFeS2 CuFeS2
Cu2 (OH)3 Cl
Figure 4 XRD Samples Diagram
Chalcopyrite is present in all the samples, being presumably the one that is initially in the
concentrate.
The sample pre-treated during 15 days, doesn´t show changes in the copper sulfides. However, it
dissolved an 8.32% of copper in the previous wash, which would have been in sulphate form.
After 30 days of rest, there is no presence of bornite, which indicates that it has been transformed
into mooihoekite (Cu9 Fe9 S16 ) and a copper chlorate compound (paratacamite). It is expected, that
there was a transformation of bornite into non stoichiometric compounds, in non-easy detectable
percentages. Washing of this sample has a high concentration of copper in solution, which means
that there was a large formation of copper sulphates during pre-treatment. The percentage of
copper dissolution reached 20.15%.
The compound Cu9 Fe9 S16 would be formed as the bornite becomes more deficient in copper and
would have refractory characteristics to the leaching process. This can explain the drastic decrease
in the copper leaching rate, after the dissolution of the copper sulphates formed during the pre-
treatment
6
Weight
Element
percentage
Cu 59,52
Fe 7,44
S 28,87
Weight Weight
Element Element
percentage percentage
Cu 60,54 Cu 67,56
(a)Fe 10,52 Fe
(b)
1,10
S 26,08 S 30,11
Figure 5 SEM analysis for bornitic concentrate a) without pre-treatment (500x); b) pre-treated with 60 kg
NaCl/ton of concentrate and 15 days of repose (10kx)
According to Figure 5, the conditioning affects both copper and iron present in the bornite, so there
is a reduction in the cell parameters of this one, which translates into an effect of cracking. There is
an iron deficiency in the surface reaching a composition close to the coveline. There is no formation
of elemental sulfur, as a reaction product of the pre-treatment for 15 and 30 days of rest.
CONCLUSIONS
 NaCl – H2SO4 pre-treatment, generates an increase in copper dissolution from the
concentrate.
 Higher repose time and NaCl dosage during pre-treatment, lead to an increase in the
formation of more soluble compounds, possibly copper sulphates.
 The sample with 60 kg of NaCl/ton and 30 days of repose time, favors the transformation of
bornite to other compounds of greater solubility. This is observed by the absence of this
mineral in its XRD analysis.
7
REFERENCES
1. Schlesinger ME, king Matthew J, Sole KC, Davenport WG. Extractive Metallurgy of Copper.;
2011.
2. Domic E. Hidrometalurgia, Fundamentos, Procesos Y Aplicaciones.; 2001.
3. Dreisinger D. Copper leaching from primary sulfides  : Options for biological and chemical
extraction of copper. 2006.
4. Pesic B, Olson F. Leaching of bornite in acidified ferric chloride solutions. Metall Trans.
1983:577-588.
5. Dutrizac J, Macdonald R, Ingraham T. The kinetics of dissolution of bornite in acidified
ferric sulfate solutions. 1970;1(January):225-231.
6. Dutrizac J, Chen T, Jambor J. Mineralogical changes occurring during the ferric ion leaching
of bornite. Metall Trans. 1985:679-693.
7. Ibañez J, Ipinza J, Guerrero F, González J, Vásquez J. Cooper concentrate leaching in
chloride-sulfate medium. 2013.
8. Ipinza J, Ibañez J, Flaquer J. Effect of Pretreatment of the Chalcopyrite with NaCl- H2SO4
on Copper Extraction in the Leaching Process. 2015.
9. Quispe N. Estudio electroquímico preliminar del mecanismo cinético de la lixiviacion de la
calcopirita en medio ácido sulfúrico-cloruro de sodio. 2014.
10. Herreros O, Bernal N, Quiroz R, Fuentes G, Viñals J. Lixiviación de concentrados de cobre
utilizando NaCl y el cobre soluble aportado por el mismo mineral. Rev Metal Madrid. 2005:384-392.
8
Environmental Benefits of the CESL Process for the
Treatment of High-Arsenic Copper-Gold
Concentrates
Darren Schwartz1, Vanya Omaynikova2 and Susan Stocker1
1. Teck, Canada
2. Aurubis, Germany
ABSTRACT
The ongoing development and implementation of hydrometallurgy for the processing of copper
concentrates is driven by several factors, including: the increasing trend in global copper
consumption, the increasing development of challenged resources (complex mineralogy, lower
grade ores, deleterious elements), increasingly stringent environmental and occupational health
and safety regulations, and the high cost and limited availability of treatment and refining options
for complex concentrates. The traditional method for processing high-arsenic concentrates is
blending with large amounts of clean concentrate. This is followed by the traditional processing
route of smelting and refining, which results in the generation of an unstable arsenic trioxide
product.
Through a partnership formed in 2009 between Teck, Canada’s largest diversified resource
company, and Aurubis, a leading custom concentrate refiner and the world’s largest copper
recycler, extensive integrated pilot scale tests have been completed using the CESL Process to treat
high-arsenic copper and copper-gold concentrates. The key unit operations of the CESL Process are:
concentrate regrind, oxidative pressure leach with a chloride catalyst, followed by conventional
solvent extraction and electrowinning. For concentrates also containing precious metals, the residue
from the CESL Process is processed through a pressure cyanidation circuit followed by a traditional
precious metals recovery circuit. The result is a sustainable and cost effective process for the
production of high-quality copper cathode and precious metals.
This paper describes the environmental benefits of the CESL Process for the treatment of high-
arsenic copper and copper-gold concentrates in comparison to traditional processing routes. The
CESL Process provides tangible environmental benefits to water, air, climate and soil such as:
decreased fresh water consumption; decreased particulate (as arsenic trioxide) and sulfur dioxide
emissions; decreased greenhouse gas emissions; and decreased unstable arsenic species for ground
disposal.
1
INTRODUCTION
About 80% of the copper ore reserves are found in porphyry deposits and about half of those
contain arsenic-bearing minerals (Schwartz, 1995). Approximately 60% of the 306 copper mines in
operation today contain some level of arsenic (WoodMac, 2016). Increasing arsenic levels presents
an emerging challenge for the mining and smelting industry. Many existing deposits that produced
clean concentrates a few years ago are now facing arsenic levels above the penalty limit of 0.2%, as
shown in Figure 1.
Figure 1 Trend of select mines with >0.2% arsenic in copper concentrates
Two mines that recently started operations, Toromocho (Peru) and Mina Ministro Hales (Chile), are
distinguished by appreciable arsenic contents, 1.3% and 3.6% in concentrate, respectively
(WoodMac, 2016). Many large development projects such as La Granja (Peru), Quellaveco (Peru),
Frieda River (Papua New Guinea), and Cañariaco Norte (Peru) are also reported to contain arsenic
(Schwartz, 1995; Candente, 2011).
The global copper smelting industry has limited capacity to treat deleterious elements due to
environmental standards and requirements for copper product quality. For example, the Ministry
of Environment in Chile established a new policy regulating fugitive emissions of arsenic, sulfur
dioxide, particulate matter and mercury from smelters. Existing smelters in Chile need to comply
with emission standards of 95% capture for arsenic and sulfur dioxide, and any new installations
have even more stringent emission standards of 99.98% capture for arsenic and 98% for sulfur
2
dioxide (Voisin, 2015). China has imposed limits on arsenic import levels of copper concentrates
restricting the import of concentrates containing over 0.5% arsenic.
With the amount of arsenic in concentrates increasing and with environment, occupational health
and safety regulations becoming more stringent, there is a need for an alternative processing
method. The ideal processing route for high-arsenic copper concentrates would result in no arsenic
emissions and would capture all of the arsenic while immobilizing it in a compound that is stable
under a wide range of conditions so it is suitable for long-term disposal. The long-term stability of
arsenic compounds depends on a number of factors including disposal site characteristics, particle
crystallinity and size distribution, the presence of complexing agents and the effect of bacterial
activity (Riveros et al., 2001). Compounds containing ferric iron (Fe III) and arsenic in the
pentavalent state (As V) are considered to be the most suitable forms for long-term arsenic disposal,
specifically as crystalline ferric arsenates such as basic ferric arsenate sulfate (“Type 2 Scorodite”)
and scorodite (Demopoulos, 2014).
The CESL Process, developed by Teck and Aurubis, is capable of processing high-arsenic copper
and copper-gold concentrates and fixing arsenic as scorodite without generating any particulate or
sulfur dioxide emissions. The advantages of, and results from, the CESL Process for the processing
high-arsenic concentrates (from 1 to 12% arsenic) have been presented previously (Mayhew,
Salomon-De-Friedberg & Lossin, 2016; Salomon-De-Friedberg et al., 2015; Mayhew et al., 2014;
Bruce et al., 2011). Results include: production of LME Grade A copper cathode, copper extraction
over 97%, copper recovery over 95%, silver extraction up to 95%, gold extraction up to 90%, and
arsenic deportment to a stable residue over 99%. The stability of the leach residue from the CESL
Process has been demonstrated through short- and long-term testwork. Mineral characterization by
X-Ray Diffraction (XRD), Mineral Liberation Analyzer (MLA) and Fourier Transform Infrared
Spectroscopy (FTIR) has confirmed the CESL Process residues consist of scorodite and basic ferric
arsenate sulfate.
The sustainable processing of high-arsenic concentrates requires a global perspective. The
environmental benefits of the CESL Process for processing of high-arsenic copper-gold concentrates
were quantified and compared to traditional processing methods as presented in this paper.
CESL Process
The major steps of the CESL Process are shown in Figure 2.
3
Figure 2 Major steps of the CESL Process
Copper concentrates are reground to a p80 of less than 15 microns and subjected to a chloride
catalyzed oxidative pressure leach at 150°C and 1380 kPa pressure to favor the precipitation of
arsenic as scorodite. Leach retention time is from 60 to 90 minutes to promote complete oxidation of
the copper sulfide minerals and maximize arsenic precipitation. Depending upon the slurry pH
leaving the autoclave, additional acid may be required in an atmospheric leach to extract further
copper. The final residue is washed before long-term disposal or precious metal processing if gold
and silver are present.
The combined leach solution and wash water containing 30-60 g/L copper is directed to solvent
extraction and electrowinning to recover the copper as cathode. Due to the high copper tenor
entering SX, the extractant concentration in the organic is typically 30-40%, which helps keep the
iron concentration in electrowinning below 300 ppm. Electrowinning otherwise operates under
standard conditions. A portion of the raffinate from solvent extraction is recycled to the leach
circuit and another portion can either supply acid to a nearby heap or be neutralized with limestone
to maintain the overall sulfate balance. The neutralized solution is recycled to the leach circuit
except for a small bleed stream which is treated with lime to remove impurities. An evaporator may
be required to maintain the overall water balance, with the condensate being used as wash water,
lowering fresh water requirements.
Residue processing for precious metal recovery comprises pressure cyanidation, metal adsorption
onto activated carbon, and carbon stripping followed by electrowinning to produce a precious
metal sludge. Cyanide-bearing solutions are recycled. Copper and cyanide are recovered from a
small bleed stream prior to cyanide destruction. Residue containing minor amounts of copper is
directed back to the copper process, improving overall copper recovery.
Conventional processing – low arsenic concentrates (<1%)

To reduce the arsenic in copper concentrates to meet smelter thresholds (~0.2% arsenic) and to meet
China import restrictions (<0.5% arsenic), miners and traders resort to diluting the impurities below
the threshold levels thus dispersing the arsenic over larger areas and in larger amounts of waste.
After blending, the concentrates are traditionally processed by smelting and refining. During
smelting, some of the arsenic volatilizes together with sulfur and reports to the flue dusts as sulfide
4
(As2S3) or oxide (As2O3) while the rest deports to the slag and off-gas. In order to have sufficiently
low levels of arsenic in the gas before entering acid plant, the gases are cooled and the majority of
arsenic is removed as arsenic tri-oxide (As2O3) dust. Since there is a limited market for this and
because its high solubility makes it unsuitable for long-term disposal, smelters tend to cycle it
through the smelter, thus increasing the overall arsenic levels in the system.
Conventional process – high arsenic concentrates (>1%)

Besides being less than optimal from an economic and environmental perspective, blending is only
applicable to concentrates with lower arsenic levels. Blending concentrates containing several
percentages of arsenic requires up to twenty times the amount of clean concentrate which may not
be available. When the ore body contains areas with high arsenic, either the area is not mined and
the metal value is lost or the areas are mined and stockpiled without ever being concentrated and
the metal value is again lost. Today, some concentrates with very high arsenic content are processed
in a few specialized smelters (e.g. Tsumeb, Shandong Humon), where the arsenic is either disposed
of in a lined storage facility or stockpiled for further treatment in its highly soluble and toxic form.
Codelco’s Mina Ministro Hales concentrates are roasted to low-arsenic calcine. The arsenic is
concentrated into a roaster dust which requires treatment or copper recovery and arsenic fixation
but no proven technology is available for long-term disposal. In 2014, EcoMetales invited several
companies to help develop a process to treat the roaster dust; the dust was being stored temporarily
at the EcoMetales site (EcoMetales Sustainability Report, 2014).
Arsenic Disposal
Historically, arsenic has been disposed as calcium arsenate (e.g. in the majority of effluent treatment
plants of the smelters in Chile) and arsenic sulfide (e.g. Lepanto in Philippines and Saganoseki in
Japan) (Valenzuela, 2000). These arsenic compounds have not proven to be stable (Riveros et. al,
2001) and with health and environmental focus increasing, new methods for arsenic stabilization
are emerging. Co-precipitation with ferric ions is considered the best demonstrated available
technology for the removal of arsenic from solution (Rosengrant & Fargo, 1990), with ferric arsenate
sulfate (especially as scorodite) being the preferred stable compound for disposal (Demopoulos,
2014). Some plants are using atmospheric precipitation of scorodite, e.g. EcoMetales, treating
Codelco’s flue dusts, and arsenic removal from bleed electrolyte at the Kosaka smelter in Japan
(Kubo, 2010). Atmospheric scorodite precipitation is costly due to the oxidizing and energy
requirements. There are currently no facilities using pressure leaching processes for the
precipitation of scorodite.
METHODOLOGY
Teck and Aurubis contracted Offsetters Clean Technology Inc. to help quantify the environmental
benefits of the CESL Process for processing high-arsenic copper-gold concentrates through to
copper metal when compared to conventional processing routes. The processing of high-arsenic
copper-gold concentrates using the CESL Process at a planned custom refinery in Peru was
compared to two baseline scenarios that represent business-as-usual in the industry: 1. high-arsenic
copper-gold concentrates are sent for direct smelting to the Tsumeb smelter in Namibia (Baseline 1);
and 2. high-arsenic copper-gold concentrates are sent to a blending facility, are blended with low-
arsenic concentrates, and the blended concentrate is sent to a smelter located in China (Baseline 2).
5
A standard life cycle methodology was used to evaluate the environmental benefits of using the
CESL Process to treat high-arsenic copper-gold concentrates in a custom refinery in Peru. This
involved creating a detailed inventory of all the significant material, energy and water inputs to the
processes, as well as discharges of wastes in stack gases, solids and effluents. Two concentrates
were evaluated, with the compositions as shown in Table 1.
Table 1 High-arsenic copper-gold concentrates evaluated for environmental benefits
Copper Arsenic Iron Sulfur Gold

% % % % g/tonne
Concentrate 1 26 8 19 38 2.5
Concentrate 2 33 4 18 32 1.5
The boundary conditions start from the shipment of the concentrate from a mine in Peru located
250 kilometers driving distance from Lima and end prior to the shipment of copper cathode and
precious metals byproducts from the production location (the custom refinery or the smelters).
Assumptions included:
 The custom refinery is located 50 km north of Lima and 110 km from the port
 Transportation environmental impacts post-production are excluded from the analysis
 The use and disposal phases of the copper and precious metals life cycles are assumed to
have the same impacts for each scenario and are hence excluded from the analysis
 The smelters in China and Namibia achieve 95% sulfur dioxide emissions capture and 95%
arsenic capture (i.e. 5% goes out the stack as an air emission), based on China’s current
smelter emission standards for sulfur dioxide and arsenic (95%) and Dundee Precious
Metals’ statement of achieving up to 95% capture of sulfur dioxide for the Tsumeb smelter.
New smelters may have marginally better capture efficiency, however the assumed capture
is for what is considered to be a typical smelter using smelting and gas capture technology
 Arsenic trioxide produced by smelters is bioavailable and water soluble unless treated
further
 Over 99% of arsenic fed to the CESL custom refinery ends up in a highly stable residue
with short- and long- term stability tests confirming it to be a non-hazardous material
 Input materials to the refinery and smelters (other than concentrate) are transported
approximately 100 kilometers
 Energy is sourced from the regional grid except for the smelter in Namibia which is
sourced from coal
 The custom refinery has no particulate emissions nor sulfur dioxide emissions
 The custom refinery achieves an extraction of 97-98% copper, up to 95% gold and up to 90%
silver; the smelters achieve a recovery of 99% copper and virtually 100% of gold and silver
 Some minor reagent inputs are not included in the analysis as they were considered
immaterial to the quantification results; these include HCl and CaCl for the CESL Process
6
Environmental benefits were quantified in four areas: water (fresh water consumption), air (arsenic
trioxide and sulfur dioxide emissions), climate (GHG emissions), and soil (unstable arsenic species).

The environmental benefits of using the CESL Process in a custom refinery in Peru versus the two
baseline cases for two high-arsenic copper-gold concentrates are presented in Table 2.
Table 2 Environmental benefits of the CESL Process (net reduction of refinery versus baselines)
Arsenic Sulfur Unstable

Water GHGs
trioxide dioxide arsenic
consumption emissions
emissions emissions species to soil
(m3/tonne (tonnes/tonne (tonnes/tonne (tonnes/tonne (tonnes/tonne

Cu) Cu) Cu) Cu) Cu)
Concentrate 1 3.18 0.020 0.15 0.88 0.39

Baseline 1
Concentrate 2 2.28 0.008 0.10 1.33 0.15
Concentrate 1 3.18 0.020 0.15 2.21 0.39

Baseline 2
Concentrate 2 2.28 0.008 0.10 2.39 0.15
For the production of 60,000 tonnes of copper per year, using the CESL Process instead of
traditional processing routes would result in decreased:
 fresh water consumption of at least 136,800 m3 per year
 particulates of arsenic trioxide to the air of at least 480 tonnes per year
 sulfur dioxide emissions of at least 6,000 tonnes per year
 greenhouse gas emissions (carbon dioxide) of at least 52,800 tonnes per year
 unstable arsenic species to ground (as arsenic trioxide) of at least 9,000 tonnes per year
Water
For areas where water is scarce and must be shared with local communities, agriculture and other
industry, the use of the CESL Process for processing high-arsenic copper-gold concentrates versus
the traditional treatment route would result in 20 to 23% less water consumption annually. In Peru,
annual water use per person is estimated at 3 m3/day (Mekonnen & Hoekstra, 2011). For
perspective, a savings of 136,800 m3/year water consumption is equivalent to the annual
consumption of 45,600 people.
7
Air
By reducing air pollution levels, countries can reduce the burden of disease from stroke, heart
disease, lung cancer, and both chronic and acute respiratory diseases, including asthma (WHO,
2016). In 2014, 92% of the world’s population was living in places where the WHO air quality
guidelines were not met (WHO, 2016). A custom refinery using the CESL Process would not emit
any particulates or sulfur dioxide to the air. The traditional treatment routes are estimated to emit
480 tonnes per year of particulates as arsenic trioxide and 6,000 tonnes per year of sulfur dioxide.
Climate
The use of the CESL Process in a custom refinery to treat high-arsenic copper-gold concentrates
versus traditional treatment routes would result in a 27% to 57% reduction of carbon dioxide
emissions, depending on the concentrate feed. In Peru, annual carbon dioxide emissions are
estimated at 1.9 tonnes per person per year (World Bank, 2017). A savings of 52,800 tonnes/year
carbon dioxide emissions is equivalent to the carbon dioxide emissions of 28,235 people.
Soil
A custom refinery using the CESL Process in a custom refinery for high-arsenic copper-gold
concentrates versus the traditional treatment routes would result in no unstable arsenic species for
ground disposal, in comparison to the estimated 9,000 tonnes per year generated by a smelter. The
stability of CESL Process residues has been proven through both short and long-term stability tests.
Residue Stability
Residues from the CESL Process exhibit excellent short-term stability with 0.05 to 0.10 mg/L
solubilized arsenic in leachates from the United States EPA’s Toxicity Characteristic Leaching
Procedure (TCLP) tests. The stability of the residues for long-term disposal has been continuously
tested under accelerated conditions for nearly four years, with arsenic dissolution well below the
TCLP limit at an average of 4% of the TCLP limit of 5 mg/L arsenic in solution.
CONCLUSIONS
The environmental benefits of using the CESL Process to process high-arsenic copper-gold
concentrates and produce 60,000 tonnes per year of copper metal, compared to conventional
processing routes include at least:
1. 136,360 m3 of fresh water saved
2. 480 tonnes of arsenic trioxide particulates to air avoided
3. 6,000 tonnes sulfur dioxide emissions to air avoided
4. 52,800 tonnes of carbon dioxide emissions to air avoided
5. 9,000 tonnes of unstable arsenic species for ground disposal avoided
8
ACKNOWLEDGEMENTS
The authors wish to express their gratitude for permission to publish this paper and acknowledge
our respective companies, Teck Resources Limited and Aurubis AG. Teck and Aurubis
acknowledge Offsetters Clean Technology for their work in quantifying the environmental benefits
and Sustainable Development Technology Canada for their support of our project.
REFERENCES
Bruce, R., Mayhew, K., Mean, R., Kadereit, H., Nagy, N., Wagner, O. (2011) Unlocking value in copper
arsenic sulphide resources with the copper-arsenic CESL technology, Hydrocopper 2011 Conference.
Demopoulos, G. (2014) Arsenic immobilization research advances: past, present and future, COM 2014
Conference.
EcoMetales (2014) Sustainability Report, http://www.ecometales.cl/wp-
content/uploads/2017/02/Sustainability-Report-2014.pdf
Kubo, H., Abumiya, M., Matsiomoto, M. (2010) DOWA Mining Scorodite Process – Application to
Copper Hydrometallurgy, Copper 2010, (GDMB Society for Mining, Metallurgy, Resource and
Environmental Technology, Clausthal – Zellerfeld, Germany, 2010), Vol.7, pp. 2947-2958.
Mayhew, K., Salomon-De-Friedberg, H., Lossin, A. (2016) Scorodite in the CESL Process for copper-
arsenic concentrates, COM IMPC 2016 Conference.
Mekonnen, M., Hoekstra, A. (2011) National water footprint accounts: The green, blue and grey water
footprint of production and consumption, Volume 1: main report.
Riveros, P., Dutrizac, J., Spencer P. (2001) Arsenic disposal practices in the metallurgical industry,
Canadian Metallurgical Quarterly, Vol. 40, No 4 pp. 395-420.
Salomon-De-Friedberg, Mayhew, K., H., Lossin, A., Omaynikova, V. (2015) Hydrometallurgical
considerations in processing arsenic-rich copper concentrates, Hydroprocess 2015 Conference.
Salomon-De-Friedberg, H., Robinson, T., Lossin, A., Omaynikova, V. (2014) Developing copper arsenic
resources with CESL technology, COM 2014 Conference.
Schwartz, M. (1995) Arsenic in porphyry copper deposits: economic geology of a polluting element,
International Geology Review, Vol. 37, pp. 9-25.
WoodMac (2016) Wood Mackenzie copper concentrates and blister markets database, online.
The World Bank (2013) World DataBank, online.
The World Bank (2016) Ambient (outdoor) air quality and health fact sheet.
Rosengrant, L. Fargo, L. (1990) Final best demonstrated available technology background document for
K031, K084, K101, K102, characteristic arsenic wastes (D004), characteristic selenium wastes (D010) and P
and U wastes containing arsenic and selenium constituents, USEPA.
Valenzuela, A. (2000) Arsenic management in the metallurgical industry, M.Sc. Thesis, University of
Laval, Department of Mines and Metallurgy, Quebec, Canada.
9
Voisin, L. (2012) New Strategies for the Treatment of Copper Concentrates with High Arsenic Content in
Chile, http://mric.jogmec.go.jp/public/kouenkai/2012-11/briefing_121108_5new.pdf.
10
Outotec Process Solutions and Equipment for
Hydrometallurgical Treatment of Cu Sulfides
Janne Karonen1,Kaarlo Haavanlammi1, Boris Merino2 and Claudio Rodríquez2
1. Outotec, Finland
2. Outotec, Chile
ABSTRACT
This paper outlines hydrometallurgical copper sulfide leaching options as alternatives to the more
conventional pyrometallurgical processing route for copper sulfides. Three copper sulfide leaching and
refining processes are discussed, total pressure oxidation, ferric sulfate leaching and copper chloride
leaching. Ferric sulfate leaching and copper chloride leaching are carried out at atmospheric pressure while
total pressure oxidation takes place at elevated pressures.
In general the selection of a hydrometallurgical process for use in a commercial application will require
that many of the following characteristics are satisfied by the process selected:
- The use of proven unit processes and equipment.
- High metal recovery and good product quality.
- The recovery of other valuable metals such as gold and silver can be carried out economically.
- The process is flexible in terms of the mineralogy, grade and impurity concentrations it can handle,
while still delivering a safe and robust operation with minimal environmental impact.
- The technology should be suitable for retrofits e.g. the conversion of a copper heap leach, solvent
extraction (SX) and electrowinning (EW) facility once the oxide and transition material is exhausted
(Valkama 2013).
Throughout this paper, ‘copper sulfides’ describe both mixed copper iron sulfides, such as bornite and
chalcopyrite (Cu5FeS4 and CuFeS2, respectively) as well as copper sulfides, such as chalcocite, digenite
and covellite (Cu2S, Cu9S5 and CuS, respectively).
INTRODUCTION
Hydrometallurgical processing routes may be sought for a number of reasons as alternatives to more
conventional pyrometallurgical processing (Dreisinger 2006). In general the selection of a
hydrometallurgical process for use in a commercial application will require that many of the following
characteristics are true of the process selected:
 The use of proven unit processes and equipment.
 High metal recovery and good product quality.
 The recovery of other valuable metals such as gold and silver can be carried out economically.
 The process is flexible in terms of the mineralogy, grade and impurity concentrations it can handle,
while still delivering a safe and robust operation with minimal environmental impact.
 The technology should be suitable for retrofits e.g. the conversion of a copper heap leach, solvent
extraction (SX) and electrowinning (EW) facility once the oxide and transition material is exhausted
(Valkama 2013).
Throughout this paper, ‘copper sulfides’ describe both mixed copper iron sulfides, such as bornite and
chalcopyrite (Cu5FeS4 and CuFeS2, respectively) as well as copper sulfides, such as chalcocite, digenite
and covellite (Cu2S, Cu9S5 and CuS, respectively).
LEACHING OPTIONS
Three copper sulfide leaching processes are discussed in the sections that follow. Total pressure oxidation
(POX) and ferric sulfate leaching are carried out in environments that are sulfate based while copper
chloride leaching takes place in a chloride based solution environment.
Total pressure oxidation

Total POX plants operated in the USA in the 1950s and more recently continue to operate at the Freeport
McMoRan Bagdad plant in Arizona as a result they should now be considered proven technology
(Dreisinger 2006).
Total POX is carried out in an autoclave reactor run in a continuous manner that is designed to operate in
an oxidising, acidic environment at elevated temperature and pressure. The autoclave environment
consists of a complex combination of vapour, liquid and solids phases through which many of the reagents
and products of the reactor chemistry transit. For this reason, the chemical reactor design of the autoclave
is very important to the successful operation of a total POX leach circuit.
Total POX autoclaves operate in sulfate based environments at a temperature of greater than 200°C. At
these elevated temperatures the total POX autoclave is classified as a high temperature pressure leaching
process (Marsden 2007a). The pressure range at which total POX autoclaves operate is between 30–40
atmospheres (Dreisinger 2006). This combination of high pressure and temperature as well as the
continuous operation of the autoclave make the mechanical design of the autoclave reactor another very
important aspect to a successful total POX circuit delivery.
High pressure oxygen gas is introduced into the autoclave in such a way as to maximise the dissolution of
the gas into the solution phase. Once dissolved in the solution, oxygen reacts exothermically with sulfide
minerals at the surface of the solid phase forming sulfates ions that enter the solution phase (sulphuric
acid). For this reason, dissolved oxygen (DO) levels in the aqueous phase are an important parameter in
enhancing the rate of the sulfide oxidation reaction. In general however, the solubility of oxygen in an
aqueous phase reduces as the temperature increases. Due to the lower oxygen solubility at elevated
temperatures the importance of the following design requirements is enhanced:
 Oxygen dispersion in the liquid phase,
 Maintenance of the oxygen partial pressure in the vapour phase, and;
 The degree to which the vapour phase is reincorporated into the slurry.
The mixing system design within the autoclave addresses the oxygen dispersion and vapour phase
reincorporation design requirements. The oxygen partial pressure design requirement is managed by
maintaining the autoclave pressure with the addition of pressurised oxygen gas and the regular purging
of the autoclave vapour phase and subsequent analysis of the off gas.
Many of the minerals fed to a POX autoclave contain significant amounts of iron. As a result the reactions
that the iron containing minerals undergo as well as the form of iron that occurs in the leaching reaction
mechanisms and ultimately exits the autoclave is of particular importance to the overall process. With
sufficient dissolved oxygen in solution and under the total POX conditions described above, ferric sulfate
leached from solid minerals in the autoclave hydrolyses with water to form preferred solid haematite
crystals (Marsden 2003). At lower temperatures and higher acidity however, the ferric sulfate in solution
will tend to favour the formation of basic iron sulfate (Fe(OH)SO4) (Fleming 2009).
At high temperature pressure leaching conditions the formation of sulphuric acid from sulfides in the ore
is favoured however, at medium and low temperature conditions (150 – 165°C and >140°C, respectively)
elemental sulphur formation occurs. At these temperatures the elemental sulphur is molten and causes
issues in further leaching. A high yield of elemental sulphur reduces the oxygen requirement in the
autoclave reactions and, in addition, the downstream acid neutralisation (Dreisinger 2006) if no acid sink
such as a heap leach is available on site. For these reasons medium to low temperature POX conditions may
be worth considering in some copper sulfide leaching scenarios.
Simplified flowsheet
A simplified flowsheet outlining total POX in a copper circuit is shown in
Figure 1 Two points are worth noting, firstly the acid generated in the oxidation of the sulfides in the
concentrate pressure leaching step as well as that produced in the extraction of copper from the pregnant
leach solution (PLS) is available for use in the copper heap leaching unit process. In this way an acid credit
to the operating cost is derived (Dreisinger 2006).
Secondly, it is worth noting that the POX residue can be leached in an atmospheric halide leaching step to
recover precious metals such as gold and silver that may be present in the copper concentrate. This
additional step is likely to improve the economics of the circuit if there are sufficient precious metals in the
concentrate.
Figure 2 Simplified Ferric Figure 3 Copper Chloride
Leaching Flowsheet Leach Process
Figure 1 Simplified Flowsheet
Indicating the Integration of Total
POX in a Copper Heap Leach
Circuit
Leaching chemistry
As outlined earlier, the leaching chemistry that takes place within a total POX autoclave is very complex
and will vary from case to case according to the mineralogy of the concentrate fed to the autoclave.
However simplified representations of the leaching of chalcopyrite (CuFeS2), pyrite (FeS2), chalcocite
(Cu2S) and covellite (CuS) are presented in equations (1) to (5).
4CuFeS2 [s] + 17O2 [g] + 4H2O [l] → 4CuSO4 [aq] + 2Fe2O3 [s] +4H2SO4 [aq] (1)
4FeS2 [s] + 15O2 [g] + 8H2O[l] → 2Fe2O3 [s] +8H2SO4 [aq] (2)
Cu2S [s] + O2 [g] + 2H2SO4 [aq] → 2CuSO4 [aq] + S [l] + 2H2O [l] (3)
CuS [s] + 0.5O2 [g] + H2SO4 [aq] → CuSO4 [aq] + S [l] + H2O [l] (4)
S [l] + 2O2 [g] + H2O [l] →H2SO4 [aq] (5)
Ferric sulfate leaching
Ferric sulfate leaching of secondary sulfide ores has been successfully commercialised at the Cobre Las
Cruces (CLC) and Sepon copper plants.
Cobre Las Cruces

Outotec was involved from the early stages of the CLC project starting in 2002 where research work was
done to re-estimate the investment costs required for an atmospheric leach rather than a pressure leach
process. From 2004 to 2005 the leaching process was further developed before basic engineering (similar to
a definitive feasibility study level of detail) was completed by Outotec in 2006. The implementation phase
followed and the production of first copper was achieved in June 2009.
More detail on the development of this project is outlined later in this paper. The final CLC leaching
parameters that Outotec defined through test work, process design, optimisation and validation are
summarised below:
Ore feed - 165t/h Installed motor size - 500kW

Leach residence time - 8h Solids concentration - 500 – 550 g/l
Number of leach reactors -8 Copper leach extraction - ~ 92%
Effective volume per leach reactor - 350m3 Leach temperature - ~ 90°C
Agitation power -1.4kW/m3 (with Oxygen supply - 98% pure
oxygen)
2.2.3 Simplified flowsheet

A simplified ferric sulfate leaching flowsheet is presented in
Figure 2.
2.2.4 Leaching chemistry

The simplified chemistry of ferric sulfate leaching of chalcocite (Cu2S) is presented in equations (6) and (7).
Equation (8) shows the overall reaction without the ferric/ferrous intermediate mechanism.
Cu2S [s] + 2Fe2(SO4)3 [aq] → 2CuSO4 [aq] + 4FeSO4 [aq] + S0 [s] (6)
4FeSO4 [aq] + O2 [g] + 2H2SO4 [aq] → 2Fe2(SO4)3 [aq] + 2H2O [l] (7)
Cu2S [s] + O2 [g] + 2H2SO4 [aq] → 2CuSO4 [aq] + S0 [s] + 2H2O [l] (8)
Copper chloride leaching

Outotec’s copper chloride leaching process is carried out in atmospheric leach reactors with cupric ions,
Cu(II), in a chloride media at a pH of between 2 and 2.8. The leach conditions are suitable for the leaching
of all copper sulfide minerals such as chalcopyrite, bornite, chalcocite, covellite and digenite (Valkama
2013). These leach conditions have delivered high recoveries of copper and silver (95-98% and 93-96%,
respectively) in batch tests and pilot runs. Chloride from sodium chloride enables the leaching reactions
but it is not consumed and sulphuric acid is used as a makeup acid. Because of the nature of the leaching
solution and the subsequent solvent extraction, neither chemical has stringent purity requirements. Silver
and gold can be recovered also if they are present in the feed. As a result the technology is suited to a wide
variety of copper containing feed materials.
The copper leached is subsequently recovered with conventional SX/EW technology and LME grade A
copper cathode is produced. Pyrite, haematite and magnetite have been shown not to dissolve in the
environment (Lundstrom 2009). This offers benefits in the downstream solution purification steps and the
possibility to accept a lower copper grade concentrate as feed.
The copper chloride leaching process developed by Outotec and outlined by Valkama (2013) has been
developed from this engineering expertise and experience in technology development. Laboratory and
demonstration plant test work coupled with exceptional material selection knowledge have allowed this
promising and versatile leaching technology to develop to the stage where it is ready for industrial
application using standard and proven equipment.
Simplified flowsheet
A simplified flowsheet outlining the Outotec copper chloride leach process is presented in Figure 3. Silver
is leached together with copper and depending on the silver content of the feed material; silver can be
recovered either from the main circuit or from bleed. If gold is present it can be recovered from the leaching
residue.
Leaching chemistry
The chemistry of the copper chloride leaching of chalcopyrite (CuFeS2), cupric oxidation and simultaneous
haematite precipitation is presented in equations (9), (10) and (11). Equation (12) shows the overall reaction.
2CuFeS2 [s] + 6Cu2+ [aq] → 8Cu+ [aq] + 2Fe2+ [aq] + 4S0 [s] (9)
10Cu+ [aq] + 2.5O2 [g] + 10H+ [aq] → 10Cu2+ [aq] + 5H2O [l] (10)
2Fe2+ [aq] + 2Cu2+ [aq] + 3H2O [l] → Fe2O3 [s] + 2Cu+ [aq] + 6H+ [aq] (11)
2CuFeS2 [s] + 2.5O2 [g] + 4H+ [aq] → 2 Cu2+ [aq] + Fe2O3 [s] + 4S0 [s] + 2H2O [l] (12)
Secondary copper sulfides are leached in a similar fashion. The same as ferric sulfate leaching, this process
requires acid as opposed to POX where excess acid is produced. A small part of elemental sulphur will
oxidize to sulphuric acid but the acid balance still remains negative. Most of the acid comes from solvent
extraction raffinate, the same as in ferric sulfate leaching.
IMPORTANCE OF MINERALOGY
When considering the leaching of copper sulfides it is very important to understand the mineralogy of the
ore body as not all leaching options are suitable for all minerals. A very effective way to develop the
required understanding of the mineralogy is to do test work on the site specific ores. It is important that
this test work is done on representative samples from the ore body. In addition, it is important to
understand any variability of different zones of the ore body to the leach conditions, particularly material
that will be fed during the early stages of operation.
Table I outlines the response a selection of minerals has when presented to the copper sulfide leaching
conditions detailed in this paper.
Table I High level mineralogical response to copper sulfide leaching conditions
Mineral Total POX Leach Ferric Sulfate Leach Copper Chloride Leach
Copper leaches Copper leaches
Chalcopyrite
Iron forms hematite Inert Iron forms mainly haematite
(CuFeS2)
Sulphur forms H2SO4 Sulphur forms mainly S°
Copper leaches Copper leaches
Bornite
Iron forms hematite Inert Iron forms mainly haematite
(Cu5FeS4)
Sulphur forms H2SO4 Sulphur forms mainly S°
Chalcocite Copper leaches Copper Leaches Copper Leaches
(Cu2S,) Sulphur forms H2SO4 Sulphur forms mainly S° Sulphur forms mainly S°
Digenite Copper leaches Copper Leaches Copper Leaches
(Cu9S5) Sulphur forms H2SO4 Sulphur forms mainly S° Sulphur forms mainly S°
Covellite Copper leaches Copper Leaches Copper Leaches
(CuS) Sulphur forms H2SO4 Sulphur forms mainly S° Sulphur forms mainly S°
Pyrite Iron forms hematite
Virtually inert Inert
(FeS2) Sulphur forms H2SO4
Hematite
Iron forms hematite Virtually inert Inert
(Fe2O3)
Magnetite
Iron forms hematite Virtually inert Inert
(Fe3O4)
The sulphuric acid from all the sulfide minerals formed in total POX will need to be consumed or
neutralized elsewhere in the process. Additionally, the amount of oxygen required in the autoclave will be
significantly higher than that required in the other two leaching conditions. Therefore the operating costs
for the total POX option may be significantly higher than copper chloride leaching if there is a high cost for
oxygen supply (electricity) and no heap leach available to neutralize the additional acid formed.
The mineralogical association of any precious metals present in the ore is also an interesting point to
consider. For example, if gold is associated with pyrite it can be seen that total POX will be the most effective
means to liberate it from the pyrite matrix.
DISCUSSION ON UNIT PROCESSES
The following sections introduce a selection of the key unit processes that typically form part of the overall
process in the three leaching options presented in this paper.
Pressure oxidation
The autoclave and ancillary equipment that make up the pressure oxidation unit process operate under an
extreme set of conditions (temperature, pressure, corrosion, etc.). This demands that all aspects of the
design and subsequent operation are particularly well understood, defined and then addressed in the
delivery of the unit process.
In general it is important to understand the life of mine feed to the POX circuit in order to suitably define
these design parameters. For example key variables such as changes in the mineralogy over time can have
a dramatic effect on the amount of energy evolved during the oxidation reaction, oxygen demand and the
recovery of copper. These variables impact on design considerations such as the selection of materials of
construction, oxygen plant sizing, operator training, scale formation and steam provision.
A single source for the technology, engineering design and process equipment for the complete delivery
offers benefits as this minimises intercompany and discipline. Figure 4 outlines the main critical equipment
required in a typical autoclave plant delivery. The ability to deliver this wide scope should be underpinned
by extensive test work capabilities and a long history in autoclave plant delivery and an experienced team
of engineers to tailor the design to the requirements of the ore body.
Additionally it is important to consider recent enhancements to the autoclave agitation system, energy and
water recovery. These enhancements significantly improve the oxygen mass transfer from the gas phase
into solution enhancing the oxygen utilisation. Additionally, novel energy and water recovery technology
allows for further off sets in the operating costs of the unit process (Tiihonen et al. 2013).
Figure 4 Typical POX autoclave delivery scope
Outotec has recently developed a POX project with these features from the concept study through to
detailed design and delivery for the Russian gold producer Petropavlovsk Group (Tiihonen et al. 2013).
Atmospheric leach
Atmospheric leaching of copper sulfides is carried out in challenging conditions of elevated temperature,
low pH and high chloride ion concentrations. In addition the reactors need to optimally cater for a three
phase reaction dynamic in which gaseous oxygen, solid copper concentrate and metal containing aqueous
solution all interact.
Other very important factors to consider include the heat balance management of the reactor as heating
may be required for start-up and cooling during operation and the correct specification of the materials of
construction. The demands of this environment require a technically sound evaluation by a highly skilled,
experienced and therefore competent engineering team. An excellent overview of the importance of reactor
design in hydrometallurgy as well as the many recent innovations available in this area is given in Latva-
Kokko, 2014.
The design cycle, including physical modeling, leaching and precipitation tests, fluid dynamics analysis,
mechanical design, life cycle analysis, quality control and assurance, built in safety procedures should be
considered for the optimal reactor design for each unique process.
Figure 5 Athmospheric leaching reactor delivery
HYDROMETALLURGICAL PROCESSING BENEFITS

The following sections outline benefits that may be possible if a hydrometallurgical process is selected over
the sale of concentrate to an existing pyrometallurgical copper smelter. It is important to note that each ore
body will bring with it a unique set of characteristics that will determine whether any of these benefits can
be realised in practice.
Grade vs. recovery

In general the onsite hydrometallurgical processing of copper concentrates will allow for a re-evaluation
of the optimal point to operate the flotation circuit in terms of the flotation grade vs. recovery curve.
Removing or relaxing the need to reduce concentrate mass for subsequent transportation or to meet higher
copper or sulphur grades in the concentrate can allow for a higher overall copper recovery to be achieved.
This will in turn enhance the revenue that can be generated due to a higher copper production per ton of
ore processed.
Impurities
New hydrometallurgical copper sulfide leaching processes can be designed to have a greater tolerance to
impurities such as As, Sb, Bi, and halides than existing copper concentrate smelters are able to process. This
will allow for difficult or complex deposits that contain relatively high levels of such impurities to be
processed by hydrometallurgical routes when the economics of the specific cases is favorable.
Use of saline water

The supply of fresh water is limited in some regions which drives the related costs for alternative sources
of water up. Copper chloride leaching can make use of some saline water sources, reducing the need for
sodium chloride make-up. In addition this flexibility can reduce the raw water demand of the overall
process.
Sulphur
In the processes outlined in this paper sulphur exits the process as either elemental sulphur or as
neutralised solids such as gypsum. In both of these forms the sulphur compound is a solid and therefore a
relatively dense product. In this form it is relatively cost effective to handle when compared to gaseous
forms such as SO2 or SO3 generated in smelting. Gaseous sulphur compounds at elevated temperatures
require large ducting, gas cleaning and sulphuric acid plant equipment to capture the sulphur and limit
the emission of this pollutant.
CONCLUSIONS
The conclusions that can be drawn from the contents of this paper are:
 Hydrometallurgical leaching of copper sulfides is an option to consider regardless of the feed
material.
 A number of developing countries have adopted policies that target downstream value addition to
their economies. The production of a refined copper product is a good fit and is therefore expected
to enhance the case for the development of copper sulfide leaching projects, particularly in Africa.
 The local acid market can be taken into account when identifying hydrometallurgical options for
the leaching of copper sulfides as sulphur in the feed can either be converted into sulphuric acid
or elemental sulphur.
 When considering the leaching of copper sulfides it is very important to understand the mineralogy
of the ore body as not all leaching options are suitable for all minerals. Table I outlines the response
a selection of minerals has when present in the copper sulfide leaching conditions detailed in this
paper.
 A detailed and thorough test work and pilot campaign is a critical aspect to the successful
development of a complex hydrometallurgical project such as the leaching of copper sulfides.
 The mineralogical association of any precious metals present in the ore is also an interesting point
to consider.
 The unit processes required in the production of copper cathode from the leaching of copper
sulfides are not novel.
 In order to select the right process for an ore body the options available for processing need to be
studied and evaluated accurately and objectively.
 There are a number of benefits to engaging an integrated technology partner to do these
evaluations. Such a technology partner would offer world class research and development, test
work and piloting facilities as well as the ability to offer complete plant deliveries around
proprietary equipment from ore to copper cathode.
REFERENCES
M.E. Schlesinger, M.J. King, K.C. Sole, W.G. Davenport, Extractive metallurgy of Copper, 5th ed., Elsevier,
Oxford, UK, 2011.
Dreisinger, D., 2006. Copper leaching from primary sulfides: Options for biological and chemical extraction
of copper. Hydrometallurgy, 83 (2006) 10-20.
Fleming, C., 2009. Basic iron sulfate – a potential killer for pressure oxidation processing of refractory gold
concentrates if not handled appropriately. SGS Minerals Services Technical Paper 2009-06.
Halbe, D., 2003. Business aspects and future technical outlook for hydrometallurgy. Hydrometallurgy 2003
– Fifth International Conference in Honor of Professor Ian Ritchie – Volume 2: Electrometallurgy and
Environmental Hydrometallurgy. pp. 1091-1104.
Latva-Kokko, M., et al. 2014. Influence of reactor design to process performance in hydrometallurgical
applications. Proceedings of the Hydro 2014 conference. Victoria, Canada 2014. MetSoc.
Lundstrom, M., et al. 2009. Dissolution of six sulfide concentrates in the Hydrocopper® environment.
Proceedings of the Base Metals Conference 2009. pp. 127-138. The Southern African Institute of Mining and
Metallurgy.
Marsden, J., Brewer, R. 2003. Hydrometallurgical processing of copper concentrates by Phelps
Dodge at the Bagdad mine in Arizona. Proceedings of the ALTA copper conference. Melbourne, Australia
2003. ALTA Metallurgical Services.
Marsden, J., et al. 2007a. Medium-temperature pressure leaching of copper concentrates Part I: Chemistry
and initial process development. Minerals & Metallurgical Processing, Vol.24, No.4, pp.193-204.
Marsden, J., et al. 2007b. Medium Medium-temperature pressure leaching of copper concentrates Part II:
Development of direct electrowinning and an acid-autogenous process. Minerals & Metallurgical
Processing, Vol.24, No.4, pp.205-217.
Marsden, J., et al. 2007c. Medium-temperature pressure leaching of copper concentrates Part Ill:
Commercial demonstration at Bagdad, Arizona. Minerals & Metallurgical Processing, Vol.24, No.4, pp.218-
225.
Marsden, J., et al. 2007d. Medium-temperature pressure leaching of copper concentrates Part IV:
Application at Morenci, Arizona. Minerals & Metallurgical Processing, Vol.24, No.4, pp.226-236.
McDonald, R., Muir D. 2007. Pressure oxidation leaching of chalcopyrite. Part I. Comparison of
high and low temperature reaction kinetics and products. Hydrometallurgy 86 (2007) 191 – 205.
Murphy, K., 2014. Strategic Report - Copper Production Pipeline, 2014: Mine Development and Production,
2004-19. SNL Metals & Mining.
Tiihonen, J., et al. 2013. Outotec Pressure Oxidation — More out of Sulfide Ore. Proceedings of the World
Gold Conference. Brisbane, 26- 29 September 2013, pp.197-205.
Valkama, K., Karonen, J., 2013. Outotec’s chloride based process for production of copper cathode from
primary copper sulfide concentrates. Proceedings of copper 2013. Santiago, Chile 2013. pp. 285-295.
Vizsolyi, A., et al. 1967. Copper and elemental sulphur from chalcopyrite by pressure leaching. Journal of
Metals, November 1967. pp. 52-59.
New Electrolytic Process to Remove Copper
Impurities from Molybdenite Concentrate by
Simultaneously Electrowinning Copper and
Regenerating a Ferric Chloride Leaching Agent
Jaime Simpson
Protech, Chile
ABSTRACT
This paper presents the foundations, modeling and experimental results of a new electrolytic
system that allows the replacement the troublesome process utilized today of removing copper
from molybdenite concentrate by leaching with ferric chloride, recovering the copper put in
solution by cementation and regenerating the leaching agent by oxidation with gaseous chlorine.
The new process is based on a modified electrolytic cell that can regenerate the leaching agent by
electro-oxidizing ferrous chloride to ferric chloride, while simultaneously electrowinning
commercial-quality copper cathodes from the leach solution.
This process was developed in the laboratory and then field-tested, utilizing actual solutions
leached from molybdenite concentrates in an industrial facility. Typical solutions contained 52.7
g/L of copper and 170 g/L of total iron, of which 167.3 g/L were Fe (II ) and 2.7 g/L were Fe (III).
Experimental results show that copper cathodes of commercial quality can be deposited on 316L
stainless steel electrodes and simultaneously ferrous chloride can be oxidized to ferric chloride on
graphite electrodes. The electrolyte system did not generate acid mist, the efficiency of the Faradian
current was 90% and the energy consumption was between 1250 and 1350 kWh/ton of copper.
1
BioCobre® Technology: an Improved Methodology
for Leaching Mineral Concentrates
Raimundo Bordagorry2,3,4, Miguel Herrera1, Gustavo Rodríguez1,2 and Juan
Rivadeneira1,2,4
2. Laboratorio de Investigación Aplicada, Chile
3. Universidad Diego Portales, Chile
4. Minera Pucobre, Chile
ABSTRACT
There is a great reward in the concentration and the pyrometallurgical approach to process the copper
sulphates, beyond the possibility of recovering not only the copper in the leaching base processes,
but other metals as Au, Ag or Mo. By the other hand the enormous environmental impacts of this
approach have increase the costs and business sustainability. As the mineral reserves of copper
oxides are rapidly diminishing in Chile, there is a 2 Million ton copper cathode production facility of
SX and EW capacity install that will decreases by half to 2025, the development of a new copper
concentrate leaching reactor (BIOCOBRE®) that allows the bioleaching of copper sulphides out of
regular smelter type concentrates may to feed SX –EW plants not losing the Cu, Au, Ag content, but
recovering it us a new commercial grade re-concentrate. The BIOCOBRE process uses a support
material specially designed to leach concentrates, the support purpose is to allow the adhesion of the
mineral concentrates in a stable form so that they can be treated by leaching in packed bed or heap
reactors. The oxidation reactions are catalysed through the action of microorganisms or chemical
elements to obtain solutions loaded with the metals of interest, contained in the concentrate matrix.
These agglomerates are composed of polymeric particles covered by a fine layer of mineral
concentrate and are obtained through a physical process that allows agglomeration through the use
of a rotary drum or similar technologies. Another attribute of the process is that it is an available
alternative to the treatment of mineral concentrates with impure metals (As). The technology of this
invention can increase of the economic value of minerals such as enargite (copper arsenic sulphide,
Cu3AsS4). The BIOCOBRE technology can less de Cost C1 between 12-5 USc/Lb de Cu.
1
INTRODUCTION
Biocobre® process technology is a sulfide mineral leaching technology were the oxidation reactions
are catalyzed through the action of microorganisms and chemical elements, were solutions loaded
with metals of interest, contained in the concentrate matrix, can be obtained (Rivadeneira, 2015).
These agglomerates are composed of polymeric particles covered by a fine layer of mineral
concentrate and are obtained through a physical process that allows agglomeration through the use
of a rotary drum or similar technologies (Figure 1). Said agglomerates can be packed homogeneously
in a reactor or placed in a heap, improving the known recoveries from mineral concentrates with high
impurity contents in comparison to the leaching processes described in the previous art. It is also an
attribute of this process to produce minimum amounts of effluents (rubble and/or tailings) and, in
general, potentially polluting and damaging emissions for the environment. In addition, it reduces
the energy demand to obtain metals of economic value.
Another attribute of the process is that it is an available alternative to the treatment of mineral
concentrates other than processes such as smelting. These processes have a higher cost of treatment,
and they can be economically infeasible to function (Rojas et al., 2016; Wiertz, Mateo & Escobar, 2006).
The technology of this invention can increase of the economic value of minerals such as enargite
(copper arsenic sulfide, Cu3AsS4)
The support is expected to bind agglomerated concentrate on its surface without blocking the
circulation of the liquid/air in the porous channels of the packed bed.
Once the oxidation or leaching process of the agglomerated concentrate occurs around the support
particles, they are to be reused for the new cycle in the reactor. The particles can be washed with
diluted acid or water and easily removed from the washing solution since their specific gravity is less
than 1, and they float to the surface (Figure 1).
The concentrate that did not react, along with the other solid mineral that were washed, is recovered,
thickened, and filtered to be commercialized as re-concentrated minerals (Figure 1). This way the
losses, which other leaching technologies have, are decreased.
Generally, in the metallurgical industry where minerals are treated via leaching and bioleaching, the
mechanical and hydraulic properties of the leaching reactors in heaps are fundamental in ensuring
high recoveries (Wang, 2005). This is achieved by agglomerating the fine mineral particles around
the thicker particles of the same mineral. This results in going from a model where the fine and thick
particles are scattered to one where the new agglomerated particles become the dominant typed
inside the reactor, maximizing the hydraulic and gaseous conductivity of the bed of the reactor,
improving the total kinetics of recovery of the oxidable metallic contents.
2
ACIDIC CONCENTRATE PULP
COPPER
NEW PLASTIC MATRIX
CONCENTRATES AGLOMERATED
CONCENTRATE TO LEACHING
REACTOR SOLUTION
Cu, Au, Ag, Mo
BLOWER
HEAT
AGLOMERATION EXANGE
RECICLED PLASTIC MATRIX LIVERATION

UNFILTERED CONCENTRATES PLS
SOLIDS
CONCENTRATES
TAIL
Cu, Au, Ag, Mo
CONCENTRATE FILTERING
Figure 1 Hydrometallurgical integration of Biocobre technology process
MATERIALS AND METHODS
Chalcopyrite concentrates leaching columns set up  

Chalcopyrite concentrates were provided by Punta del Cobre Minning Company, from Copiapo,
Atacama region, Chile. These concentrates were generated in Pucobre`s flotation plant “San José”
(PSJ), and are composed mainly by chalcopyrite (96%). Concentrate samples were agglomerate in a
plastic polymeric support matrix (PP), which may be spheres (20 mm in diameter) or pellets (5 mm
on its maximal axial length). The agglomeration process was carried out in an agglomeration drums
wherein acid content is in the range of 40 to 60 kg/ton of concentrate, water in the range of 60 to 90
kg/ton of concentrate and previously grown bacterial inoculum were added. The rotation velocity
fluctuated between 5 to 15 rpm and the residence time varied between 1 to 3 minutes until the
thickness of the adhered concentrate reach 1 to 4 mm. The particles with previous agglomeration
(Figure 2) were load in polypropylene columns in a manner to generate a homogeneous packed bed.
Fresh leaching solution is made to circulate above this bed. The column operated continuously and
the leaching solution was poured at the center of the superior extreme of the column at a surface
velocity in a  range from 7 to 20 L/hm2. The solution contained 35 to 45 mg/L of (NH4)2SO4, 35 to 45
mg/L of MgSO4*7H2O and 35 to 45 mg/L of K2HPO4. This configuration allows achieving the optimal
conditions of momentum transport, heat and mass for each support particle.
3
Chalcopyrite concentrate charge test
28
Figure 2 Photograph showing the polymeric agglomeration particle used and agglomeration tests results
After four hours of chemical leaching with H2SO4, a fresh solution containing 2.5 g/L of ferrous ion,
was introduced into the top of the columns. The pH and the Eh potential of the solution were
measured regularly as well as the concentrations of Fe3+ and Fe2+, total copper, free acid and the
concentration of bacteria in the solution. The leaching columns were maintained operating for a
maximum of 320 days. Air was administered at the base of each column with a compression bolt, oil
free. This air penetrated at the base of the column via forced convection.
BioCobre® Technology validation tests

In order to validate Biocobre® technology for chalcopyrite concentrates, six tests were carried out in
columns of 2 m height on different conditions; less than 270 days for tests using a chloride treatment
(columns 1, 3, 4), and more than 300 days for biological treatment (columns 2, 5, 6). In the tests
chalcopyrite concentrates samples provided by Punta del Cobre mining company were used.
All the experiments were initially maintained at a pH less than 2 via the addition of concentrated
sulfuric acid into the irrigation solution. Once the pH of the pregnant leachate solutions stabilized
under this value, the pH was not readjusted as done by (Herrera et al., 2016).
RESULTS
The columns loaded with PSJ concentrate agglomerated in the two types of polymer matrices (pellets
or spheres) and irrigated with the treatments (bacteria or chloride), at the end of the respective
processing cycle, the difference in recoveries of copper obtained shown a direct correlation according
to the type of Treatment used (bacterial versus chloride) and the same is observed for iron recovery
4
(Tables 1 and 2). The highest recoveries of copper are obtained by using a bacterial treatment,
doubling recovery levels when using chlorides at similar time and solution passed (compare Table 1
and 2).
Table 1 Bioleaching parameters and recovery of Cu an Fe from “PSJ” concentrates
Fresh feeding Recovery
Processing time Irrigation rate Concentrate Matrix Cu Fe
Column (Days) Matrix type (L/h/m2) (Kg) (Kg) % %

2 334 Pellets 12 11,78 12,7 87,92 75,97
5 302 Spheres 12 8,39 3,4 90,24 64,35
6 301 Spheres 12 8,60 3,4 87,69 61,60
Table 2 Chloride leaching parameters and recovery of Cu an Fe from “PSJ” concentrates
Fresh feeding Recovery

Processing time Concentrate Matrix Cu Fe
Column (Days) Matrix type Chloride utilization (Kg) (Kg) % %
1 269 Pellets NaCl + CaCl 11,3 14 49,34 30,43

3 231 Pellets NaCl + CaCl 13 13 54,35 37,62
4 238 Spheres NaCl 5,68 3,18 30,55 18,09
Copper recovery kinetics also shows the same differential trends between treatments (bacteria and
chlorides). Particularly, there is a steep more slope when using bacteria based treatments (Figure 3),
which indicate that bioleaching improve the copper recovery than using chloride (Figure 3). In
addition, it can be observed that the use of pellets improves the recovery of copper from the
concentrate when using chlorides as a leaching solution.
5
100
90%
90
Biological catalysis
(bacteria)
80
70
Cu recovery (%)
60
50
40
Chemical catalysis
(NaCl)
30
20
10
0
0 50 100 150 200 250 300 350 400
Days
C1: Pel+NaCl
Pellet + NaClPSJ C2: Pel+Bact
Pellet PSJ
+ Bacteria C3: Pel+NaCl+CaCl
Pellet PSJ
+ NaCl + CaCl
Spheres
C4: + NaCl
Esf+NaCl PSJ C5: Esf+Bact
Spheres PSJ
+ Bacteria Spheres + Bacteria
C6: Esf+Bact PSJ
Figure 3 Kinetics of Cu recoveries from different column tested
The recovery of iron over time shows the same trends as that of copper, treatment with bacteria
significantly increases iron recoveries compared to the chemical treatment (Figure 4). An
improvement in the recovery of iron is also observed when using pellet as support of the
concentrate than when using spheres (Figure 4).
6
80
70
Biological catalysis
(bacteria)
60
50
Recovery Fe, %
40
30
Chemical catalysis
(NaCl)
20
10
0
0 50 100 150 200 250 300 350 400
Days
Pellet
C1: + NaCl PSJ
Pel+NaCl Pellet
C2: + Bacteria
Pel+Bact PSJ Pellet
C3: + NaCl + CaClPSJ
Pel+NaCl+CaCl
C4: Esf+NaCl
Spheres PSJ
+ NaCl C5: Esf+Bact
Spheres PSJ
+ Bacteria C6: Esf+Bact
Spheres PSJ
+ Bacteria
Figure 4 Kinetic of Fe recoveries from different column tested
DISCUSSION
In a first step, this work involved the operation of bioleaching columns according to the heap reactor
design, based on the agglomeration of copper concentrates rich in primary sulphides around heat
resistant polypropylene particles in order to allow to support the mineral concentrate, and to control
variables required to maximize copper recovery by bioleaching. The operation was carried out at
high temperatures in the presence of thermophilic microorganisms, obtaining high copper recovery
rates in a specific operation time.
The use of pellets improves recoveries of copper and iron, possibly because this support increases
the contact surface, which implies a better chemical or bacterial catalysis in the dissolution of the
metals.
Biocobre® technology is competitive technology versus smelters, specially when concentrates have
impurities and when companies already have leaching process plants (Figure 5).
7
Figure 5 Diferenses in C1 cash Cost (cUS$) between selling concentrates to smelters (Asia) and Biocobre
tecnology aplication in Chile
The principal highlights of the Biocobre technology testing program was:

 Allows processing clean and unpure concentrates (Arsenic impurities)
 Lower environmental impact compared to traditional smeltering/refining.
 Generates copper rich solutions to directly feed SX-EW plants.
 Operates in common temperature and pressure conditions.
 Generate the acid needed.
 Flexible technology able to operate with different leching mediums.
 Allows recovery of by-products (Au, Ag, Mo)
 Can operate in different reactor configurations allowing the use of underuse in conventional
oxide SX-EW plants install capacity.
REFERENCES
Herrera, M.N., Rivadeneira, J., Bordagorry, R., Barrientos, C. and Valeria, M., (2016) Optimization of
a bioleaching process for copper concentrates agglomerated on polypropylene support particles
(under peer review).
RIVADENEIRA HURTADO, Juan. Polymer support and method of leaching of mineral concentrates. U.S.
Patent Application No 14/622,962, 16 Feb. 2015.
Rojas, D., Garay, V. and Cantallopts, J., (2016) Informe De Tendencias Del Mercado Del Cobre Enero
De 2016, pp. 1–37.
Wang S., (2005) Copper leaching from chalcopyrite concentrates. Jom, 57( 7) pp. 48–51.
Wiertz, J.V., Mateo, M. and Escobar, B., (2006) Mechanism of pyrite catalysis of As(III) oxidation in
8
bioleaching solutions at 30 oC and 70 oC. Hydrometallurgy 83 (1–4), pp. 35–39.
9
The Evolution of Complex Ores in the Copper
Industry: Lessons learned from the Gold Industry
and the Acceptance of Pressure Hydrometallurgical
Flowsheets
William McCombe, Kevin Fraser, Brad Hewitt and Frank Cheuk
Hatch, Canada
ABSTRACT
In the mid-1980s the gold industry undertook a significant step change in processing methods with
the first introduction of hydrometallurgical pressure oxidation for complex gold ores and
concentrates. Although roasting had been the standard processing option for complex ores for
hundreds of years, the venture into pressure hydrometallurgy unlocked the value of many complex
ores types. Over the past 30 years gold pressure hydrometallurgy has grown from a few initially
small tonnage operations, to several large tonnage facilities worldwide. Pressure hydrometallurgy
has become accepted standard technology within the gold industry and most of the major gold
producers now have such operations in their portfolios.
It could be argued that copper industry currently faces the same technological step change that the
gold industry faced over three decades ago. Copper concentrates have continued to become more
complex, and the concentrations of some key impurities such as arsenic continue to rise. Pressure
hydrometallurgy is directly applicable to the copper industry and presents the opportunity to add
value in the face of higher treatment penalties and environmental liabilities. More importantly,
pressure hydrometallurgy flowsheets can be integrated into existing common copper circuits such as
heap leaches and SX plants, adding additional synergistic value.
This paper reviews the development of pressure hydrometallurgy in the gold industry to its current
level of accepted technology, and reviews the potential for this technology to add significant value
to the copper industry.
1
INTRODUCTION
In the early 1980’s, Homestake Mining began development of their McLaughlin Mine in Napa
County, California, USA. Faced with both a refractory orebody and mercury mineralization, the
common approach for refractory gold treatment of roasting would not meet environmental off-gas
regulations. Forced to look at alternate processing options due to their feed impurities, Homestake
drew on knowledge of pressure hydrometallurgical processing from the nickel and uranium
industries, resulting in the construction of first commercial gold autoclave facility.
It could be argued that this was a significant technological step change at the time, as it involved the
first application of this processing technology to the gold industry. Moreover, it was also one of the
first generation of commercial pressure metallurgy plants that involved oxidation of the ore,
following the footsteps of oxidation circuits in the uranium industry during the previous decade.
Although McLaughlin represented a technological step change, it was a successful facility, and had
the hallmarks of proper technology development. During design and engineering, a pilot plat
program was conducted, and several lessons learned from the uranium industry were adopted.
McLaughlin set the stage for wide scale adoption and acceptance of this technology in the gold
industry in the subsequent decades.
In recent years, pressure hydrometallurgy has been applied to additional metals, including copper.
While pressure hydrometallurgy technology may be ‘new’ to the copper industry, there is essentially
no significant technological step change as the designs being applied (both from a mechanical and
chemistry standpoint) are identical to those seen in modern mature gold pressure hydrometallurgy
plants. Thus, as disruptive forces make the pressure hydrometallurgical processing of copper more
attractive, the associated technology risk is minimized as it supported by three decades of success
and improvement in the gold industry.
Pressure Hydrometallurgy
Pressure hydrometallurgy is a subgroup of extractive metallurgy, utilizing high temperature and
pressure conditions to oxidize and or leach metals into solution as the primary treatment step prior
to downstream metal recovery. Pressure hydrometallurgy, using pressure vessels typically known
as autoclaves, makes use of the thermodynamic and kinetic advantages of operating at high pressure
and temperature in order to economically recover metals.
Pressure Hydrometallurgy has existed for over a century, with its first application on aluminium ores
in the early 1900’s. Since then, the general technological principals have been applied to a variety of
other metals. In the last three decades the use of pressure hydrometallurgy in gold processing has
grown from an initial few small tonnage operations in the USA into a number of large scale tonnage
operations worldwide.
PRESSURE HYDROMETALLURGY IN THE GOLD INDUSTRY

Over the years there has have been a number of disruptive forces in the gold industry that have led
to the adoption of pressure hydrometallurgical flowsheets. These have included:
 Changes in plant feed characteristics and mineralogy:
- Discovery of more refractory and double refractory ores, which are not amendable
to direct cyanidation.
2
- Discovery of more polymetallic deposits, including those containing copper and zinc
which often are not economically amendable to direct cyanidation due to high
cyanide consumption and/or potential for additional metal recovery credits.
 Global changes towards stricter environmental limitations:
- Tighter limitations on process off-gas emissions:
 Stricter limitations on sulphur dioxide generated from the process and reporting
to the off-gas
 Stricter limitations on mercury generated from the process and reporting to the
off-gas.
- Increased focus on achieving final residue stability for long term storage:
 The requirement to generate a stable residue, in the case of detrimental elements
such as arsenic.
Pressure metallurgy was first commercially applied to the gold industry in the early in 1980’s. The
first commercial facility, built by Homestake Mining at McLaughlin in California, USA was designed
to treat 3000 tpd. The mineralogy of the deposit was refractory, and additionally contained significant
amounts of mercury. Roasting was a viable option for precious metal recovery, however
environmental limitations ultimately drove the selection of pressure hydrometallurgy (Bancroft
Library).
Over the years the application of pressure hydrometallurgy in the gold industry has grown
substantially. In parallel, the ‘technology’ of pressure hydrometallurgy in relation to gold ores has
matured as well. While the general operation of horizontal autoclaves with associated feed, agitation
systems and pressure let down systems has not dramatically changed over the years, many
mechanical improvements have been made in order to achieve higher equipment availability and
production rates.
The history of gold pressure hydrometallurgical facilities can be categorized into three generations:
First – McLaughlin (USA), Sao Bento (Brazil), Mercur (USA), Getchell (USA).
Second – Goldstrike (USA), Lone Tree (USA), Campbell (Canada), Porgera (Papua New Guinea),
Twin Creeks (USA).
Third – Lihir (Papua New Guinea), Kittila (Finland), Pueblo Viejo (Dominican Republic).
With each generation of gold pressure hydrometallurgical plant, the processing technology has
matured, the process intensity has increased, and mining companies have developed the confidence
to expand the capacity of these facilities. As can be seen in Figure 1, over the years both the oxidation
capacity (in tonnes of sulphide sulphur, per day, per cubic meter) and mechanical size of these
facilities has continued to increase. Within the gold industry essentially all pressure hydrometallurgy
projects have been hugely successfully. In many instances gold pressure metallurgy sites represent
some of the largest gold producing facilities in the world, as ‘flagship’ properties for their owners
with multiple sites producing over 1Moz Au/a.
3
Figure 1 Gold and Copper Pressure Hydrometallurgy Plant Growth
Although the gold industry has had a very successful track record with pressure metallurgy, there
have been some pressure metallurgy projects in the nickel industry that have underperformed. As a
result there is a common misconception surrounding pressure metallurgy projects in general that
these processes are highly complex and require significant capital expenditure. In his 1988 paper,
McNulty (McNulty, 1998) looked at the ramp up of various processing facilities, and examined the
key drivers that defined successful projects versus unsuccessful projects. Those that were successful
often had the common themes of reliance on mature technology of similar size and thorough pilot
plant testing. Conversely a number of unsuccessful projects were characterized by having “new”
technology, but often were plagued by poor ore body definition, insufficient piloting and
understanding of chemistry, and improper scale up of equipment and poor engineering. With each
generation of gold pressure hydrometallurgical plants, the technology has become more mature, and
as equipment sizes have grown, and gold mining companies have continued to invest in proper
piloting prior to constructing new facilities. As a result, new gold pressure metallurgy plants typically
meet all of the McNulty criteria for successful projects and associated low risk ranking.
4
DISRUPTIVE FORCES IN THE COPPER INDUSTRY AND THE NEED FOR
ALTERNATE TECHNOLOGIES
In recent years the copper industry has had its own disruptive forces to manage, specifically related
to an increase in the production of complex concentrates and stricter environmental regulations. It is
currently estimated that the average copper concentrate will contain 0.22% arsenic by 2020, with this
value expected to grow in the subsequent years (Mayhew).
The copper industry currently finds itself squeezed between rising arsenic concentration in complex
concentrates and tightening environmental regulations. The key issue with complex concentrates,
and in particular arsenic content, is that arsenic has limited stable forms for long term deposition. It
is essentially a closed circuit element, with no other significant downstream use, representing only
an environmental liability.
In many cases the primary methodology for reducing arsenic content in concentrate is blending with
clean concentrates. As clean concentrates become less prevalent, this approach becomes more
difficult; already limitations can be seen on importing complex concentrates to China that contain
more than 0.5% arsenic.
On the other hand the industry has continued to use roasting as a primary method for treating
complex concentrates, however this process faces an ongoing challenge with respect to roaster dust
that is generated. Roaster dust, typically containing hazardous arsenic trioxide, must be further
treated to stabilize the arsenic.
Finally, recent changes in environmental regulations further complicate matters for the copper
industry. In Chile, new environmental norms requiring reduced arsenic and sulphur emissions place
further strain on roasting technology.
With all of these factors considered, it is clear the current status quo will not be sustainable for the
copper industry. Alternate processing options are required which allow for arsenic in concentrate to
exit the metal supply chain in stable form, while also reducing and or eliminating all environmental
discharge with the associated process.
PRESSURE HYDROMETALLURGY APPLICABILITY TO THE COPPER INDUSTRY

In many regards copper pressure hydrometallurgy is analogous to gold pressure hydrometallurgy.
Table 1 outlines some of the key comparisons between the two processes. It can be seen that they are
indeed very similar.
5
Table 1 Gold versus Copper Pressure Hydrometallurgy
Gold versus Copper Pressure Hydrometallurgy

Parameter Gold Copper
Production Rates No limitation No limitation
Sulphur Oxidation Capacity 0.5 to 1 tS=/d/m3 0.5 to 1 tS=/d/m3
Mechanical Equipment High Pressure Feed Pump High Pressure Feed Pump
Horizontal Autoclave Horizontal Autoclave
Flash Pressure Letdown Flash Pressure Letdown
Typical Operating Temperature >200oC >200oC
Typical Operating Pressure >3000 kPa >3000 kPa
Typical Residence Time varies, >45min varies >45mins
Primary Chemistry Ferrous/Ferric Oxidation
Iron Sulphide to Iron Ferrous/Ferric Oxidation
Sulphate/Oxide Copper Sulphide to Copper Sulphate
Iron Hydrolysis Iron Hydrolysis
Typical Metal Recovery varies, >99% varies, >99%
Reagents High Purity Oxygen High Purity Oxygen
High Pressure Cooling Water High Pressure Cooling Water
In addition to the similarities between the processes, the reality is that pressure hydrometallurgy is
not new to the copper industry. Table 2 outlines operations have already successfully applied
pressure hydrometallurgy for the production of copper.
Table 2 Copper Pressure Hydrometallurgy Facilities
Project Company Location Year Capacity (tpa Cu) Cu Form

Bagdad Freeport McMoRan USA 2005 16,000 Cathode
UHC Vale (CESL) Brazil 2005 10,000 Cathode
Morenci Freeport McMoRan USA 2007 75,000 Cathode
Kansanshi First Quantum Zambia 2007 30,000 Cathode
Pueblo Viejo Barrick Gold Dominican 2013 6,000 Mixed

Republic Sulphide
(Cole 2009), (Fluor, 2008), (Marsden, 2003), (Marsden, 2007)

In addition to the past success utilizing pressure hydrometallurgy in the copper industry, it could be
argued that as the copper pressure oxidation technology is analogous with the gold pressure
hydrometallurgy, copper pressure hydrometallurgy should be treated as a proven technology.
Pressure Hydrometallurgy Value Proposition for the Copper Industry

The use of pressure hydrometallurgy presents tremendous value to the copper industry on a number
of fronts. Pressure hydrometallurgy flowsheets represent an opportunity to process copper to
cathode on site in conjunction with well-established solvent extraction and electrowinning,
regardless of impurity level, and with no penalty costs nor concentrate transport charges and at very
high overall recoveries.
6
The first and foremost advantage of this technology is that pressure hydrometallurgy has the ability
to form environmentally stable residues, with arsenic disposed in a stable form. Stable residues,
which have the ability to be stored in dry impoundment facilities, present the opportunity to remove
arsenic from the metal supply chain, without significant long term liability. Moreover,
hydrometallurgical processes have extremely low emissions, and operate well within forthcoming
environmental regulatory emission limit changes.
Pressure hydrometallurgical flowsheets also provide many potential synergies further enhancing
project economics. In the case where the complex concentrate could be processed in conjunction with
a heap leach operation, the use of pressure metallurgy has the additional advantage of being a net
acid producer, which provides an operating cost credit for the heap leach operation. Moreover, there
is the potential to integrate such a process with an existing operation, as the pregnant liquor stream
produced by the pressure hydrometallurgical facility has in many cases shown to be compatible with
existing solvent extraction circuits.
Depending on the characteristics of specific ores and locations, there are other general potential value
opportunities such as treating other water or process waste streams, other hazardous material
streams containing copper metal credits, and also the potential for heat recovery from the autoclave
circuit for additional process applications. Even without the operational costs saving opportunities
pressure hydrometallurgy potentially includes, the key consideration for the technology is that it
offers a licence to operate for the copper industry as it continues to produce increasingly complex
concentrates. This licence to operate is not often considered in company businesses cases, and will
become more financially apparent as costs increase to make existing production technologies
conform to new environmental regulations.
Lessons Learned from the Gold Industry

In reviewing how pressure metallurgy took hold in the gold industry, it is paramount to note that
changing mineralogy and environmental regulations played a key role in driving the industry to look
at pressure metallurgical options. As pressure metallurgy was implemented, it not only addressed
the environmental concerns, but demonstrated a process route for the very high recovery levels in a
complex mineralogy, answering both primary concerns.
In regard to the environmental considerations, pressure hydrometallurgy represents a process option
that meets environmental requirements for many challenging feeds. In the gold industry, roasters
have long been core process technology; however they too have faced stricter environmental
limitations on environmental emissions, including sulphur dioxide, arsenic, and mercury. Pressure
metallurgy has found its place alongside other technologies such as roasters, especially in situations
where emissions cannot be successfully managed though alternate technologies.
Pressure metallurgy was not accepted overnight in the gold industry. It has seen three generations
of facilities, although after the first generation of plants it had become a generally accepted
technology. While technology risk presents challenges in many industries, methodologies were used
within in the gold industry to reduce this risk. A prime example is Barrick Gold’s approach at
Goldstrike, where the current facility was built in three stages, allowing proof of concept and
economic viability before capital investment for the full facility.
Years of technological development in the gold industry have resulted in the most recent generation
of plants being designed as even larger tonnage operations. Mechanical improvements have resulted
7
in extremely safe and reliable operating facilities. These are successes that are directly applicable to
the copper industry.
CONCLUSIONS
It is clear that the forecasted increase in production of complex concentrates in the copper industry
presents an environmental challenge that needs to be addressed with new technologies. Pressure
hydrometallurgy offers a solution to the core challenge of environmentally safe copper production.
Pressure metallurgy has already been applied in the copper industry. Based on the similarities in
general metallurgy, operating conditions, and mechanical design to the gold industry, pressure
metallurgy should not be considered a new or novel technology. By all intents it is a proven
technology.
A proven solution exists to the copper industry’s growing environmental problem. As economic
pressures continue to put strain on existing technologies from an environmental standpoint, the
copper industry would benefit from the lessons learned in the gold industry from its own challenges
in this area. Through acceptance of pressure hydrometallurgy, the gold industry has been able to
economically and safely develop many new ore types, while maintaining high levels of
environmental compliance.
8
REFERENCES
Cole, J. (2009). Morenci Concentrate Leach Plant First Year Review. SME Annual Meeting.
Fluor. (2008). DC-0000-03-0001 Process Design Criteria (Pueblo Viejo).
Marsden, J. (2003). Copper Concentrate Leaching Developments by Phelps Dodge Corperation.
Hydrometallurgy 2003.
Marsden, J. (2007). Freeport-McMoRan Developments in Copper Concentrate Leaching.
COM2007/Cu2007.
Mayhew, K. (n.d.). Teck – Aurubis: An integrated mine to metal approach to develop high arsenic copper
deposits using the CESL process.
McNulty, T. (October 1988). Developing Innovative Technology. Mining Engineering, 50-55.
The Bancroft Library, U. o. (2000). The Knoxville Mining District, The McLaughlin Gold Mine, Northern
California, Volume VII, an oral history conducted in 1993, 1994, 1995, 1997, and 1999, Regional Oral History
Office.
9
The FLSmidth® ROL Process: BASF-FLS Pilot Plant
Testing
David Chaiko1, Jack Bender2, Carlos Eyzaguirre1, Sara Rocks1, Chase Dickinson1 and
Frank Baczek1
1. FLSmidth, USA
2. BASF, USA
ABSTRACT
The copper mining industry faces two significant challenges: 1) economic stress during the
transition from oxide to sulfide ores, and 2) high smelting costs and environmental issues in
treating arsenic laden concentrates. BASF and FLSmidth are working together to develop and
demonstrate alternative hydrometallurgical process technologies to meet these challenges. The
development of the FLSmidth ROL process has successfully progressed to continuous, pilot-plant
operation with integrated SX/EW utilizing BASF's Captiva SX reagent. The ROL process uses a
mechano-chemical leach to overcome passivation by coupling Stirred Media Reactors (SMRt) in
series with Continuous Stirred Tank Reactors (CSTR's). The innovative SX reagent functions at high
temperatures and low pH's and offers superior copper extraction efficiencies and very high
selectivity for copper over iron. The new ROL/SX/EW system is a highly efficient process
technology for copper recovery from sulphide concentrates using acidic ferric sulfate lixivants
under atmospheric conditions. A pilot plant test of the ROL/SX/EW system yielded 93% copper
recovery from chalcopyrite and an exceptionally high Cu/Fe extraction selectivity with iron transfer
within the limits of detection once the system reached equilibrium.
1
INTRODUCTION
The FLSmidth® Rapid Oxidative Leach (ROL) technology is an atmospheric, 80-90°C, acidic ferric
sulfate process for leaching copper from primary and secondary copper sulfide concentrates. An
enabling feature of this mechano-chemical technology is the incorporation of inter-stage Stirred
Media Reactors (SMRt) within a series of Continuous Stirred Tank Reactors (CSTR's). In December,
2015, FLSmidth and BASF announced a joint development effort to expedite ROL
commercialisation, and the first integrated, pilot-plant test was conducted in 2016. The joint effort
brings together FLSmidth's leach technology with BASF's innovative solvent extraction reagents
(Captiva®) and processes.
In this paper, we report on the pilot test of an integrated copper recovery process, consisting of
leach, solid/liquid separation, SX/EW, raffinate recycle, and a raffinate bleed to maintain iron and
sulfate balance. The goal was several fold: a) to demonstrate that efficient copper dissolution could
be maintained in the presence of entrained organic from the SX system, b) determine the extent of
elemental sulphur oxidation during chalcopyrite leaching, c) demonstrate an ability to chemically
control frothing within the leach circuit with minimal downstream impact on the SX process, d)
demonstrate an efficient and selective copper SX process with a high-grade (HG) pregnant leach
liquor (PLS) having a pH range between 0.7-0.9 & a high level of entrained solids, and e) the
production of LME Grade A Cu cathodes.
MEHODOLOGY
Concentrate Leach Circuit

A chalcopyrite concentrate, with the composition listed in Table 1, was ground to a P80 of
approximately 20-25µm using an FLSmidth VXP mill. Ground concentrate slurry, at approximately
50 wt% solids, was reductively activated using a Cu(II) metathesis process at 60°C and a
Cu2+/CuFeS2 mol ratio of 0.005 as previously described (Chaiko and Rocks, 2016). Activation
modifies the surface and bulk phase properties of chalcopyrite by doping the mineral with minute
amounts of Cu(II). This process serves multiple functions: a) it introduces lattice strain within the
particle crystallites and thereby increases leach rates, b) alters the surface wetting properties to
reduce frothing during oxidative leach, and c) increases the conversion of sulfide to sulfate/sulfuric
acid during chalcopyrite dissolution which reduces purchased acid requirements. Not included in
this pilot test were precious metals recovery with sulphur isolation & deportment as a final waste
form.
After combining with recycled raffinate (redox potential of ~720mV), the activated slurry entered
the leach circuit at a slurry density of 6-7wt%. The leach circuit, consisting of two inter-stage SMRt
reactors with two 40L CSTR's, was operated with an overall residence time of 4 hrs. and produced a
high-grade PLS of approximately 15-17 g/L Cu. The SMRt reactors had a mean slurry residence
time of 2.5 min. and were charged with 9.3 Kg of ceramic media (2.0-2.5 mm dia. & density of 6.2
Kg/L). The power draw, as determined from shaft torque measurements, was slightly under 35
kW/m3 of media.
2
Table 1 Major mineral constituents of the chalcopyrite concentrate as determined by XRD
Mineral Weight Percent

Chalcopyrite 55.7
Pyrite 34.7
Quartz 3.4
Covellite 2.6
Sphalerite 2.2
Figure 1 Integrated leach/SX/EW system for copper recovery from chalcopyrite
Solvent Extraction/Electrowinning Circuit

The configuration of the SX/EW plant is illustrated in Figure 2. The system was built in the standard
configuration for a simple SX plant containing countercurrent extraction, wash, and strip stages.
Solutions were generated on site and added to the system where they were equilibrated. The first
several hours of operation were used to adjust mechanical systems, flows, electrolyte solutions and
heating system. Feed solutions from ROL were used on the extraction system. A 220 g/L acid
solution was used to initiate the electrolyte generation, with the copper coming from the extraction
of metal from the PLS solution. The organic solution was a mixture of the BASF high temperature
reagent (Bender, Emmerich, and Nisbett, 2013 and 2014) Captiva blend, in SX 80. The pH of the PLS
was approximately 0.7 throughout the campaign. Five 316 SS cathodes and six standard Pb/Sn/Ca
mix anodes (lead: 95.5%, tin: 0-1.3%, calcium: 0.01-1.1%), were operated at approximately 315 A/m2
of current density. 200 g/t of guar was used as a smoothing aid.
Surge tanks were used to buffer liquor flows between the ROL system and the SX system. PLS was
collected before entering the SX system and raffinate from SX was accumulated before returning to
the ROL system. Throughout the operation of the integrated plant, operational and analytical
deficiencies were identified and implemented to compensate for the needs of the ROL and SX/EW.
3
Integrating Continuous Mechano-Chemical Leach with SX/EW

Various mechano-chemical leach/SX flowsheet configurations can be considered for copper sulfide
treatment systems. Firstly, there is the choice of intra- versus inter-stage placement of the stirred
media reactor(s). The second configurational choice regards integration of the leach and SX circuits.
One possibility is a conventional, multi-stage leach circuit that produces a single PLS stream.
However, this approach is less efficient than the various Split Circuit™, and sequential circuit
configurations that are designed to produce both a high-grade and a low-grade PLS (Nisbett, et. al.,
2009; Kordosky and Nisbett, 2010).
Leach testing has shown that only 1-2, inter-stage SMRt reactors, coupled with four CSTR leach
stages, are sufficient to achieve 97+% Cu recovery from chalcopyrite in 8 hrs. or less (FLSmidth,
unpublished results). For operational simplicity of the integrated pilot test, we used a two-stage,
leach circuit to produce a high-grade PLS feed for the SX system. Based on batch leach data and a
total reactor residence time of four hrs., the expected Cu recovery was 90+% (Eyzaguirre, et. el.,
2015).
The process flow diagram for the pilot test is shown in Fig. 2. Solutions were recycled in the
traditional Leach/SX/EW manner and included PLS clarification, SX/EW, iron bleed and raffinate
recycle. The SX circuit consisted of a series of 2 extraction (E), 1 wash (W) and 1 strip (S) stages. The
EW cell consisted of five cathodes (316 SS), six anodes (standard Pb/Sn/Ca mix) and was operated
with a targeted current density of 315 A/m2.
Chalcopyrite Leach Circuit

The Cu leach circuit was purposefully operated at a lower than optimal pH to demonstrate the
exceptional capabilities of the Captiva® SX reagent. The pH of the PLS varied between 0.7 and 0.85
with no detectable impact on leach rates or Cu recoveries within the leach circuit. Higher operating
pH's, such as 1-1.5 are acceptable, but jarosite formation during oxidative leaching can become an
issue at pH's ≥ 2.0.
Effect of Entrained Organic on Cu Leach

In the absence of a SMRt reactor, batch leach testing showed that recycled raffinate containing
entrained organic as low as 20 mg/L, could significantly inhibit chalcopyrite dissolution to <20%
(FLSmidth, unpublished results). Consequently, a primary goal of the pilot test was to demonstrate
an ability to achieve high Cu recoveries with continuous raffinate recycle containing entrained
organic. Not only did the test results show that the SMRt reactor is able to overcome this problem,
but the resulting steady-state dissolution rate of the Cu-bearing minerals was fast enough to
autogenously heat the two 40L CSTR's to 85-90°C. Autogenous heating at this CSTR size was
unexpected because of the large reactor heat loses due to the high surface-to-volume ratio and
evaporative cooling effects of O2 injection.
4
Figure 2 Operational diagram of the integrated pilot plant
Multi-Stage Leach Performance

The leach results in Table 2 show that covellite and sphalerite were completely leached within the
first CSTR stage. Pyrite dissolution within stage 1 was minimal and increased to 11% at stage 2. X-
ray analysis of the leach residue showed that only 50% of the sulfide was oxidized to elemental
sulphur, while the remainder was oxidized to sulfuric acid. This level of in situ generation of acid is
an advantage as it helps to meet process demands for a) reactions with acid consumers during
concentrate pre-treatment and b) oxidation of copper sulfides (i.e., CuFeS2 + 2.5O2 + H2SO4  CuSO4
+ FeSO4 + H2O + S°).
Table 2 Stage-wise dissolution of sulfide minerals
Percent Leached
Mineral CSTR-1 CSTR-2
Pyrite ~0 11
Chalcopyrite 66 92
Covellite 100 100
Sphalerite 89 97
5
100 0.12
ROL, 20 Micron Feed

(a) Stage 2 0.1 (b)
80
Cu Leach Rate(Mol/h*L)
0.08
Cu Recovery, %
Stage 1
60
0.06
40
ALBION, US Patent 5,993,635
0.04 4 hr. residence time
10 Micron Feed
20
0.02
20 hr. residence time

0 0
0 1 2 3 4 5 6 7 8 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Leach Time (h) Mol Cu Remaining to Leach/L
Figure 3 Comparison of pilot plant chalcopyrite leach with (a) batch test results and (b) the Albion process
Progressing from a batch, intra-stage SMRt/CSTR configuration to a continuous, inter-stage

configuration shows no noticeable reduction in Cu leach rates (see Fig. 3a). Furthermore, inter-stage
mechano-chemical systems can be more efficient than the alternative of ultra-fine grinding of the
concentrate prior to chemical leaching. In Fig. 3b we compare our continuous, stage-wise ROL leach
rates with published data for the Albion process. The Albion pilot-plant data were extracted from
U.S. Patent 5,993,635, Example 7 (Hourn, Turner & Holzberger, 1999) and show ~93% Cu recovery
in stage 2 after 13 hrs. residence time, while the ROL process produced ~92% Cu recovery in stage 2
with only 4 hrs. overall residence time. The ROL process is also less sensitive to feed particle size.
A significant benefit of inter-stage SMRt reactor placement is faster chalcopyrite leach rates at
coarser particle sizes (e.g., 20- vs. 10-micron for Albion).
Mechano-Chemical Energy Efficiency

Because the SMRt reactor is a mechano-chemical reactor, and not a grinding mill, comparable
power is only ~1/10th that of the Isa- and VXP-mills. In this pilot test, the SMRt reactors were
operated at just under 35 kW/m3 of media. Total SMRt reactor mixing energy was quite low (i.e., 0.5
kWh/kg Cu leached) and compares quite favourably to other mechano-chemical processes. For
example, a two-stage, turbo-mill reactor system, used by the US Bureau of Mines (Cobble et. Al.,
1993), required ~2 kWh/kg Cu leached to achieve ~90% Cu recovery from chalcopyrite in 8.5 hrs
using a stoichiometric amount of ferric in the leach liquor. Thus, overall process efficiency gained
by splitting the mechano- and chemical-functions between two separate reactors, within a
continuous inter-stage configuration, is significant.
Froth Control
The amphiphilic nature of partially-leached metal sulfide particles, coupled with a need to inject an
O2 containing gas to maintain the leach reaction, means that frothing can be a serious problem
when leaching flotation concentrates. If uncontrolled, frothing leads to short circuiting through the
leach reactor and excessive solids holdup within a froth layer. In the Albion process, froth control
was maintained with the use of 2 kg lignosol/t (Hourn, Turner & Holzberger, 1999). FLSmidth has
developed a series of froth inhibitors that are effective at significantly lower concentrations (e.g.,
6
0.05-0.5 kg/t solids). Our new chemistries & low dosages are more economical and do not interfere
with post-leach S/L separation and SX processes.
Solvent Extraction/Electrowinning Operation

The solvent extraction configuration was comprised of a 2E, 1W, and 1S system. This was not
expected to be the eventual configuration used in the ROL/SX/EW process; however, it was the
simplest design to confirm the operation of the SX plant using an ROL PLS. The PLS used by the SX
system was generated by ROL. This was used to equilibrate the organic and to build the electrolyte.
Initially, we had decided to run the SX plant at full flows for part of the day and shut down as the
ROL built up an inventory of PLS. Once the campaign started running it was decided to alter the
conditions to be able to run continuously based on the rate of PLS production. The consequence of
running in this fashion is that the hydrometallurgical results are not valid for standard operation.
Therefore, the retention times and flows would not be relevant to a standard run. The result was
mixing times that were near equilibrium times. Since the results would be more optimistic, it was
decided not to report the metallurgical results. In addition, the organic to aqueous ratio was skewed
dramatically so that the low volume of aqueous could be handled. Planned modification to the
CSTR reactors (i.e., increasing reactor volumes from 40L to 100L) will enable future campaigns to be
run under typical operating conditions to determine hydrometallurgical data.
The physical operation of the pilot plant was optimal. Even though several solids excursions were
seen throughout the run, there was no evidence of crud. Upon removal of the solutions at the end
of the run, there was no evidence of solid stabilized emulsion. There was little evidence of
entrainment throughout the run. The wash stage, which recycled its own aqueous solution and was
used as a gauge for entrainment, showed almost no transfer of copper after three days of
continuous operation.
Copper cathode generated in the process can be seen in Figure 4. The electrowinning operation was
slightly undersized for the amount of copper generated by the ROL plant. However, due to the
short operation of the pilot plant campaign, this was not an issue.
Figure 4 Copper cathode from the ROL/SX/EW integrated process
7
CONCLUSIONS
An integrated ROL/SX/EW system was operated for several days. This system recycled solutions in
the traditional L/SX/EW method illustrated in Figure 5. Although the operation of the integrated
process was successful, optimization of the SX configuration and the ROL/SX integration needs to
be accomplished.
Figure 5 Typical leach, solvent extraction, electrowinning system
Physical reagent operation was excellent throughout the SX system, despite relatively high solids
being present. We were able to plate smooth copper cathode from a copper electrolyte generated
wholly from copper generated by the ROL process.
It is in the future runs of the integrated system that hydrometallurgical results and the optimization
of the SX configuration will be determined. A continuously operating system with a split circuit
design is the eventual goal of the piloting process.
REFERENCES
Baláž, P. and Achimovicova, M. (2006) 'Mechano-chemical leaching in hydrometallurgy of complex
sulphides,' Hydrometallurgy, 84, pp.60-68.
Bender, J., Emmerich, N., and Nisbett, A. (2014) ‘Evaluation of the Next Generation of Copper
Solvent Extraction Reagents’, Alta Nickel, Cobalt, Copper Conference 2014, ALTA Metallurgical
Services, Perth.
Bender, J., Emmerich, N., and Nisbett, A. (2013) ‘Development of a New Generation of Copper
Solvent Extraction Reagents’. Proceedings Copper 2013.
Chaiko, D. J., Rocks, S. S., (2016) 'Activated semiconductor compounds having increased
electrochemical reactivity and associated methods thereof,' U.S. Patent 9,422,610 B2.
8
Cobble, J. R., Jordan, C. E., and Rice, D. A., (1993) 'Hydrometallurgical Production of Copper From
Flotation Concentrates,' USBM, RI 9472.
Eyzaguirre, C., Rocks. S., Klepper, R., Baczek, F., and Chaiko, D. (2015) 'The FLSmidth Rapid
Oxidative Leach (ROL) process: A mechano-chemical approach for rapid metal sulfide dissolution,'
7th International Seminar on Process Hydrometallurgy, Antofagasta, Chile, Graber, t., Taboada, M.
E., Valenzuela, F. Eds., Gecamin Digital Publications, Chapter 2, pp. 1-11.
Hourn, M. M., Turner, D. M., and Holzberger, I. R. (1999) 'Atmospheric Mineral Leaching Process,'
U.S. Patent 5,993,635.
Kordosky, G. A., and Nisbett, A., (2010) 'Methods for improving the recovery of metal leaching
agents,' U.S. Patent 7,799,294 B2.
Nisbett, A., Baxter, K., Marte, K., and Urbani, M., (2009) 'Flowsheet Considerations for Copper-
Cobalt Projects,' The Southern African Institute of Mining and Metallurgy Base Metals Conference,
pp. 139-151.
Welham, N. J., (2001) 'Processing of Gold-bearing sulphides,' Mineral Engineering, 14, No. 3, pp.
341-347.
9
CHAPTER 5
Fundamentals and
Operation of Solvent
Extraction and Ion
Exchange
High Chloride in PLS and their Impact on Copper
Solvent Extraction
Hector Yáñez, Leonor Ardiles and Cristóbal del Río
BASF, Chile
ABSTRACT
Due to water scarcity and lower copper grades of oxides and mixed resources, the use of seawater
(Montes, 2016) and the implementation of new leach technologies using chloride salts addition in
Chile and Peru, are increasing. This means into the next future will be more operations with leach
solutions containing high concentrations of chloride, bringing new challenges to the downstream
process, solvent extraction and electrowinning. It is well known and accepted in the region how to
get under control the risk of chloride transfer to electrowinning (i.e. coalescers, active loaded organic
tank, wash stages, low viscosity reagent), however the chemical behaviour of the solvent extraction
process has not been intensively studied for mixed sulphate and chloride media. A laboratory study
involving PLS (pregnant leach solution) with sulphate and chloride using BASF copper organic
extraction reagents was conducted. The principal results show an important improvement in organic
copper maximum load and extraction kinetics. As an example, when the chloride in the PLS has
concentration, more than 20 g/L, the copper loaded in organic increase at least 7% when PLS´s pH is
low (equal or below 1.5). Both effects indicated are even improved when the chloride concentration
in rich leach solution is increased above 20 g/L to pH 1.5 or lower in comparison with the behaviour
of PLS with only sulphate to the same conditions.
1
INTRODUCTION
The hydrometallurgy future is facing several challenges like: How to fulfill the actual production
capacity of SX-EW while the oxide resources are decreasing in quantity and quality, and Which will
be the best leaching technologies to do it: improving Dump or Heap leach, Concentrate leach, White
metal Leach, or In Situ leach. Ore leach in chloride media is a very promising technology to improve
the recovery in copper sulfides in heap or dump leach. One of the principal concerns in the SX EW
processes, when plant is processing pregnant leach solutions (PLS) with high chloride concentration
(>5 g/L), is the control of the chloride transfer to the electrolyte to avoid corrosion by pitting of the
stainless plates (permanent cathodes) in electrowinning. The use of some devices such as active
organic tanks to wash the organic, coalescers and/or wash stages to remove aqueous entrainment in
organic are some of the methods used into the industry with this purpose. The right selection of the
extractant is another key factor control entrainment. Reagents based on Ketoxime, having lower
viscosity than others reagents, are certainly an adequate alternative for these cases. The oximes´
chemical behavior in sulphate media is described in Table 1 (Redbook BASF Mining Solutions). The
Ketoxime have moderate strength while the Aldoxime or modified Aldoximes are stronger. There
are only a few studies of chemical behavior in sulphate with chloride media (Lu & Dreisenger, 2013).
However, extraction in only chloride media had been described in technical literature (Szymanowski,
1943)
Table 1 Chemical behavior of Oximes in Sulphate Media (Source: Redbook BASF Mining
Solutions)
Non-modified Modified
Property Ketoxime Aldoxime
blend aldoxime
Extractive Strength Moderate Very strong Customized Customized
Stripping Very good Poor Customized Customized
Cu/Fe selectivity Excellent Excellent Excellent Excellent
Extraction kinetics Very good Very fast Fast Very fast
Leaching in Sulphate and Chloride media

The chloride is a strong leaching agent, and leach processes have been developed to leach sulfides
copper ores in high chloride media. These processes add salt to the leach solution or add reagents
CaCl2 and/or NaCl and H2SO4 to the curing process. The cured ore is then stacking in heaps to be
leached after a rest stage of the ore curing at the heaps. An example of this kind of process is
CuproChlor® developed by Antofagasta Minerals S.A. (Aroca & Backit, 2012). The PLS on this
process can reach 40 to 120 g/L of chloride concentration.
To study the chemical behavior of oximes in extraction stages with and without chloride in PLS
solution (Sulphate and Chloride media), a laboratory test plan was conducted.
2
EXPERIMENTAL
Pregnant leach solution (PLS): Synthetic PLS was prepared in the laboratory, with component
concentrations (Al+3, Mg+2, Fe+3, Fe+2, Mn+2) adjusted to average conditions in Chilean operations (95 g
SO4-2/L). Chloride concentrations of 0, 20, 40 and 90 g/L were studied. Solutions were adjusted by
NaCl addition. Other cations were added as sulphate salts. In addition, the pH was adjusted to 1.5
and 1.0 by H2SO4 addition. (pH-meter Thermo Scientific Orion Star and Electrode “8157BNUMD ROSS
Ultra Triode epoxy-body pH/ATC)
Table 2 Pregnant leach solutions (PLS) conditions
Solution PLS Cl- g/L SO42- g/L pH

PLS 1 A1 0 95 1,0
PLS 2 A2 0 95 1,5
PLS 3 B1 20 95 1,0
PLS 4 B2 20 95 1,5
PLS 5 C1 40 95 1,0
PLS 6 C2 40 95 1,5
PLS 7 D1 90 95 1,0
PLS 8 D2 90 95 1,5
Organic phase was prepared at 24% v/v with diluent and BASF extractants were based on Ketoxime
(LIX®84I) and Modified Aldoxime (LIX®684N-LV).
Lean electrolyte was prepared having; Cu 35 g/L and Acid 180 g/L (lean electrolyte). The electrolyte
was a standard electrolyte. The electrolyte does not vary when PLS has a higher chloride
concentration, due to the measures taken by the operations or projects to control the chloride transfer
to the electrolyte.
Standard parameters of performance

The standard parameters to be analyzed are Extraction and Strip isotherms, which give us the
metallurgical performance approach and the Extraction kinetic tests to give us an approach to the
industrial mixing efficiency expected. Isotherms and kinetics tests were determined for each PLS
solution contacted with the organic solution prepared at 24% v/v, LIX®84I or LIX®684N-LV. The
results are provided in Table 2. All tests were determined according to the BASF standard
procedures.
3
Chemical characterization of PLS

Chemical characterization of the Synthetic PLS is given in Table 3.
Table 3 Chemical characterization of PLS
Ion Unit Value

Cu2+ g/L 4.5
SO 42- g/L 95
Cl - g/L 0; 20; 40; 90
Fe T g/L 2.0
Fe 2+ g/L 0.4
Fe3+ g/L 1.6
Mn2+ g/L 2.0
Al3+ g/L 6.1
Mg2+ g/L 11.2
Ni+ g/L 0 – 58
pH 1.0; 1.5
Acid and pH relationship, with high Chloride concentration

For samples containing the same acid content, higher chloride concentration leads to a lower pH.
This behavior is described in the Figure 1. For example, in the case of a PLS with 2-4 g/L of sulfuric
acid, the pH is expected to be 1.5-2.0, however, with high chloride concentration the pH is in the
range of 1.0-1.2. The equilibrium of the sulfate/bisulfate/sulfuric acid is altered by the addition of
chloride. This is due to the addition of the chloride ions and their effect of the overall intimate ion
pairing in the system.
Figure 1 Acid and pH depending on and Chloride concentration
4
Extraction Isotherms
As was described, extraction isotherms were prepared at laboratory, to study the chemical
equilibrium with different levels of chloride concentration at pH 1.5 and 1.0. Figure 2 shows the
isotherms for pH 1.0, with and without chloride in PLS.
Figure 2 Extraction Isotherms at pH 1.0
An increase of copper loading in the organic was noted when the chloride concentration is high (90
g/L Cl-) at lower pH (pH 1.0). This effect is more important when using a Ketoxime reagent than
when using a Modified Aldoxime. Table 4 summarize the results obtained at pH 1.0-1.5.
Table 4 Maximum copper loading according PLS and reagent
Copper load in organic PLS pH 1.0 Copper load in organic PLS pH 1.5
LIX®684N- LIX®684N-
LIX®84I LIX®84I
LV LV
90 g/L Cl- 9.5 11.4 90 g/L Cl- 11.2 13.2
0 g/L Cl- 7.1 9.5 0 g/L Cl- 10.6 12.6
Diff. 2.4 1.9 Diff. 0,6 0.6
% increase 34 20 % increase 6 5
Stripping Isotherms
Stripping isotherms were prepared for each reagent tested to have both isotherms (extraction and
stripping) and to evaluate the copper extraction in the circuit. Tables 5 contains the strip isotherm
data to each case indicated.
5
Table 5 Strip Isotherms (Cu in g/L)
O/A LIX84I LIX684N-LV

ratio aq org aq org
1/10 37 0,45 37 2,09
1/4 38 0,49 38 2,23
1/3 39 0,50 39 2,34
1/1 47 0,66 46 2,80
3/2 52 0,88 51 3,31
5/2 58 1,13 58 3,98
LE: Cu 35 g/L, acid 180 g/L
Extraction kinetics
Extraction kinetic tests were performed at pH 1.5 and 1.0, with PLS having 0 and 90 g/L of chloride
concentration. Isotherm Graphs are illustrated in Figure 3. PLS without Chloride content resulted in
good extractions kinetics, considering the mixing time is industrial operations is 150-180 seconds.
When the PLS has high chloride concentration (90 g/L) the resulting kinetics show a relevant
improvement, with the results similar for both reagents, Ketoxime or Modified Aldoxime.
Figure 3 Extraction Kinetics
Circuit evaluation
To evaluate the metallurgical performance, a 2E 1S configuration was evaluated using the BASF
ISOCAL™ software to model the isotherms prepared previously. PLS with pH 1.0 having 0 or 90 g/L
of chloride concentration was modeled for Ketoxime (LIX®84I) or Modified aldoxime (LIX®684N-
LV) reagents. Principal parameters evaluated are; copper recovery, Max. copper load (ML), Cu in
organic unloaded (UO) and Cu in organic loaded (LO).
6
Table 6 Circuit conditions
PLS, g/L Conc. LE, g/L Conc. Stream Flow, m3/h SE, %
Cu+2 4.4 Cu+2 35 PLS 1000 E1 90
SO4-2 95 Acid 180 LE 230 E2 90
Cl- 0-90 Organic 1200 S 95
pH 1 O/A ratio 1.2
PLS: Pregnant leach solution, LE: Lean Electrolyte and SE: Stage Efficiency
The details of the copper deportment in the organic is described in the Figure 4 It can be noted that
without chloride, the Modified Aldoxime can load more copper at this pH, but the copper transfer is
similar in both cases due to the better stripping of the Ketoxime. However, when the chloride
concentration is high (90 g/L), the copper transfer in the circuit with Ketoxime reagent is slightly
better than with Modified aldoxime. (Copper transfer = LO – UO)
Figure 4 Copper in organic. Circuit 2E 1S, PLS (pH 1.0, Cl- 0 and 90 g/L)
Table 7 contains a summary of the copper recovery obtained. The Ketoxime performs better than a
Modified Aldoxime at a low pH, when the chloride concentration in PLS is high (90 g/L).
Table 7 Circuit conditions
Copper extraction in 2E 1S circuit (%)

Cl g/L
- LIX®84I LIX®684N-LV
0 76.8 79.4
90 88.5 87.2
Diff. +11.7 +7.8
7
CONCLUSION
For South America, hydrometallurgical operations are expected to increase the use of seawater
and/or the addition of chloride salts to the leaching process to improve the leaching performance of
refractory and/or secondary sulfides ores. Therefore, in South America, a 30% or 40% increase of the
hydrometallurgical operations in the next future will have high chloride concentration in their PLS
(higher than 25 g/L).
For these plants, PLS will have a low pH, with values between 1.0 to 1.5. This is a challenge to solvent
extraction in terms of copper transfer. While the higher chloride concentration in PLS means lower
pH, it improves the chemical behavior of the oximes in extraction stages, having a positive effect on
copper loaded in organic and in the extraction kinetics.
Ketoximes (LIX®84I) have more improvement than Modified Aldoxime (LIX®684N-LV). For a PLS
with 4.4 g Cu/L and pH 1.0, the maximum copper load increase is 34% for Ketoximes, while in the
case of the Modified Aldoxime the increase is 20%.
Due to the better stripping performance of Ketoxime over Modified Aldoxime in a conventional
circuit with configuration 2E 1S with PLS at pH 1.0, the Ketoxime (LIX®84I) performs slightly better
than the Modified Aldoxime (LIX®684N-LV) in terms of copper transfer.
For a PLS having higher chloride concentration and low pH, the reagents based on Ketoxime are
excellent alternatives in terms of copper transfer and physical behavior. A positive physical behavior
is reported in actual operations due to the low viscosity of the reagent based on ketoxime without
equilibrium modifiers.
REFERENCES
Aroca, F, Backit, A, Jacob, J, 2012. Cuprochlor® a hydrometallurgical technology for mineral sulfide
leaching. Minera Michilla, Antofagasta Minerals. Hydroprocess 2012
Lu, J, Dreisenger, D, 2013b. Solvent extraction of copper from chloride solution I-loading isotherm,
Hydrometallurgy 137, 13-17
Lu, J, Dreisenger, D, 2013. Solvent extraction of copper from chloride solution II-Cuprous oxidation
by oxygen coupled with simultaneous cupric solvent extraction, Hydrometallurgy 138, 48-53
Montes, C, Water use in copper mining: Trends of a critical input. Chilean copper Commission, April
2016. (www.cochilco.cl)
Redbook BASF Mining Solutions
Szymanowski, J 1943, Hydroxioximes and Copper Hydrometallurgy, CRC Press. 283-288
8
Effect of Degradation Products on the Performance of
Hydroxyoxime Extractants
Wang Chao-hua, Xu Zhi-gang, Ji Shang-jun, Zou Qian, Peng Xue, Ren Jiao and Yang
Zheng-shu
Kopper Chemical Industry, China
ABSTRACT
Hydroxyoxime is the main extractant in the copper solvent extraction industry. In the course of
using the hydroxyoxime extractant it can degrade because of long-term contact with acid and other
harmful ingredients. The degradation products consist of a series of substances, such as aldehyde,
ketone, organic acids, amides and other organic debris. These degradation products accumulate in
the organic and may affect the performance of the extractant. In this paper, the effect of degradation
products on the performance of hydroxyoxime extractant was studied. Finally, various methods to
eliminate the adverse effect of degradation products on extractants are discussed. The results
showed that: (1) Degradation products such as aldehyde, ketone etc could change the extraction
and stripping equilibrium, weaken the extraction ability and increase copper content in the
raffinate. The higher content of degradation products in the organic phase, the more the extraction
capacity decreased. (2) Degradation products could slow down the extraction kinetics. (3) The
Cu/Fe selectivity of the extractant declines, which increases the iron concentration in the loaded
organic. (4) Degradation products, especially surfactants, can prolong the phase separation time
and accelerates the degradation of hydroxyoxime extractants.
1
1. INTRODUCTION
Hydroxyoxime reagents, which can selectively extract Cu2+ under acidic condition, have become the
main extractants in modern copper hydrometallurgy(PEI Shi-hong,2009).
However, hydroxyoxime extractants degrade due to long-term exposure to acids and other harmful
substances such as MnO4-, NO3-, Cl-,etc(Xu zhi-gang,2014). The degradation of the extractants not
only reduces the extraction ability of the reagent, but also harms plant production. In severe cases,
the extraction production can not be carried out and the organic is even scrapped, which greatly
increased the cost. Moreover, if the waste organic is treated improperly, the environment may be
significantly affected. Therefore, it is important to study the influence of the degradation products
on the performance of extractants to provide guidance for the recovery of degraded organic and the
reuse of waste organic.
The degradation products of hydroxyoxime extractants contain aldehyde, ketone, surface active
substances and other organic debris(Zhu Tun. 2002), these degradation products will significantly
affect the performance of extractant. For example, degradation products can reduce extraction
ability, prolong phase separation time and lead to more entrainment(Xu zhi-gang, 2016). Therefore,
the operators in extraction plant should pay attention to the degradation of organic phase and
response measures. The treatments of degradation products include chemical and physical
methods.Aldehyde and ketone can be oximated to the corresponding aldoxime and ketoxime
through the oximation reaction. So aldehydes and ketones can be reused by chemical method. This
approach helps to reduce the consumption of extractant and reduce costs. The effect of surface
active substances on the phase separation is obvious (.Menon V B,1988. Liu Jiang-she,2002). Many
scholars have studied its impact mechanism(.Liu Xiao-rong,2001. Tambe D E,1993.) Removal of
these surfactants is generally carried out by active clay treatment, which has been applied in many
extraction plants successfully.
In this paper, the influence of these degradation products on extraction performance was studied to
provide reference and solution for the copper extraction plant to repair the degraded organic and
reuse the waste organic.
2. PERFORMANCE TEST METHODS OF EXTRACTANT

2.1 Maximum copper load
2.1.1 The organic is mixed with standard feed A1(6.0 ± 0.1g/L Cu 2 +, 3.0 ± 0.1 g/L Fe3 +, pH=2.0 ± 0.1)
at O/A = 1: 1 ( 25℃) for 3min, then discharge the aqueous, this procedure repeats 4 times.
2.1.2 Take the organic obtained from 2.1.1 to test Cu concentration, and marked as Maximum
copper load.
2.2 Isotherm, kinetics, Cu/Fe selectivity and phase separation time
2.2.1 The organic was mixed with stripping solution A2 (Cu35.0g/L, H 2SO4160.0g /L) at O/A = 1: 1
for 3 min to obtain the organic O1.
2.2.2 The organic O1 is mixed with A1 at O/A = 1: 1 ( 25℃) in the performance test device.
2
2.2.3 30s later, the organic phase is sampled as O2, then Cu in O2 is determined and marked as E30.
300s later, the stirring is stopped, start to record the phase separation time. After finished phase
separation, the loaded organic O3 is obtained.
2.2.4 Take O3 to test Cu and Fe concentration, and marked as E300(Cu) and E300(Fe) respectively.
2.2.5 The organic O3 was mixed with A2 (O/A = 1: 1, 25°C), 30s later, the organic phase is sampled
and obtained organic O4, then the Cu content is determined and marked as S30(Cu). 300s later, the
stirring is stopped and start to record the phase separation time, then the loaded organic O5 is
obtained.
2.2.6 Take organic O5 to measure Cu concentration, and marked as S300(Cu), which is the stripping
isotherm.
2.2.7 Extraction kinetics(WE) = E30／E300×100
2.2.8 Extraction isotherm(E): E=E300
2.2.9 Cu/Fe selectivity = E300(Cu)／E300(Fe)
2.2.10 Stripping kinetics(Ws)=E300(Cu)-S30(Cu)/E300(Cu)-S300(Cu)×100
2.2.11 Stripping isotherm(S): S=S300
3. EXPERIMENTAL RESULTS AND DISCUSSION

3.1 Main ingredients in the degraded organic
To understand the degradation products, the components of the following three degraded organics
have been analyzed. The results are shown in Table 1.
Table 1 Main ingredients in degraded organic
Degradation products
Aldoxime Ketoxime Modifier
Organic No.
（%）（%） (%) Aldehyde Ketone Other organic
（%）（%） debris（%）
1# Organic 6.67 0 4.53 6.26 0 5.85
2# Organic 2.95 4.81 0 5.25 3.38 5.75
3# Organic 0 0 0 5.97 5.21 6.45
As shown in Table 1, the degradation products from hydroxyoxime extractants are primarily
aldehydes, ketones and other organic compounds.
Table 2 lists the physical and chemical properties of the above degraded organics.
3
Table 2 The physical and chemical properties of the degraded organics
Viscosity Surface tension

Organic No. Specific gravity
（mPa.s）（mN/m）
1# Organic 0.85 4.68 25.1
2# Organic 0.86 4.75 25.0
3# Organic 0.86 4.56 24.8
Table 2 shows the surface tension of degraded organics is lower than normal organic. This
indicates that the degradation products contain surface active substances. In addition, the specific
gravity and viscosity of the degraded organics were higher than the standard organic. This is due to
the accumulation of the degradation products in the organic.
3.2 Effect of degradation products on the performance of hydroxyoxime extractant
Table 3 shows the effect of aldehyde on the main parameters of aldoxime extractants. Wherein the
organic contained 0.18mol/L aldoxime(2-hydroxy-5-nonyl-benzaldehyde oxime), the remainder
were different aldehyde plus diluent in different proportions.
Table 3 The performance of 0.18mol/L aldoxime extractants with different aldehyde content
The content of aldehyde in the Maximum copper Extraction

Stripping isotherm（g/L）
organic load（g/L） isotherm（g/L）
0% 5.71 5.59 3.46
2.5% 5.71 5.41 3.17
5.0% 5.70 5.06 2.52
7.5% 5.68 4.92 2.10
10.0% 5.66 4.79 1.81
FromTable 3 it can be seen that the maximum copper loading, extraction isotherm and stripping
isotherm of aldoxime extractant decreased with an increase in aldehyde. Table 3 also shows that
degradation products can change the extraction isotherm and stripping isotherm of the extractant.
Changing the extraction isotherm in this manner results inhibiting extraction. Changing the
stripping isotherms in this manner results making the reagent easier to strip.
Table 4 showed the influence of degradation products of aldehyde and ketone on the performance
of Mextral 984H. Mextral 984H contains equal parts aldoxime and ketoxime.
4
Table 4 Performance of Mextral984H(10%)with different contents of degradation products
Maximum copper Extraction Stripping isotherm

The organic
load（g/L） isotherm（g/L）（g/L）
Mextral984H(10%)+ diluent(90%) 5.31 4.86 1.72
Mextral984H(10%)+diluent(80%)+3#
5.29 4.80 1.65
organic(10%)
Mextral984H(10%)+ diluent(40%)+3#
5.21 4.63 1.54
organic(50%)
Mextral984H(10%)+3# organic(90%) 5.16 4.51 1.42
Mextral984H(10%)
+diluent(80%)+aldehyde(5%)+ketone( 5.25 4.78 1.60
5%)
As shown in table 4, the effect of degradation products on Mextral984H is similar to that of

modified aldoxime extractants.
These test results show that degradation products have the same effect as modifiers. In other
words, degradation products reduces the extraction capability but makes stripping easier.
3.3 Influence of degradation products on the extraction and stripping kinetics
In order to investigate the effect of degradation products on the extraction and stripping kinetics,
the extraction and stripping kinetics of the organic containing degradation products was studied
and compared with the organic without degradation products. In the experiment, the fresh Mextral
984H, diluent and the above 3# degraded organic sample were prepared as the organic. The
concentration of new Mextral984H in organic was 10%, the total proportion of diluent and 3#
degraded organic was 90% . The experimental results are shown in table 5.
Table 5 Influence of degradation products on the extraction and stripping kinetics
30 seconds extraction 30 seconds

The organic
kinetics stripping kinetics
Mextral984H(10%) +diluent(90%) 98.5% 99.0%
98.0% 98.6%
organic(10%)
96.5% 97.8%
organic(50%)
Mextral984H(10%)+3# organic(90%) 94.2% 96.8%
Table 5 shows, the degradation products decrease the kinetics of the reagents both in extraction and
stripping performance.
5
3.4. The effects of degradation products on the extraction process
The test results shown in Table 1, 2, 3, 4 and 5 were done under standard conditions and show that
the degradation products affect the extraction performance of hydroxyoxime extractants. Next, the
extraction parameters under certain extraction process were investigated to study the influence of
degradation products on the extraction process. The experimental conditions and results were
shown in table 6.
Table 6 The effects of degradation products on the extraction process of Mextral984H
PLS Extraction O/A ratio in O/A ratio Raffinate

The organic
Cu（g/L） process extraction in strip Cu（g/L）
4.0 2E-1S 1:1 2:1 0.09

Mextral984H(15%)+
8.0 2E-1S 2:1 2:1 0.21
diluent(85%)
12.0 2E-1S 3:1 2:1 0.35
4.0 2E-1S 1:1 2:1 0.09

Mextral984H(15%)
+diluent(75%) + 3# 8.0 2E-1S 2:1 2:1 0.26
organic(10%)
12.0 2E-1S 3:1 2:1 0.44
4.0 2E-1S 1:1 2:1 0.10

Mextral984H(15%)+
diluent（35%） +3# 8.0 2E-1S 2:1 2:1 0.35
organic（50%）
12.0 2E-1S 3:1 2:1 0.64
4.0 2E-1S 1:1 2:1 0.10

Mextral984H(15%)+3#
8.0 2E-1S 2:1 2:1 0.38
organic(85%)
12.0 2E-1S 3:1 2:1 0.68
It can be seen from table 6, as the concentration of degradation products (3# organic) increased, the
extraction ability of the extractant decreased. Also the higher the PLS Cu concentration, the more
the degradation products affected on the extraction ability of the reagents. When the Cu
concentration in the PLS was 4g/L, the copper concentration in the raffinate increased from 0.09g/L
to 0.1g/L with increasing degradation products concentration. When the PLS Cu concentration was
12g/L, the Cu concentration in the raffinate increased from 0.35g/L to 0.68g/L as the concentration of
degradation products increased.
3.5. Effect of degradation products on phase separation
Degradation of hydroxyoxime extractants can produce a series of degradation products. As these
degradation products accumulate in the organic phase, the viscosity and specific gravity of the
organic phase increases and the surface tension decreases. The effect of degradation products on
phase separation is shown in table 7.
6
Table 7 Effect of degradation products on the phase separation of the organic
phase
phase
The composition of the separation
separation in floc Entrainment
organic in
Extraction
Stripping
Mextral984H (10%)+ diluent almost no entrainment after

48s 50s no
(90%) 50s
Organic entrained aqueous

Mextral984H (10%)+diluent phase, entrainment was
155s 140s a little
(70%) + 3# organic (20%) basically eliminated after 5
min.

Mextral984H (10%) + diluent phase seriously, entrainment
230s 215s more
(40%) +3# organic (50%) was basically eliminated
after 7min.
Mextral984H (10%) + diluent

almost no entrainment after
(80%) + aldehyde (5%) + 55s 54s no
60s
ketone (5%)
From table 7, it can be seen that the degradation products increased the phase separation time.
Increasing the phase separation time results in greater phase entrainment. The organic without
degradation products results in a 50 second phase separation with no entrainment or floc. As the
concentration of degradation products increases, phase separation time increases. This is due to the
degradation products containing surface active substances. Surface active substances, such as
phenol, carboxylic acid, amide and so on, have high polarity, which tend to cause emulsification of
the organic(Zhou Gui-ying, 2007. Ritcey G M,1980). To reduce the effect of these surface active
substances, the organic phase should be treated by clay.
Activated clay can effectively adsorb the surface active substances in the organic. Table 8 showsthe
results of the phase separation experiment after clay treatment. The change of the phase separation
performance before and after the clay treatment can be seen.
Table 8 The results of phase degradation of degraded organic after clay treatment
phase
phase
The composition of Clay separation
separation in Flocs entrainment
the organic amount in
Extraction
Stripping
Mextral984H (10%) +
almost no entrainment after
diluent (40%) +3# 1% 60s 65s no
70s
organic (50%)
7
Mextral984H (10%) +
phase seriously, entrainment
diluent (40%) +3# 0 230s 215s a little
was basically eliminated after
organic (50%)
7min.
As shown in Table 8 the phase separation performance of degraded organic is significantly

improved after clay treatment. The deterioration of the phase separation performance would
indirectly effect the extraction performance, the following results can illustrate this point.
Table 9 Effect of phase separation on extraction under the condition of organic phase containing
degradation products
PLS Cu Extraction O/A ratio in O/A ratio Clarification Rich electrolyte Raffinate
（g/L） procees extraction in stripping time(min) Cu(g/L) Cu(g/L)
4.0 2E-1S 1.5:1 2:1 3 39.58 0.62
4.0 2E-1S 1.5:1 2:1 5 39.97 0.28
4.0 2E-1S 1.5:1 2:1 8 40.16 0.11
Note: the composition of the organic :10%Mextral984H+40%diluent +50% 3# organic.

The results in Table 9 show the effect of surface active substances on the extraction performance is
mainly due to poor phase separation Poor phase separation results in higher entrainment which
produces changes in extraction equilibrium and finally decreased extraction rate. If the phase
separation time was sufficient, the extraction performance can go back to normal levels.
3.6 Effects of degradation products on the Cu/Fe selectivity of organic
The effect of degradation products on Cu/Fe selectivity of the organic was shown in table 10.
Table 10 Effects of degradation products on the Cu/Fe selectivity of Mextral984H
The composition of the organic feed liquid O/A Cu/Fe
10%Mextral984H+50% 3# Cu2+: 6.0g/L;

1:1 320
organic+40% diluent Fe :3.0g/L; pH=2.0
3+
10%Mextral984H+20% 3# organic Cu2+: 6.0g/L;

1:1 665
+70% diluent Fe3+:3.0g/L; pH=2.0
10%Mextral984H+5% Cu2+: 6.0g/L;

1:1 2150
aldehyde+5%ketone +80% diluent Fe3+:3.0g/L; pH=2.0
10%Mextral984H +90% diluent + 0% Cu2+: 6.0g/L;

1:1 2760
3# organic Fe :3.0g/L; pH=2.0
3+
It can be seen from table 10 that the degradation products had great influence on the Cu/Fe
selectivity of the organics, the Cu/Fe selectivity of organics decreased sharply with increasing
concentration of degradation products.
8
3.7. Effects of degradation products on the stability of extractants
3.7.1 The effects of degradation Products on anti-oxidation of the extractants
The effects of degradation products on the anti-oxidation of the extractants was studied. The 3#
organic sample was used as the degradation products. The experimental conditions were as
follows: (1) the aqueous consisted of 35 g/L Cu, 180 g/L sulfuric acid, 2g/L NaClO. (2) O/A=1:1. (3)
temperature: 25 ℃. (4) using continuous stirring and mixing. The degradation or loss of the
extractant was determined by the maximum copper load. The effects of degradation products on
the anti-oxidation of extractants were shown in table 11.
Table 11 Effect of degradation products on anti-oxidation of the extractants
Max Cu Max Cu Max Cu Max Cu Max Cu Max Cu

load after 0 load after load after load after load after load after
The organic days 10 days 20 days 30 days 40 days 50 days
(g/L) (g/L) (g/L) (g/L) (g/L) (g/L)
10%Mextral984H+90
5.31 5.30 5.29 5.23 4.74 4.02
% diluent
10%Mextral984H+80
% diluent +5% 5.25 5.24 5.23 5.20 4.72 4.00
aldehyde+5%ketone
10%Mextral984H+70
%diluent +20%3# 5.29 5.08 4.75 4.32 3.62 2.87
organic
10%Mextral984H+40
%diluent +50% 3# 5.28 5.01 4.63 4.18 3.31 2.51
organic
As shown in Table 11, the degradation products containing surface active substances can accelerate
the oxidation degradation of extractants; and the higher the surface active substances concentration
the quicker the extractants are oxidized. The main degradation products of aldehyde and ketone
had little effect on the oxidation rate. From the results it is the surface active substances with large
polarity, such as phenol, carboxylic acid, amide and so on, that lead to the rapid oxidation
degradation of the extractants. The main degradation products of aldehyde and ketone, which are
low polarity molecules, do not accelerate the oxidation rate of the extractants.
3.7.2 Effect of degradation products on the stability of extractants in the presence of permanganate
The experimental conditions were as follows: (1)t he aqueous composition: Cu 35g/L, sulfuric acid
180g / L, 0.5g/L of MnO4-(supplement 3 times a day) ;(2)O/A =1:1, (3)Temperature : 25 ℃, (4) )
continuous stirring and mixing. The degradation or loss of the extractant is determined by the
maximum copper load. The results are shown in table 12.
9
Table 12 Effect of degradation products on the stability of extractants in the presence of
permanganate
The Max The Max The Max The Max

The Max Cu
Cu load The Max Cu Cu load Cu er load Cu load
The composition of the load after
after 0 load after 5 after 10 after 20 after
organic 15days
days days（g/L） days days 25days
（g/L）
（g/L）（g/L）（g/L）（g/L）
10%Mextral984H+90%
5.31 4.67 3.55 2.42 1.35 0.37
diluent
10%Mextral984H+70%di
5.29 4.56 3.46 2.29 1.15 0.25
luent +20%3# organic
10%Mextral984H+40%di
5.28 4.52 3.43 2.23 1.10 0.21
luent +50% 3# organic
Table 12 shows that in the presence of permanganate, the degradation of the extractant is different
from that of hypochlorite. In the presence of permanganate, the induction period of the oxidation
reaction is very short and the extractant was rapidly oxidized. Also the loss ratio of extractant was
almost proportional to the amount of permanganate and this results was independent of the
concentration of degradation products in the extractants.
4. ANALYSIS OF PRACTICAL PROBLEMS CAUSED BY DEGRADATION OF

EXTRACTANTS
Example
ACu producing plant using hydroxyoxime extractant, the extractant completely degraded after one
year and had no extraction capacity because the PLS contained a high Mn concentration.The
organic analysis showed that the organic contained 0% aldoxime,12%aldehyde and about 10%
other degradation products. The total organic was about 150m 3. If discarded, it may not only cause
great economic losses, but also lead to serious environmental pollution. So the plant operators
wanted to continue to use the organic. So Kopper Chem was engaged to recover the extraction
performance. The first step, the organic was adjusted by adding Mextral984H to the concentration
of 20%. Then this adjusted organic was used to process the PLS (15g/L Cu, pH=2.5) according to the
manufacturer's extraction process (3E-2W-3S). The experimental results showed that the Cu
concentration in the raffinate was 1.1g/L. But in the next experiment it was shown that the raffinate
was only 0.4g/L when processing the PLS under the same conditions by the fresh organic of
"20%Mextral984H+80%kerosene". So that further organic adjustment were carried out.
The analysis results showed that the organic of the factory contained high concentration of
degradation products, which inhibited the extraction ability of the reagentand changed the
extraction equilibrium. Since the copper concentration of the PLS was high, extracting copper
10
produces high acid concentration which further inhibited the extraction ability. These factors lead
to an increase in copper content in the raffinate. Thereafter, the organic was adjusted by adding
Mextral860H(aldoxime extractant) which had more powerful extraction ability, and resulted in a
raffinate Cu concentration of 0.41 g/l. Although the degradation products in original organic can
inhibit the extraction ability of Mextral860H too, but the powerful extraction ability of Mextral860H
just offset this effect, so as to achieve a good extraction performance.
5. CONCLUSION
The hydroxyoxime extractants used in the copper industry degrade due to a variety of reasons and
produce degradation products, such as aldehyde, ketone, surface active substances and other
organic debris. These degradation products affect the performance of the extractants: (1) Decrease
the extraction ability, resulting in a lower copper extraction rate. (2)Deteriorate the phase separation
performance. The surface active substances in the degradation products effected the phase
separation, which slowed down the speed of phase separation and increases entrainment, leading
to the deterioration of the extraction results. (3) Degradation products decreases the Cu/Fe
selectivity.(4) Degradation products also accelerates the degradation of extractants.
Understanding the effect of degradation products on the performance of extractants can help
intaking appropriate measures to eliminate or reduce the adverse effects. Knowing how to treat
these degradation products can assist plant operators to recover performance.
REFERENCES
1.PEI Shi-hong, XIE Rui-li，JIN Meng. Extractants in Copper Hydrometallurgy. Contemporary
Chemical Industry,2009,38(1):78-82.
2 Xu Zhi-gang.Some Problems in Solvent Extraction System, Hydrometallurgy,2014.33(1):1-3.
3.Zhu Tun. Modern copper metallurgy. 2002 :114-115.
4.Xu Zhi-gang. Performance and Quality Maintenance of Copper Extractant.
Hydrometallurgy,2016,35(3):65-69.
5.Menon V B, Wasan D T. A review of the factors affecting the stability of solids-stabilized
emulsions.Separation Science and Technology,1988,23(12):2131-2142.
6.Liu Jiang-she, Lan Zhuo-yue, Qiu Guan-zhou. Mechanism of crud formation in copper solvent
extraction. Central South University Technology,2002,9(3):169-172.
7.Liu Xiao-rong. Research on mechanism and Prevention of interfacial emulsion formation in
copper solvent extraction Process. Doctoral thesis,2001,9.
8.Tambe D E, Sharma M M. Factors controlling the stability of colloid stabilized emulisions:an
exprimental investigation. Colloid Interface Science,1993,157(1):244-253.
9.Zhou Gui-ying, Ruan Ren-man, Wen Jian-kang, Li Ling. Study on Mechanism of Interfacial
Emulsification in Solvent Extraction Process. Metal Mine,2007,378(12):72-74.
10.Ritcey G M, The Cause and Treatment of Crud in Solvent Extraction Processes.
Hydrometallurgy,1980,5: 97-107.
11
12
Effect of PLS Characteristics and Extractant Concen-
tration on the Iron Transfer in Copper SX Plant
Tang Qi-ming, Li feng, Liu dan, Yang Qi-hua, Zhou shu-rong, Wang Jing-hong and Chen
Shi-min
ABSTRACT
Lower iron transfer and higher copper transfer are important objectives in all copper SX plants. The
transfer Copper and iron depends greatly on the copper and iron concentration in the loaded organic.
In this paper, Cu/Fe rejection ratio was used to represent the ratio of copper concentration to iron
concentration in the loaded organic. The effect of PLS pH, PLS Cu and Fe concentration, plus extract-
ant concentration in the organic phase, on the Cu/Fe rejection ratio was researched. At first, the fresh
organic was mixed with an electrolyte (35g/l Cu, 180g/l H2SO4) for 3 minutes at O/A=1:1. After phase
separation, the organic was mixed for 3 minutes at O/A=1:1 with a simulated PLS at 35℃. Copper and
iron concentration in the loaded organic were determined. Finally Cu/Fe rejection ratio was calcu-
lated. The results indicate that Cu/Fe rejection ratio increased with increasing PLS Cu concentration.
The Cu/Fe rejection ratio decreased with increasing the PLS pH, increasing PLS Fe concentration and
increasing extractant concentration in the organic. These results can be applied to optimize SX oper-
ating parameters in order to increase copper transfer and minimize iron transfer, especially with
changing PLS composition.
1
INTRODUCTION
In copper solvent extraction (SX) plants, iron transfer from the pregnant leaching solution (PLS) to
electrolyte will increase the electrolyte iron concentration. This increased iron concentration in the
electrolyte reduces the current efficiency of copper electrowinning and increases operating costs (Y.
Khouraibchia & M.S. Moats, 2010). Fortunately hydroxyoxime extractants have high Cu/Fe selectiv-
ity. An important advantage of hydroxyoxime extractants is having a high Cu/Fe selectivity, typically
greater than 2000. Because of this high selectivity, iron transfer was usually neglected during the SX
plant design (Mariusz B. Bogacki & Jan Szymanowski, 1990). To further reduce iron transfer between
the PLS and the electrolyte, a loaded organic wash stage is typically added in the plant configuration.
This wash stage removes iron from the loaded organic due to the iron being crowded out and thus
removed by the wash water (Michael J. Virnig & G. Timothy Fisher, 2003). Increasing the effective
residence time for the PLS and organic in the mixer of E1 also can reduce the iron transfer from PLS
to the electrolyte (Gary A. Kordosky, 1986). Although ion-exchange technology could be used to re-
move Fe (Ⅲ) from the copper electrolyte (David B. Dreisinger & D. Richard Shaw, 1999), the general
method to reduce the electrolyte iron concentration is having an electrolyte bleed. However, in-
stalling an electrolyte bleed system increases operational cost due to the lost of chemicals added to
the electowinning operation.
In fact, many issues could affect the iron transfer besides the reagent Cu/Fe selectivity. For example:
entrainment in the loaded organic, PLS characteristics (including pH, Cu concentration, Fe concen-
tration) and extractant concentration the organic phase. If these issues are not addressed properly,
iron transfer will increase. When the PLS in a SX plant is used to test the Cu/Fe selectivity of an
extraction reagent, the result usually cannot reach 2000 because the standard test conditions used to
test the Cu/Fe selectivity are very different compared to the typical PLS parameters processed in
commercial SX plants (J. J. Taute et al., 2015). Actual Cu/Fe selectivity result ing from processing PLS
solutions encountered in typical commercial plants is more important for process optimization than
using standard PLS test solutions.
In a SX plant, Cu/Fe concentration ratio was usually called Cu/Fe rejection ratio. The higher the re-
jection ratio, the less the iron transfer. In this paper, the PLS effect and the reagent concentration effect
on the rejection ratio of a 1E+1S SX configuration were tested. In addition, how to consider the iron
transfer during the plant design is discussed.
METHODOLOGY
Synthetic PLS preparation: copper(Ⅱ) sulphate pentahydrate and iron(Ⅲ) sulphate were dissolved
in water, pH of the solution was adjusted by 30% sodium hydroxide. Forty-eight (48) different syn-
thetic PLS solutions were prepared. The PLS composition was shown in TABLE 1.
Table1 Composition of the synthetic PLS
PLS pH=1.0 PLS pH=1.5 PLS pH=2.0

No. Cu(g/L) Fe(g/L) No. Cu(g/L) Fe(g/L) No. Cu(g/L) Fe(g/L)
1 2.5 4.0 17 2.5 4.0 33 2.5 4.0
2 3.5 4.0 18 3.5 4.0 34 3.5 4.0
2
3 4.5 4.0 19 4.5 4.0 35 4.5 4.0
4 5.5 4.0 20 5.5 4.0 36 5.5 4.0
5 2.5 6.0 21 2.5 6.0 37 2.5 6.0
6 3.5 6.0 22 3.5 6.0 38 3.5 6.0
7 4.5 6.0 23 4.5 6.0 39 4.5 6.0
8 5.5 6.0 24 5.5 6.0 40 5.5 6.0
9 2.5 8.0 25 2.5 8.0 41 2.5 8.0
10 3.5 8.0 26 3.5 8.0 42 3.5 8.0
11 4.5 8.0 27 4.5 8.0 43 4.5 8.0
12 5.5 8.0 28 5.5 8.0 44 5.5 8.0
13 2.5 10.0 29 2.5 10.0 45 2.5 10.0
14 3.5 10.0 30 3.5 10.0 46 3.5 10.0
15 4.5 10.0 31 4.5 10.0 47 4.5 10.0
16 5.5 10.0 32 5.5 10.0 48 5.5 10.0
·Synthetic organic preparation: Mextral984H was dissolved in Mextral DT100. The organic compo-
sition was shown in TABLE 2.
Table2 Composition of the synthetic organic
Organic No. I II III IV V
Extractant concentration(%,V/V) 13 15 17 19 21
·Pre-loaded fresh organic with electrolyte: 250mL each fresh organic was mixed with 250mL synthetic
electrolyte (35g/L Cu as sulphate, 180g/L sulphuric acid) for 10 minutes. After complete phase sepa-
ration, copper concentration in the organic was determined.
·Pre-heated organic and PLS to 35℃: Place each pre-loaded organic and each synthetic PLS into a 37℃
water bath for 2hours. Then measure 200mL pre-loaded organic and 200mL synthetic PLS for the
next step operation.
·Mix PLS and pre-loaded organic for 5minutes: 200mL pre-loaded organic and 200mL synthetic PLS
were mixed in a 35℃ water bath at 1275rpm for 5minutes. The mixer was shown in figure 1. After
phase separation finished, the centrifugal phase separation at 3500rpm was used to remove any aque-
ous residue in the loaded organic. Then copper and iron concentration in the organic was determined.
·Cu and Fe concentration in the organic was determined by atomic absorption spectroscopy(AAS).
Finally calculate the rejection ratio.
3
Figure1 Mixer of the PLS and pre-loaded organic
RESULTS
Test results were shown in figure 2 to figure 5. From these results, the following conclusion could
be obtained:
·Cu/Fe rejection ratio increased with increasing the PLS copper concentration.
·Cu/Fe rejection ratio increased with decreasing extractant concentration in the organic.
·Cu/Fe rejection ratio increased with decreasing PLS pH.
·Cu/Fe rejection ratio increased with decreasing PLS iron concentration.
4
Figure2 Cu/Fe rejection ratio when PLS iron concentration was 4.0 g/L (1E+1S)
Figure3 Cu/Fe rejection ratio when PLS concentration was 6.0 g/L (1E+1S)
5
Figure4 Cu/Fe rejection ratio when PLS iron concentration was 8.0 g/L (1E+1S)
Figure5 Cu/Fe rejection ratio when PLS iron concentration was 10.0g/L (1E+1S)
When the PLS pH was 1.0, Cu/Fe rejection ratio was more flexible with changes in PLS copper and
iron concentration, and extractant concentration. Influence of copper concentration was greater than
the influence of extractant concentration and iron concentration. Therefore, Cu/Fe rejection ratio of
the same extractant may be changed from one plant to another because the PLS characteristics and
the operation parameters are different. That means the iron transfer will change from one plant to
the other even if the plants are using the same extractant. If the PLS has a higher pH(for example
pH=2.0), higher iron concentration (for example 10.0g/L) and a lower concentration of copper(for
6
example 2.5g/l) , an extractant with a higher Cu/Fe rejection ratio should be selected in order to reduce
the iron transfer from PLS to electrolyte.
DISCUSSION
In a SX plant, a wash stage is usually included to further reduce the iron concentration in the loaded
organic prior to the shipping stage. The higher the Cu/Fe rejection ratio of the wash stage, the less
iron left in the organic after the wash stage. To maximize the effectiveness of the wash stage to reduce
iron in the loaded organic, the pH and iron concentration in the wash water should be as low as
possible. Additionally, the copper concentration in the wash water should be kept as high as possi-
ble. Following these recommendations will remove more iron from the organic to the wash water
and thus minimizing the iron transfer from the PLS to the electrolyte.
As another operational consideration, the adjustment of the PLS composition and extractant concen-
tration in the organic could reduce the iron transfer from PLS to the electrolyte. For example, decreas-
ing the PLS pH and decreasing the extractant concentration in the organic reduces the amount of iron
transfer. However, this will also reduce the copper transfer from PLS to the electrolyte, which reduces
the production of copper cathode.
As shown in Figure 6, copper extraction efficiency E (%, defined as equation 1) increased when de-
creasing the PLS pH and PLS copper concentration. When the extractant concentration increased, the
copper extraction efficiency also increased. Therefore, when the copper extraction efficiency in-
creased, Cu/Fe rejection ratio decreased. Adjustment of PLS composition and extractant concentra-
tion to reduce iron transfer will sacrifice the copper recovery of a SX plant. Nevertheless, each indi-
vidual SX plant must examine the PLS composition and extractant concentration to achieve optimal
performance after balancing iron transfer and copper recovery.
Figure6 Copper extraction efficiency when PLS iron concentration was 8.0 g/L (1E+1S)
7
For example, we assume that η equals copper extraction efficiency(%) minus iron concentration in
the loaded organic(g/L). When η has maximal value, iron transfer is as low as possible in order to
keep copper extraction efficiency(%) as high as possible. Therefore, a particular SX plant can optimize
the PLS composition and extractant concentration on the η contour map. As shown in TABLE 3, the
optimal SX parameter should be located where η has the highest value. For example, at PLS pH 1.0
and PLS iron concentration 4.0g/L, the optimal PLS copper concentration is 2.5g/L to 3.1g/L and the
optimal extractant concentration is 19.5% to 21%. Note well. These results correspond to a 1E x 1S
configuration. If the plant configuration is multiple stages of extraction and stripping, a different
contour map must be constructed. In other words, for each type of plant configuration, a specific
contour map is created.
From TABLE 3, following are some results for the PLS composition and extractant concentration to
maximize copper transfer and minimize iron transfer. A high extractant concentration should be se-
lected when the PLS pH is low (for example PLS pH=1.0). When the PLS pH increases, the SX plant
should increase the PLS copper concentration or decrease the extractant concentration in the organic.
This will result in high copper transfer but low iron transfer. When the PLS iron concentration in-
creases, the optimal PLS copper concentration should increase or PLS pH should be decreased, in
order to reduce iron transfer.
CONCLUSIONS
Iron transfer in a SX plant was affected not only by the extractant property, but also by the PLS com-
position and extractant concentration in the organic. Iron transfer increased with increasing the PLS
pH, the PLS iron concentration and extractant concentration in the organic. When the PLS copper
concentration increased, iron transfer should be decreased. Optimization of the PLS composition and
extractant concentration could reduce the iron transfer while keeping the copper recovery as high as
possible. For example, when the PLS pH was 1.0, increase of the extractant concentration would be
very effective. When the PLS pH increased, SX plant should increase the PLS copper concentration
or decrease the extractant concentration in the organic. When the PLS iron concentration increased,
the optimal PLS copper concentration also should be increased or PLS pH should be decreased in
order to reduce iron transfer.
Table3 η contour map at different PLS characteristics and extractant concentration(1E+1S)
pH=1.0, Fe=4.0g/L pH=1.0, Fe=6.0g/L

PLS Cu=2.5 to 3.1g/L, extractant concentration=19.5% to 21% PLS Cu=2.7 to 2.9g/L, extractant concentration=20.5% to 21.0%
8
pH=1.5, Fe=4.0g/L pH=1.5, Fe=6.0g/L
PLS Cu=2.8 to 3.1g/L, extractant concentration=20.0% to 20.5% PLS Cu=5.0 to 5.3g/L, extractant concentration=20.1% to 20.6%
pH=2.0, Fe=4.0g/L pH=2.0, Fe=6.0g/L

pH=1.0, Fe=8.0g/L pH=1.0, Fe=10.0g/L

9
pH=1.5, Fe=8.0g/L pH=1.5, Fe=10.0g/L
pH=2.0, Fe=8.0g/L pH=2.0, Fe=10.0g/L

REFERENCES
David B. Dreisinger & D. Richard Shaw (1999) Ion exchange and regeneration process for separation
and removal of iron (Ⅲ) ions from aqueous sulfuric acid metal ion-containing solutions. US5948264.
Gary A. Kordosky (1986) Solvent extraction process, US4582689.
J. J. Taute, P. Bwando, G. Chisakuta, G. Mitshabu and A. Nisbett (2015) Improved copper/iron selec-
tivity in solvent extraction, Copper cobalt Africa ( incorporating the 8th southern African base metals
conference), pp281–290.
Mariusz B. Bogacki & Jan Szymanowski (1990) Modeling of extraction equilibrium and computer
simulation of extraction-stripping systems for copper extraction by 2-hydroxy-5-nonylbenzaldehyde
oxime, Ind. Eng. Chem. Res. 29, pp601–606.
Michael J. Virnig & G. Timothy Fisher (2003) Solvent extraction processes for metal recovery,
US6599414B1.
Y. Khouraibchia & M.S. Moats (2010) Evaluation of the effect of copper electrowinning parameters
on current efficiency and energy consumption using surface response methodology, Electrochemis-
try in Mineral & Metal Processing 8 (EMMP 8), 28(6), pp295–306.
10
Study on the Effect of Diluent on the Performance of
Extractant
Wang Chao-hua, Xu Zhi-gang*, Zou Qian, Ji Shang-jun, Wang Fei, Peng Xue and Ren
Jiao
ABSTRACT
The organic phase used for solvent extraction were consists of extractants, modifiers (in some cases)
and diluent. In almost all formulations, the diluent is the highest concentration. Diluent plays a
very important role in the solvent extraction: reduce the viscosity and specific gravity of the organic
phase, accelerate the phase separation, improve the mass transfer efficiency and improve the
extraction kinetics, and so on. The composition and properties of the diluent have a significant
effect on the performance of the extractant and then extraction operation. In this paper, the
influence of the composition and properties of the diluent on the performance and loss of the
hydroxyoxime extractants is examined. The results showed that the volatile loss of low flash point
diluent was more than that of high flash point diluent. And low flash point diluent had a greater
security risk in the extraction process. The physicochemical properties of diluent such as viscosity,
specific gravity and surface tension has an influence on the extraction performance such as kinetics,
copper-iron selectivity and phase separation. Furthermore, the aromatic compounds in the diluent
could decrease the extraction reaction speed and have some inhibitory effect on copper extraction.
The physicochemical properties of diluents such as surface tension and phase separation index
could slow down or accelerate oxidation and nitrification of the extractants.
1
1. INTRODUCTION
The organic in metal solvent extraction are consisted of extractants, diluent or modifiers. The
diluent is the main component of the organic phase and plays an important role in the metal
extraction solvent (Zhu Tun, 2002 ; Luo Aiping, 1998), and has an important effect on the
performance of extractants. The diluent can reduce the viscosity and specific gravity of extractants,
speeding up the phase separation rate. Diluents can also improve the activity of extractants and
improve the net copper transfer, increasing reaction kinetics and improving extraction efficiency.
At present, hydroxyoxime extractants are widely used in copper SX plants. The diluents used in
copper extraction are specially processed (LI Huajie, 2013). Because the viscosity of the
hydroxyoxime extractant is very high at normal temperature, these special diluents must be added
to reduce the overall specific gravity and viscosity of the overall organic phase. Thus, the choice of
diluent is very important for every extraction plant. There are many types of diluents in the market,
each having unique composition and physical properties. The properties and compositions of
diluent have great influence on the performance of the extractant (LU An, 2002; Ritcey G M, 1974),
the extraction operation, as well as a direct influence on the product quality and production cost.
Using an improper diluent may create SX operational problems and increase costs. Therefore,
selecting the appropriate diluent is very important in the overall SX operation. Even with the
importance of selecting the proper diluent, very little research or testing has been done on this
topic. In addition, there is no uniform standard for the selection of diluents in SX operations. In this
paper, the influence of the diluent on the performance of hydroxyoxime extractants is studied, so as
to provide some guidance in the selection of diluent in the extraction industry.
2. EXPERIMENTAL RESULTS AND DISCUSSION
2.1 Physico-chemical indexes and composition of several diluents
Table 1 The physicochemical indicators of diluents
Specific gravity Surface tension

Diluent No. Viscosity /mPa.s
（25℃） /mN/m
Diluent A 1.86 0.794 27.4
Diluent B 2.03 0.796 27.2
Diluent C 2.35 0.801 27.5
Diluent D 2.67 0.804 27.0
Diluent E 3.15 0.805 27.6
Diluent F 1.98 0.800 26.4
Diluent G 2.02 0.801 25.6
2
Diluent H 1.97 0.795 24.5
Table 2. The main ingredients in the diluents
main ingredients
Diluent No. naphthenes straight-chain isoparaffins Aromatics and

alkanes unsaturated
hydrocarbons
Diluent A 49.6% 24.7% 25.6% ＜0.1%
Diluent B 28.6% 33.5% 37.8% ＜0.1%
Diluent C 22.5% 39.8% 37.6% ＜0.1%
Diluent D 16.4% 38.1% 45.4% ＜0.1%
Diluent E 24.2% 39.6% 36.1% ＜0.1%
Diluent F 25.9% 31.8% 42.1% 0.2%
Diluent G 27.4% 30.6% 41.7% 0.3%
Diluent H 28.1% 31.8% 39.8% 0.3%
2.2 Effect of physicochemical properties of diluent on the performance of extractants
2.2.1 Effect of viscosity on kinetics

For the purpose of investigating the effect of diluent viscosity on the extraction kinetics, five types
of diluent with different viscosity(dliuent A,B,C,D and E) were chosen to carry out the experiments.
The physicochemical indicators of five diluent were listed in Table 1.
As can be seen from Table 1, there were large viscosity differences among the diluent A,diluent B,
diluent C, diluent D and diluent E, while the differences in specific gravity and surface tension
values were relativity small. The table 2 showed that the main components of these diluents were
alkanes (including naphthenes, straight-chain alkanes and isoparaffins), and almost no aromatic
hydrocarbons and other unsaturated hydrocarbons.
Table 3 shows the effect of diluent viscosity on the extraction and stripping kinetics of ketoxime
extractant Mextral84H and aldoxime extractant Mextral860H.
Experimental conditions: (1) extractant: aldoxime extractant was Mextral860H, ketoxime extractant
was Mextral84H; (2) the concentration of extractant was 10%(v/v); (3) the component of PLS: Cu
6.0g/L, Fe 3.0g/L, pH=2.0; (4) the component of stripping solution: Cu 35g/L, H 2SO4 160g/L; (5)
O/A=1:1, the organic and aqueous phase were both 400mL, (6) mixing time: 5min; (7) stirring speed
-1750r/min; (8) Temperature : 25℃.
3
Table 3 Effect of viscosity of diluent on extraction and stripping kinetics
Viscosity of 30s extraction 30s stripping

Diluent No. Extractants
diluents（mPa.s） Kinetics Kinetics
Mextral84H 87.9% 92.7%

Diluent A 1.86
Mextral860H 98.7% 99.6%
Mextral84H 86.8% 92.4%

Diluent B 2.03
Mextral860H 98.2% 99.2%
Mextral84H 85.7% 92.1%

Diluent C 2.35
Mextral860H 98.0% 99.0%
Mextral84H 84.7% 91.7%

Diluent D 2.67
Mextral860H 97.4% 98.7%
Mextral84H 84.2% 91.3%

Diluent E 3.15
Mextral860H 96.5% 98.1%
From Table 3 it can be seen that the diluent viscosity has an effect on the extraction and stripping
kinetics. As diluent viscosity increases, the extraction and stripping kinetics decreased. This rule
was applicable both for ketoxime extractants and aldoxime extractants.The effect of viscosity on the
kinetics can be explained: the increase of viscosity decreases the efficiency of the mass transfer and
diffusion of the organic, resulting in reduced reaction kinetics (Sun Sixiu,1996. Luo Aiping, 1998).
2.2.2 Effect of viscosity on the Cu/Fe selectivity

Table 4 showed the experimental results of the effect of diluent viscosity on Cu/Fe selectivity.
Standard performance test methods were used in these tests.
Experimental conditions: (1) extractant: aldoxime extractant was Mextral860H, ketoxime extractant
was Mextral84H; (2) the concentration of extractant was 10%(v/v); (3) the component of PLS: Cu
6.0g/L, Fe 3.0g/L, pH=2.0; (4) the component of stripping solution: Cu 35g/L, H2SO4 160g/L; (5)
O/A=1: 1, the organic and aqueous phase were both 400mL, (6) mixing time: 5min; (7) stirring
speed: 1750r/min; (8) Temperature: 25℃.
4
Table4 Effect of viscosity of diluent on the Cu/Fe selectivity
viscosity of Fe in organic
Cu in organic Cu/Fe
Diluent No. diluent Extractants
（g/L） (mg/L) selectivity
（mPa.s）
Mextral84H 3.98 1.40 2843

Diluent A 1.86
Mextral860H 5.46 1.34 4075
Mextral84H 3.96 1.43 2769

Diluent B 2.03
Mextral860H 5.45 1.41 3865
Mextral84H 3.95 1.59 2484

Diluent C 2.35
Mextral860H 5.43 1.52 3481
Mextral84H 3.95 1.78 2219

Diluent D 2.67
Mextral860H 5.43 1.73 3139
Mextral84H 3.92 1.98 1980

Diluent E 3.15
Mextral860H 5.41 1.86 2909
As shown in Table 4, as the diluent viscosity increased, the iron extracted by the organic increased
resulting in reduced Cu/Fe selectivity. These results were similar for both the ketoxime extractant
(Mextral 84H) and the aldoxime extractant (Mextral 860H).
The effect of viscosity on Cu/Fe selectivity may be related to the mass transfer process. In the course
of mixing, some Fe3+ may be extracted into the organic before Cu2+ because a little Fe3+ may contact
the extractant molecules before Cu2+, leading to more extracted iron. But this extra extracted iron
would eventually be replaced by Cu2+ as the mixing time increased. However, the diffusion rate of
the extraction complex formed by extracting iron would decrease if the organic viscosity increased,
so that the time to replace iron is increased. Therefore, if the mixing time is not sufficient, the iron
may not be completely replaced which would result in more extracted iron showing in the test data.
2.2.3 Effect of surface tension on extraction and stripping kinetics

Four kinds of diluent with different surface tension(diluent B,F,G and H) were selected for
experiments to study the effect of surface tension of diluent on the kinetics of hydroxyoxime
extractants. The physical and chemical indexes and composition of the four kinds of diluents were
shown in table 1 and table 2 respectively.
As can be seen from table 1, the specific gravity and viscosity of four kinds of diluent are very close,
while the difference of surface tension was greater. From table 2 it can be seen that the four diluents
were comprised of alkanes and a small concentration of aromatics and other unsaturated
hydrocarbon (less than 1%).
5
Table 5 shows the effect of diluent surface tension on extraction and stripping kinetics of
extractants. The experimental conditions are the same as "Effect of viscosity on kinetics" (see 2.2.1).
Table 5 Effect of surface tension of diluent on extraction and stripping kinetics
Surface tension of 30s extraction 30s stripping

Diluent No. Extractant
diluent（mN/m） Kinetics Kinetics
Mextral84H 86.8% 99.4%

Diluent B 27.2
Mextral860H 98.2% 99.2%
Mextral84H 85.6% 99.0%

Diluent F 26.4
Mextral860H 97.8% 99.1%
Mextral84H 84.5% 98.6%

Diluent G 25.6
Mextral860H 97.2% 99.0%
Mextral84H 84.0% 98.5%

Diluent H 24.5
Mextral860H 96.1% 98.7%
From Table 5, it can be seen that as the diluent surface tension increases, the reaction speed of
extraction and stripping increases.
An explanation of these results is as follows: the higher the surface tension, the faster the
condensation of organic droplet, so the frequency of small organic droplets coalescing and then
breaking up into new droplets increased. The mass transfer efficiency of the organic improved
during this process of coagulation and re-fragmentation. Thus, the extraction kinetics indices
improved.
2.2.4 Effect of surface tension on phase separation

Phase separation speed is depended upon surface tension. Diluents with four different surface
tensions (diluent B,F,G,and H) were used to study the influence of diluent surface tension on the
phase separation. Figures 1 to 4 show the results of phase separation test. The experimental
conditions of phase separation test were as follows: (1) extractant: aldoxime extractant was
Mextral860H, ketoxime extractant was Mextral84H; (2) the concentration of extractant was
10%(v/v); (3) the component of PLS: Cu 6.0g/L, Fe 3.0g/L, pH=2.0; (4) the component of stripping
solution: Cu 35g/L, H2SO4 160g/L; (5) phase ratio of O/A=1:1, the organic and aqueous phase were
both 400mL, (6) mixing time: 5min; (7) stirring speed: 1750r/min; (8) temperature: 25℃.
6
Figure 1 Effect of surface tension of diluent on the phase separation of Mextral84H (organic phase continuous)
Figure 2 Effect of surface tension of diluent on the phase separation of Mextral84H (aqueous phase
continuous)
7
Figure 3 Effect of surface tension of diluent on the phase separation of Mextral860H (organic phase
continuous)
Figure 4 Effect of surface tension of diluent on the phase separation of Mextral860H (aqueous phase
continuous)
As shown in Figure 1 to Figure 4, the speed of phase separation increased with the increase in
diluent surface tension. Results also show that diluent surface tension has a greater effect on phase
separation when the continuous phase is continuous Surface tension had the same effect on both
ketoxime and aldehyde extractants. The greater the surface tension, the higher coagulation speed of
organic droplets.
8
2.3 The Effect of aromatic hydrocarbons in diluent on the performance of extractants
2.3.1 Effect of aromatic hydrocarbons on extraction and stripping kinetics

Table 6 showed the experimental data of the effect of aromatic hydrocarbons on the extraction and
stripping kinetics of Mextral84H and Mextral860H, respectively. The effect of aromatic
hydrocarbons on the kinetics of the extractants was investigated by adding different proportions of
xylene to the diluent A (see Table 1) to prepare five diluents with different aromatic hydrocarbons
contents. The experimental conditions are the same as "Effect of viscosity on kinetics" (see 2.2.1).
Table 6 Effect of aromatic hydrocarbons content in diluent on extractants kinetics
The proportion of 30s stripping

Extractant 30s extraction Kinetics
xylenes in diluent A Kinetics
Mextral84H 87.9% 92.7%

0%
Mextral860H 98.7% 99.6%
Mextral84H 86.4% 91.0%

5%
Mextral860H 97.1% 99.2%
Mextral84H 84.5% 90.6%

10%
Mextral860H 94.5% 99.0%
Mextral84H 82.9% 90.3%

15%
Mextral860H 92.1% 98.7%
Mextral84H 81.4% 90.1%

20%
Mextral860H 90.6% 98.7%
As shown in Table 6, aromatic hydrocarbons have an influence on the speed of copper extraction.
The speed of extraction decreased with the increase of aromatic hydrocarbons content. The effect of
aromatic hydrocarbons on the stripping kinetics of hydroxyoxime extractants was similar to that of
extraction kinetics, but to a lesser degree.
2.3.2 Effect of aromatic hydrocarbons on the Cu/Fe selectivity

Table 7 showed the experimental data of the effect of diluents with different aromatic hydrocarbons
on the Cu/Fe selectivity of Mextral84H and Mextral860H, respectively. The experimental conditions
are the same as " Effect of viscosity on the Cu/Fe selectivity" (see 2.2.2).
9
Table 7 Effect of aromatic hydrocarbons on the Cu/Fe selectivity
The proportion of
Cu in organic Fe in organic
xylenes in diluent Extractants Cu/Fe
（g/L）（mg/L）
A
Mextral84H 3.98 1.40 2843

0%
Mextral860H 5.46 1.34 4075
Mextral84H 3.87 1.38 2804

5%
Mextral860H 5.36 1.32 4061
Mextral84H 3.78 1.36 2779

10%
Mextral860H 5.27 1.32 3992
Mextral84H 3.70 1.35 2741

15%
Mextral860H 5.20 1.31 3969
Mextral84H 3.65 1.34 2724

20%
Mextral860H 5.18 1.30 3954
From Table 7 it can be seen that the Cu/Fe selectivity of the hydroxyoxime extractant decreases with
increasing diluent aromatic concentration.
2.3.3 Effect of aromatic hydrocarbons on the anti-oxidation of extractant under the condition of
hypochlorite
The experimental conditions were as follows: (1) aqueous phase: Cu 35g/L, H 2SO4 180g/L; (2)
oxidants were 2g/L NaClO and 0.5g/L KMnO4, respectively. (3) the temperature was 30℃, O/A =
1:1; (4) continuous stirring. Oxidation loss was obtained by analyzing the organic regularly.
Table 8 showed the experimental results of effect of aromatic hydrocarbons on the oxidation rate of
the extractant under the condition of sodium hypochlorite. Table 9 showed the experimental results
of the effect of the aromatic hydrocarbons on the oxidation rate of the hydroxyoxime under the
condition of potassium permanganate.
10
Table 8 Effect of aromatic hydrocarbons on the oxidation rate of extractant under the condition of
sodium hypochlorite
The oxidized degradation rate in different

The proportion of xylenes in time（%）
Extractant
diluent A
10d 20d 30d 50d 60d
Mextral84H 0 0.1 1.1 13.6 22.1

0%
Mextral860H 0.2 1.5 2.2 20.5 32.4
Mextral84H 0 0 1.0 13.4 21.7

5%
Mextral860H 0.2 1.4 2.2 20.3 32.0
Mextral84H 0 0 1.0 13.2 21.5

10%
Mextral860H 0.2 1.4 2.1 20.1 31.8
Mextral84H 0 0 1.0 13.1 21.5

15%
Mextral860H 0.2 1.3 2.1 20.0 31.8
Mextral84H 0 0 1.0 13.0 21.4

20%
Mextral860H 0.2 1.2 2.0 20.0 31.7
11
Table 9 Effect of aromatic hydrocarbons on the oxidation rate of extractant under the condition of
potassium permanganate
The proportion of The oxidized degradation rate in different time（%）

Extractant
xylenes in diluent A 1d 5d 10d 15d 20d
Mextral84H 0.1 9.6 23.8 38.5 53.9

0%
Mextral860H 0.2 21.3 40.7 59.7 78.8
Mextral84H 0.1 9.5 23.5 37.5 52.8

5%
Mextral860H 0.2 20.8 40.5 58.6 77.9
Mextral84H 0.1 9.5 23.4 37.3 52.7

10%
Mextral860H 0.2 20.6 40.2 58.5 77.6
Mextral84H 0.1 9.4 23.4 37.2 52.5

15%
Mextral860H 0.2 20.5 40.1 58.5 77.5
Mextral84H 0.1 9.4 23.3 37.2 52.4

20%
Mextral860H 0.2 20.4 40.0 58.3 77.4
It can be seen from Table 8 and Table 9 that aromatic hydrocarbons reduce the oxidation rate of the
extractant in the presence of strong oxidants, but its effect is not significant.
2.3.4 Effect of aromatic hydrocarbons on anti-nitrification of extractant
The experimental conditions were as follows: (1) aqueous phase: Cu35g/L, H 2SO4 180g/L, the
concentration of NO3- was maintained to 20g/L; (2) the temperature was 30℃; (3)the concentration
of extractant was 10% (4) continuous stirring, oxidation loss was obtained by analyzing the organic
regularly. The results are shown in Table 10.
12
Table 10 Effect of aromatic hydrocarbons on the anti-nitrification of hydroxyoxime extractant
The proportion of The nitrification rate in different time（%）

Extractant
xylenes in diluent A 10d 20d 30d 40d 50d
Mextral84H 0 1.5 21.7 69.4 94.7
0% 100(41d
Mextral860H 0.2 5.7 56.8 94.5
later)
Mextral84H 0 2.8 21.7 75.4 100

10%
Mextral860H 0.2 6.8 64.5 100 100
Mextral84H 0 3.2 25.4 82.6 100

20%
Mextral860H 0.3 8.5 73.8 100 100
It can be seen from Table 10 that aromatic hydrocarbons accelerate the nitrification rate of the
hydroxyoxime extractants. Therefore, the nitration degradation of the extractant increases as the
concentration of aromatic hydrocarbons increases in the organic.
2.4 Effect of unsaturated hydrocarbon on performance of extractants
2.4.1 Effect of unsaturated hydrocarbon on anti-oxidation of hydroxyoxime extractant

The experimental conditions were as follows: (1) aqueous phase: Cu35g/L, H 2SO4 180g/L, oxidant
was NaClO and maintained the concentration to 2g/L(added once a day); (2)the concentration of
extractant was 10%（v/v).(3) the temperature was 30℃.(4) phase ratio of O / A = 1: 1. (4) continuous
stirring. Oxidation loss was obtained by analyzing the organic regularly. The results are shown in
table 11.
Table 11 effect of unsaturated hydrocarbon on anti-oxidation of hydroxyoxime extractant
The proportion of The degradation rate in different time（%）

Extractant
decene in diluent A 10d 20d 30d 50d 60d
Mextral84H 0 0.1 1.1 13.6 22.1

0%
Mextral860H 0.2 1.5 2.2 20.5 32.4
Mextral84H 0 0.1 1.0 13.4 21.6

0.5%
Mextral860H 0.2 1.5 2.3 20.6 32.5
1% Mextral84H 0 0.1 1.0 13.3 21.6
13
Mextral860H 0.2 1.6 2.3 20.6 32.6
Mextral84H 0 0.1 1.0 13.3 21.6

1.5%
Mextral860H 0.2 1.6 2.3 20.6 32.7
Mextral84H 0 0.1 0.9 13.3 21.5

2.0%
Mextral860H 0.2 1.7 2.4 20.6 32.7
It can be seen from Table 11 that unsaturated hydrocarbons have little antioxidant effect both for
ketoxime extractants and aldoxime extractants.
2.4.2 Effect of unsaturated hydrocarbon on phase separation performance of extractants
The experimental conditions were as follows: (1) aqueous phase: Cu35g / L, H2SO4180g/L, oxidant
was NaClO and maintained the concentration to 2g/L(added once a day); (2)the concentration of
extractant was 10% （ v/v ） ; (3) the temperature was 30℃; (4) phase ratio of O/A = 1:1; (4)
continuous stirring, oxidation loss was obtained by analyzing the organic regularly. The
experimental results were showed in table 12.
Table 12 Effect of unsaturated hydrocarbon on phase separation performance
The proportion The time of phase separation in different periods（s）

of decene in Extractant
diluent A 0d 10d 30d 50d 60d
Mextral84H 45 48 65 79 116
0%
Mextral860H 41 43 69 90 125
Mextral84H 45 50 69 81 121
0.5%
Mextral860H 42 45 73 94 129
Mextral84H 45 50 69 83 127
1%
Mextral860H 41 45 75 97 138
Mextral84H 45 50 72 88 130
2.0%
Mextral860H 41 47 79 102 145
As can be seen from Table 12, unsaturated hydrocarbons have little effect on the phase separation
during the initial stage, but as the organic is oxidized, the phase separation time increases.
2.5 Influence of volatility of diluent on extraction process
The diluent in the hydroxyoxime extractants used to extract copper was composed mainly of
alkanes with different carbon chains and generally with little or no aromatics. Alkanes with
different carbon numbers have a great influence on the volatile index of a diluent. The general rule
was that the less the number of carbon atoms, the higher the vapor pressure and the stronger the
14
volatility, and the greater the safety risk. The effect of alkanes with different number of carbon
atoms on the performance of the extractant was verified by experiments.
Table 13 showed the extraction performance of the extractants diluted by several alkanes with
different number of carbon atoms. The experimental conditions are the same as "Effect of viscosity
on kinetics" (see 2.2.1).
Table 13 Effect of alkanes with different number of carbon atoms on extraction performance
Organic
extraction stripping
Ingredients of Concentratio 30 s extraction
Extractant isotherm isothermal point
diluent n kinetics（%）
point (g/L) (g/L)
（v/v,%）
Hexane Mextral984H 10 98.5 4.94 1.72
Octane Mextral984H 10 98.3 4.91 1.70
Dodecane Mextral984H 10 98.2 4.89 1.69
As can be seen from table 13, the extraction performance of Mextral984H changed very little when
diluted by the alkane with 6 to 12 carbon atoms. Therefore, the influence of alkanes with a low
number of carbon number on extraction production is mainly a safety issue as well as consumption
cost. In general, the less the number of carbon atoms, the greater the volatility of alkanes. It not only
increased the consumption of diluent, but also increased the risk of safe operation, and would cause
greater harm to the health of workers.
3. CONCLUSION
Diluents have great influence on the performance, phase separation and stability of copper
extractants. The viscosity and surface tension of the diluent have an influence on the extraction
kinetics and phase separation. In the aspect of composition, the aromatic hydrocarbons in the
diluent have influence on the extraction kinetics, extraction isotherm point and stripping isotherm
point of the hydroxyoxime extractants. Aromatic hydrocarbons will reduce the extraction kinetic
index, at the same time the extraction isothermal point and stripping isothermal point would
decrease, and the extraction ability weakens. When the aqueous phase contains nitrate, the aromatic
hydrocarbons will accelerate the nitration rate of the extractants. The effect of unsaturated
hydrocarbon mainly lies in the phase separation. Because of the unsaturated bond, the structure of
the unsaturated hydrocarbon will change with time and effect the phase separation. Substances
(such as low alkanes) with low boiling point generally have little effect on the performance of the
extractants, but these substances will increase the loss of diluent and cause operational safety issues
because of the high volatility.
15
REFERENCES
1. Zhu Tun. Modern copper metallurgy. 2002 :120-122
2. Luo Aiping, Zhang Qixiu. Influence of Diluents on Kinetics and Phase disengagement of Copper
extraction. Mining and Metallurgical Engineering, Vol.18,No.2,June 1998,57-60.
3. LI Huajie. The Comparison of Escaid 110 and Sulfonate Diluent as Extration Diluents, Journal of
Salt and Chemical Industry, Vol. 42 No. 5,May 2013,17-19.
4. Lu An, He lin, Yao Wen, Wu Meng.Relations of Kerosen Chemical Constitutions with Diluent
Property. Hydrometal lurg y of China, Vol . 21 No. 3( Sum. 83)Sep. 2002.131-135.
5.Ritcey G M, Lucas B H. Diluents and modifers-their effect on mass transfer and
separation.In:Proceedings of the international solvent extraction conference(ISEC) , Lyons ,1974 , S
ociety of Chemi cal Indyst ry , London , 1974.2437 ～2481.
6.Sun Sixiu,Li Yan,Yang yonghui,Shen Jinglan.Effeets of Diluent Polarity on the Extraction
Kineties.ACTA Chemical sinica,1996,54,1101-1106.
16
Study on the Effect of Modifiers on the Extraction
Performance of Hydroxyoxime Extractants
JI Shang-jun, Xu Zhi-gang, Zou Qian, Luo Xing, Yu Li-yan, Xiao Xue-mei and Jiang Xue
ABSTRACT
Recent work has raised interest in the effect of different kinds of modifiers on the performance of
hydroxyoxime extractants. Hydroxyoxime extractants are aldoxime, ketoxime or their blends. This
study measured the effect of various modifiers on extraction performance including maximum
copper loading, extraction and stripping isotherm points, Cu/Fe selectivity, and net copper transfer.
The modifiers used in this study were TXIB (2,2,4Trimethy1-1,3-pentanediol diisobutyrate), TDA
(Tridecanol), DBA(Dibutyl adipate) and NP(Nonylphenol). Results showed that the addition of the
modifiers had a great influence on the extraction performance of the hydroxyoxime extractants,
especially for the extraction and stripping isotherm points, the net copper transfer, and Cu/Fe
selectivity. With the addition of the modifiers, the extraction and stripping isotherm points are
decreased, The net copper transfer changes with varying degrees: for aldoxime, the net copper
transfer increases significantly; for ketoxime, the net copper transfer decreases; and for various
blends, the net copper transfer at first increases but as modifier concentration increases the net
copper transfer of the blends decreases. The addition of modifiers also has an effect on the Cu/Fe
selectivity: NP in the selected modifier is the only one that can decreases the Cu/Fe selectivity,
while TDA, TXIB and DBA improve the Cu/Fe selectivity slightly.
1
INTRODUCTION
There are two main methods for separating and producing copper — pyrometallurgy and
hydrometallurgy. Pyrometallurgy processes are mainly for high grade sulfide ore. This production
process is complex, is energy intensive and creates air pollution. Hydrometallurgy, however, has
the characteristics of low energy consumption, low production cost and little environmental
pollution. In recent years, due to the reduction of copper grade and the diversification of copper
resources, the use of hydrometallurgical extraction of copper from low grade copper ore and
industrial waste is increasingly popular ( ZHU M.L. et al., 2016; Ewa R. , Maciej P.& Piotr H.,2016 ;
Lala B. S. et al., 2009; Sandeep P. et al., 2012).
Hydrometallurgy of copper has a long history and has been used in the industrial production of
copper in the early twentieth Century, in order to obtain a certain production efficiency and benefit,
solvent extraction method is gradually introduced into the production of copper. Solvent extraction
and electrowinning of copper is the most popular technology in copper hydrometallurgy.
Hydroxime-based extractants are widely used in copper solvent extraction and electrodeposition
systems due to their strong ability of copper extraction and excellent separation selectivity. And so
far the copper extraction reagents are mainly 2-hydroxy 5-nonyl acetophenone oxime and 2-
hydroxy 5-nonyl benzaldoxime. So far there are many kinds of commercial solvents in the market,
which can be divided into 3 categories according to their main components, the first category is the
aldoxime reagent, the second kind is the ketoxime reagent, the third one is the mixed of ketoxime
and aldoxime reagent (Ismael, M.R.C., Correia, M.J.N.&Carvalho, J.M.R.,2010; JOHN S.
Preston&ZOFIA B. Luklinska.,1980).
To improve the extraction process，a certain amount of modifier is often added to the extracted
organic phase. Depending on the effect of the modifier, the modifiers can be divided into a wide
variety of species, some for improving the phase separation performance, some for improving the
extraction equilibrium, and some for the selectivity. Aldoxime has strong extraction ability,
resulting in poor stripping in the stripping stage. It is necessary to add a modifier to reduce the
ability to bind to metal ions, so as to achieve better stripping performance. The balance modifier is
needed to be added. The balance modifiers are mostly long chain alcohols, ethers, esters, or other
extractants. It is reported that the addition of such modifiers can improve the net copper transfer
capacity to a certain extent. Some of the equilibrium modifiers reduce the extraction / stripping
isotherm point and the maximum copper loading of the extractant, to a certain extent reduce the co-
extraction of iron and have a certain effect on the extraction kinetics ( S. Kamila,V. Chakravortty&S.
Jena.,2004; Zeinab Pouramini& Ali Moradi Res. ,2012; Shiva Agarwal, Lala B. S. et al., 2010; Zeinab
Pouramini &Ali Moradi Res. ,2012; Joseph A. Conno , Neil Tindale&Raymond F. Dalton. ,1991).
At present, there are several kinds of copper extractants and the effective components are divided
into three categories. The first category are the aldoxime reagents, the second category are the
ketoxime reagents, and the third one is the mixture of ketoxime and aldoxime reagents. In order to
improve the extraction performance, it is often necessary to add modifiers. The copper extractant
modifiers are nonylphenol, alcohols (such as Tridecanol ) and esters (such as 2,2,4Trimethy1-1,3-
pentanediol diisobutyrate and Dibutyl adipate). In order to test the effects on the performance of
the three categories of extractants, the following modifiers were selected: NP (nonyl phenol), TDA
(Tridecanol), TXIB (2,2,4Trimethy1-1,3-pentanediol diisobutyrate) and DBA (Dibutyl adipate)( S.
2
Kamila, V. Chakravortty& S. Jena,2004; S. P. Mohanty. et al., 1998; Hossein Kamr an Haghighi, D.
Moradkhani & M. M. Salarirad,2014; R. N. MOHANTY. et al., 1991).
1. REAGENTS AND MATERIALS

Aldoxime, ketoxime, Aldoxime and ketoxime blend (a blend of equal parts aldoxime and ketoxime
reagent) and diluent MextralDT100 were provided by Chongqing Kopper Chemical Industrial
Corporation Limited. The other reagents used are CuSO4 (AR), FeSO4 (AR),H2SO4 (AR) and NaOH
(AR). The instruments used are pH meter and atomic absorption spectrophotometer (AAS).
2. EXPERIMENTAL METHOD
2.1 Preparation of organic phase and aqueous phase

A certain volume of extractant and modifier were blended with diluent to a certain concentration.
The synthetic PLS was prepared using CuSO4, Fe2(SO4 )3 and purified water and contained the
following: Cu2+: 6g/L, Fe3+: 3g/L, pH=2. The concentration of Cu and Fe were determined by AAS.
The stripping solution was prepared using CuSO4 and purified water, and contained the following
concentrations: Cu2+: 35g/L, H2SO4 :160g/L.
2.2 Experimental procedure

Mix equal volumes of organic and synthetic PLS for 3 minutes. Separate the two phases and discard
the aqueous. Repeat this process four (4) times, which results in obtaining a MAX loaded organic.
Using an O/A=1, combine a new organic phase and the synthetic PLS in a flask, and shake
vigorously for 5 minutes，separate the two phases and discard the aqueous. The organic phase
obtained is labeled
E300 organic phase. Next, using an O/A=1, blend the E300 organic phase and the stripping solution
in a flask, and shake vigorously for 300 seconds，separate the two phases and discard the aqueous.
The organic phase obtained is labeled S300 organic phase. Determine the Cu concentration in the
organic phase of MAX, E300, S300. Determine the Fe concentration in E300 organic phase.
Extraction isotherm point = E300Cu
Stripping isotherm point = S300 Cu
Cu/Fe selectivity = E300Cu / E300Fe
Net copper transfer =E300Cu -S300Cu
E300Cu: the copper concentration in E300
E300Fe: the iron concentration in E300
S300Cu: the copper concentration in S300
3
3 RESULTS AND DISCUSSION
3.1. Effect of modifiers on the extraction performance of aldoxime

For these tests, a modified aldoxime organic phase was prepared using aldoxime and the following
modifiers: TXIB, TDA, DBA and NP. Four groups of modified aldoxime samples were prepared —
one group for each of the four modifiers. Within each group, six different modifier concentrations
were prepared: each extraction reagents contain 0%, 10%, 20%, 30%, 40% and 47% of modifier. In
total, 24 samples were prepared and tested. Figure 1 shows the effect of the four modifiers on the
maximum copper loading of reagents.
3.1.1 Effect of modifiers on maximum copper loading of aldoxime
Figure 1 Effect of modifiers on maximum copper loading of aldoxime
As shown in Figure 1, the maximum copper loading of aldoxime decreased as the modifier
concentration increased. TDA had the greatest effect on copper loading followed by NP, DBA and
TXIB. In other words, TXIB had the smallest effect on maximum copper loading.
3.1.2 Effect of modifiers on the extraction and stripping isotherm point of aldoxime
The effect of the modifiers on the extraction and stripping isotherm point of aldoxime is shown in
Figure 2. From Figure 2 it can be seen that as the concentration of modifier increases the extraction
isotherm point of aldoxime decreases and the stripping isotherm point of aldoxime also decreases.
For the extraction point isotherm, TDA had the greatest effect, followed by DBA and TXIB; NP had
the least effect. For the stripping iso therm point, TDA had the greatest effect, followed by DBA
and TXIB; NP had the least effect.
4
Figure 2 Effect of modifiers on the extraction and stripping isotherm point of aldoxime
1: Extraction isotherm point; 2: Stripping isotherm point
3.1.3 Effect of modifiers on the Cu/Fe selectivity of aldoxime

The addition of modifiers have a great influence on the Cu/Fe selectivity of aldoxime. Figure 3
displays the effect of different modifiers on the Cu/Fe selectivity of aldoxime. NP has a significant
negative effect on the Cu/Fe selectivity. As shown, at a NP concentration of 20 %, the Cu/Fe
selectivity decreased to less than 2000. TXIB and DBA have a positive effect on Cu/Fe selectivity.
At a DBA concentration of 30%, the Cu/Fe selectivity was 5000. The effect of TDA concentration on
maximum copper loading was minimal. Figure 3 shows a slight increase in Cu/Fe selectivity as the
concentrations of TDA increases.
Figure 3 Effect of modifiers on the Cu/Fe selectivity of aldoxime
3.1.4 Effect of modifiers on the net copper transfer of aldoxime

The net copper transfer is an important performance index of the reagents For this study, the net
copper transfer was determined by the difference between the copper concentration of sample E300
minus and S300 (E300-S300). Figure 4 shows the effect of modifier concentration on the net copper
transfer of aldoxime. As shown in Figure 4, as the modifier concentration increases, net copper
5
transfer increases. Modifiers TDA and DBA had almost identical results and showed the greatest
improvement in net copper transfer. TXIB had a lesser effect on net copper transfer at low modifier
concentrations but as the modifier concentration increased the improvement in net copper transfer
was almost the same as with TDA and DBA, NP had the smallest improvement in net copper
transfer. The improvement in net copper transfer for all four modifiers is the result of better
stripping. Unmodified aldoxime has very strong extraction capability but very poor stripping
capability. With the addition of modifiers, the extraction of aldoxime changes slightly but the
stripping improves greatly. In other words, as modifier concentration increases, the decrease in the
extraction isotherm point is less compared to the decrease in the stripping isotherm point. This
results in an increase in net copper transfer as modifier concentration increases.
Figure 4 Effect of modifiers on the net copper transfer of the aldoxime
3.2 Effect of modifiers on the extraction performance of ketoxime

In the previous experiment, the effect of modifiers on the extraction performance of ketoxime was
studied. In this part, the effect of modifiers on the extraction performance of ketoxime was studied.
Ketoxime reagent was used in these tests. The preparation of organic phase is the same as the
previous.
3.2.1 Effect of modifiers on maximum copper loading of ketoxime

The maximum copper loading is an important performance index. Figure 5 shows the results of
increasing modifier concentration on the maximum copper loading of ketoxime. As seen in Figure
5, almost all the modifiers had a negative effect on maximum copper loading. TDA had the greatest
negative effect followed by DBA. Modifiers TXIB and NP had a slightly negative but not a
significant effect.
6
Figure 5 Effect of modifiers on maximum copper loading of ketoxime
3.2.2 Effect of modifiers on the extraction and stripping isotherm point of ketoxime
Aldoxime is a stronger extractant compared to ketoxime; however, ketoxime strips better compared
to aldoxime. In other words a reagent having strong extracting capabilities, aldoxime, is also
difficult to strip. A weaker extracting reagent, ketoxime, is easier to strip. To improve the stripping
capabilities of aldoxime, modifiers are added to the formulation. However, the effect of modifiers
on ketoxime performance needs further study. In this section, the effect of modifiers on the
performance of extraction and stripping of ketoxime were studied. Figure 6 shows the effect of
increasing modifier concentration on the ketoxime extract isotherm point and strip isotherm point.
The effect is similar to that shown with aldoxime. Adding modifiers to ketoxime decreases both the
extract isotherm point and the strip isotherm point. TDA had the greatest effect on the isotherm
points, followed by NP and TXIB. NP had the least effect on both the extract isotherm point and the
strip isotherm point.
Figure 6. Effect of modifiers on the extraction and stripping isotherm point of ketoxime
1: Extraction isotherm point; 2: Stripping isotherm point
7
However, the effect on the strip isotherm point is small compared to the effect on modifier
concentration on the extract isotherm point.
3.2.3 Effect of modifiers on the Cu/Fe selectivity of ketoxime

The effect of modifiers on the Cu/Fe selectivity of ketoxime was shown in Figure 7.
Figure 7 Effect of modifiers on the Cu/Fe selectivity of ketoxime
As can be seen from Figure 7, the effect of modifier on the Cu/Fe selectivity has three distinct
results, depending on the modifier: 1) NP had a significant negative effect; 2) TDA and TXIB
produced an improvement in Cu/Fe selectivity as modifier concentration increased; 3) DBA
produced a significant improvement in Cu/Fe selectivity until modifier concentration reached 27.3
g/L and then selectivity decreased with further increase in modifier concentration.
3.2.4 Effect of modifiers on the net copper transfer of ketoxime

The effects of the modifiers on the extraction and stripping isotherm point of ketoxime were
studied in 3.2.3 This section studies effect of the net copper transfer after adding modifiers to
ketoxime. These results are shown in Figure 8. As shown in Figure 8, adding modifiers to ketoxime
decreases the net copper transfer. This is the opposite effect compared to aldoxime. As discussed
in Section 3.1.4, net copper transfer is increased when modifiers are added to aldoxime. A possible
explanation for net copper transfer decreasing with increasing modifier concentration is that
ketoxime is a weaker extractant compared to aldoxime, but ketoxime strips better compared to
aldoxime. When the modifiers were added to the ketoxime, the reduction of the extraction isotherm
point is greater than that of the stripping isotherm point. As a result, there would be a gradual
decline in net copper transfer with the addition of modifier. The influence of the four kinds of
modifiers on the order from strong to weak was TDA>DBA>TXIB>NP.
8
Figure 8 Effect of modifiers on the net copper transfer of the ketoxime
3.3 Effect of modifiers on the extraction performance of mixed aldoxime and ketoxime
In Sections 3.1 and 3.2 the effects of the modifiers on the extraction performance of the
aldoxime and the ketoxime were studied. In this Section the effect of the modifiers on the
extraction performance of a blend of aldoxime and ketoxime, was examined. Which was used
as the blend. The preparation of organic phase is the same as the previous.
3.3.1 Effect of modifiers on maximum copper loading of mixed aldoxime and ketoxime
The experimental results are shown in Figure 9. As shown in Figure 9, as modifier
concentration increases, maximum copper loading of the mixed reagent decreases, DBA, TXIB
and TDA had little effect on the maximum copper loading when the modifier concentration
was no more than 10%. At 20 g/L and greater modifier concentration, the effect on maximum
copper loading is more dramatic. The amount of reduction from large to small was
TDA>NP>TXIB>DBA.
Figure. 9 effect of modifier on maximum copper loading of mixed aldoxime and ketoxime
9
3.3.2 Effect of modifiers on the extraction and stripping isotherm point of mixed
aldoxime and ketoxime
The effect of the modifiers on the extraction and stripping isothermal point of the mixed aldoxime
and ketoxime is shown in Figure 10. As presented in Figure 10, the results were similar to those of
aldoxime and ketoxime reagents. Figure 10-1 displays the results for the extract isotherm point. As
the concentration of modifiers increase, the extract isotherm point decreases. As indicated in Figure
10-1, TDA has the largest effect, followed by DBA and TXIB. NP displays the smallest effect.
Figure 10 - 2, shows how increasing modifier concentration affects the strip isotherm point. As the
modifier concentration increases, the strip isotherm point decreases. TDA has the most effect on
the strip isotherm point, followed by DBA and TXIB. NP had the smallest effect on the strip
isotherm point
.
Figure 10 Effect of modifiers on the extraction and stripping isotherm point of aldoxime and ketoxime
1 Extraction isotherm point; 2: Stripping isotherm point
3.3.3 Effect of modifiers on the Cu/Fe selectivity of mixed aldoxime and ketoxime
The effect of the modifiers on the Cu/Fe selectivity of the mixed aldoxime and ketoxime is
shown in Figure 11. As Figure 11 indicates, NP reduces the Cu/Fe selectivity sharply. The other
modifiers increase the Cu/Fe selectivity with increasing concentrations of modifier. DBA has
the largest effect, followed by TXIB, then was TDA.
10
Figure 11 Effect of modifiers on the Cu/Fe selectivity of aldoxime and ketoxime
3.3.4 Effect of modifiers on the net copper transfer of mixed aldoxime and ketoxime
The effects of the modifiers on the net copper transfer of the mixed aldoxime and ketoxime were
investigated, The results are shown in Figure 12. As can be seen from Figure 12, net copper transfer
increased initially as the modifier concentration increased until a maximum value was obtained.
Further increases in modifier concentration decreased net copper transfer.
The most likely explanation for these results is as follows: The blended extractant contains both
aldoxime and ketoxime. As shown in Section 3.1.4, increasing modifier concentrations increases net
copper transfer for aldoxime. But for ketoxime, as shown in Section 3.2.4, increasing modifier
concentration decreases net copper transfer. This phenomenon is explained as follows: At lower
modifier concentrations, the increase in net copper transfer for aldoxime is greater than the
decrease in net copper transfer for ketoxime. Thus for the blended reagent, the overall effect is an
increase in net copper transfer. This effect continues until the modifier concentration reaches about
20%. However, above a modifier concentration of 20%, the decrease in net copper transfer for
ketoxime is greater than the increase in net copper transfer for aldoxime. Thus, the overall effect on
the blend of aldoxime and ketoxime shows the net copper transfer decreasing when the modifier
concentration is 20% and greater. In other words, for a blend of aldoxime and ketoxime, the
maximum copper transfer occurs at a modifier concentration of 20%.
11
Figure 12 Effect of modifiers on the net copper transfer of mixed aldoxime and ketoxime
4. CONCLUSIONS
This paper investigated the influence of the modifiers on the extraction performance of aldoxime,
ketoxime and a blend of aldoxime and ketoxime. For aldoxime, modifiers decrease maximum
copper loading, with TDA having the greatest effect and TXIB having the least effect. The overall
ranking of the modifiers is TDA>NP>DBA>TXIB. Increasing modifier concentrations decrease both
the extraction isotherm point and the strip isotherm point. TDA has the greatest effect and NP the
smallest effect. The overall trend is TDA>DBA>TXIB>NP. Net copper transfer increased with
increasing modifier concentration with TDA having the largest effect and NP the smallest effect.
The overall rankings: TDA>DBA>TXIB>NP. For Cu/Fe selectivity, the trend was different
depending on the modifier used. NP decreased Cu/Fe selectivity while the other modifiers
increased Cu/Fe selectivity.
For ketoxime, TXIB and NP had a minimal effect on maximum copper loading. Using TDA and
DBA, maximum copper loading of ketoxime decreased significantly Both the extraction and
stripping isotherm points decreased with the addition of each modifier, the decreasing trend from
strong to weak was TDA>DBA>TXIB>NP. The net copper transfer decreased with increasing
concentration of each of the modifiers. TDA had the smallest effect, followed by DBA, TXIB and
NP. NP was the only modifier that reduced Cu/Fe selectivity of the ketoxime. The remaining
modifiers showed a slight improved in Cu/Fe selectivity of the ketoxime
For the aldoxime and ketoxime blend, TXIB, DBA and NP produced a slight decrease in maximum
copper loading as modifier concentration increased. TDA produced the greatest reduction in
maximum copper loading. Increasing modifier concentration decreases both the extraction and
stripping isotherm points with TDA producing the greatest decrease, followed by DBA, TXIB and
NP. Net copper transfer showed an increase for all modifiers until the modifier concentration
reached 20%, At modifier concentrations greater than 20%, net copper transfer decreased for all
modifiers. Results for Cu/Fe selectivity varied depending on the modifier: NP decreased Cu/Fe
selectivity; DBA and TXIB increased Cu/Fe selectivity; TDA resulted in minimal changes in Cu/Fe
selectivity.
12
REFERENCE
ZHU M.L., XIONG J.C., HU, Z.B., TONG, C.Q., WANG, R.X. (2016)Research Progress in
Resource Utilization of Iron and Copper in Copper Smelting Slag.China Academic Journal
Electronic Publishing House,37,15-27.
Ewa R. , Maciej P., Piotr H. (2016) Ammoniacal leaching and recovery of copper from alloyed
low-grade e-waste.Mater Cycles Waste Manag, 18, 318-328.
Lala B. S., Kailash C. N., Joystna R. M.,Sradhanjali S., Snehasis B., Karanam S. R.,Tondepu S.,
Barada K. M. (2009) Recovery of copper values from bio-heap leaching of low grade
Malanjkhand chalcopyrite ore. Korean J. Chem. Eng., 26, 1668-1674.
Sandeep P., Chinmaya K. S., Nilotpala P., Tondepu S., Lala B. S.,Barada K. M., Gur L.B.,
Mullukutlashivram P., Subrat K. R. (2012) Bio-hydrometallurgical processing of low grade
chalcopyrite for the recovery of copper metal.Korean J. Chem. Eng., 29,781-785.
Ismael, M.R.C., Correia, M.J.N., Carvalho, J.M.R.(2010) Extraction of copper from acidic leach
solution with Acorga M5640 using a pulsed sieve plate column. Hydrometallurgy, 104 (1), 66-
75.
JOHN S. Preston, ZOFIA B. Luklinska. (1980)Solvent extraction of copper(II) with ortho-
hydroxy oximes-I Kinetics and mechanism of extraction . inorg. nucl. Chem, 42, 431-439.
S. Kamila,V. Chakravortty,S. Jena. (2004) Studies on Acoustic Behavior, Viscosity, and density
of some commercial extractants and their molecular interaction with diluent, modifier, and
extractant. Journal of solution chemistry,33, 365-380.
Zeinab Pouramini. Ali Moradi Res. (2012) Characterization of 5-nonylsalicylaldoxime
production and the effects of modifiers on its extracting/stripping properties. Chem Intermed,
38, 2401-2409.
Shiva Agarwal, Ana E. Ferreira, Sílvia M.C. Santos, M. Teresa A. Reis, M. Rosinda C. Ismael,
M. Joana Neiva Correia, Jorge M.R. Carvalho. (2010) Separation and recovery of copper from
zinc leach liquor by solvent extraction using Acorga M5640. International Journal of Mineral
Processing, 97, 85–91.
Zeinab Pouramini, Ali Moradi Res. (2012) Characterization of 5-nonylsalicylaldoxime
production and the effects of modifiers on its extracting/stripping properties. Chem Intermed,
38, 2401-2409.
Joseph A. Conno, Neil Tindale, Raymond F. Dalton. (1991) Mechanistic studies of extraction of
copper (II) from aqueous acid by 5-nonyl-2-hydroxybenzaldoximes in organic solvents. The
effects of mixed solvents and modifiers. Hydrometallurgy, 26, 265-280.
13
Separation of Didymium from Lanthanum by Liquid-
Liquid Extraction using Organophosphorus Acids
and Acetic Acid
João Silva1 and Ysrael Vera 1
Center for Mineral Technology, Brazil
ABSTRACT
Due to their many high-tech applications and the dominance of China as a supplier, rare earth
elements (REEs) are considered to be critical materials by many countries. The motivation of this
study arose from the need to obtain rare earth elements by a more efficient and sustainable process.
REEs appear together in nature in different minerals, making their separation and purification
necessary. Liquid-liquid extraction (SX) is the most widely used technique for this separation and
organophosphorus acids are the most frequently used extractants in industry. Saponification of the
extractant acid considerably improves the separation of REEs and is commonly used in industrial
applications. Nonetheless, this practice generates wastewater containing sodium or ammonia ions,
thus requiring treatment before disposal in the environment. An alternative to saponification that
maintains high extraction and good separation is the addition of carboxylic acids to the rare earth
feed solution. This article reports the separation of didymium (Pr + Nd) from lanthanum by liquid-
liquid extraction using different organophosphorus acids as extractants and acetic acid as the
carboxylic acid. The batch extraction assays were performed using the organophosphorus acids di-
(2-ethylhexyl) phosphoric acid (D2EHPA), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester
(P507) and bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex272). We evaluated the effect of pH
variation of the feed solution and acetic acid concentration on extraction and separation. The results
showed that the rare earth extraction and didymium/lanthanum separation factor increased as the
feed solution’s pH increased. The extraction of the lanthanides was favored when the acetic acid
concentration increased. The lanthanum separation from didymium increased with rising acetic acid
concentration values at pH 3.5. Cyanex272 was the most selective extractant. However, it was
necessary to carry out the liquid-liquid separation from a less concentrated feed solution to avoid
organic phase emulsification.
1
INTRODUCTION
Because of the variety of applications of rare earth elements (REEs), especially in high-tech industries,
strong interest exists in many countries to produce these elements domestically. Among the most
important applications of these elements are the production of magnets, fuel cells, hybrid vehicle
batteries, photovoltaic panels, batteries to store energy from renewable sources and LEDs. In the near
future, demand for rare earths will grow in Brazil due to the increasing production of electricity from
renewable sources and greater capacity to refine hydrocarbons. Due to this outlook, efforts are under
way to develop domestic sources of REEs. In this respect, the Ministry of Mines and Energy (MME)
included rare earths as a priority in its National Mining Plan for 2030.
Liquid-liquid extraction, or solvent extraction, is the main method for industrial-scale separation and
purification of rare earth elements. When coming into contact with organic extractants, some of these
elements pass from the aqueous to organic phase in greater quantity than others, thus allowing their
separation. In the case of organophosphorus acid extractants, the extraction mechanism consists of
cationic exchange between the metal ions present in the aqueous phase and the hydrogen ions of the
extractant acid. The extraction reaction using organophosphorus acids strongly depends on the pH
of the aqueous solution. The higher the initial pH of the feed liquor, the more thorough the extraction
reaction will be. However, the increase of the initial pH faces constraints because high pH levels can
trigger unwanted precipitation of rare earth hydroxides.
Saponification of the extractant acids raises the extraction percentage and thus improves the
separation of rare earth elements because the pH of the aqueous solution declines less drastically
during the extraction process. However, the use of saponified extractants produces wastewater
containing ammonium or sodium ions, making it necessary to treat this effluent before disposal in
the environment or recycling for the industrial process. As an alternative to saponification,
researchers have been investigating the addition of a complexing agent, such as lactic or citric acid,
to the feed liquor, obtaining good extraction and separation results (Sun, Wang & Li, 2006; Yin et al.,
2013).
The objective of this study was to evaluate the effect on the separation of didymium (neodymium +
praseodymium) from lanthanum through liquid-liquid extraction, with the addition of acetic acid to
the rare earth liquor. The extractants tested were the organophosphorus acids D 2EHPA, P507 and
Cyanex272, at pH of 3.5.
METHODOLOGY
Reagents
The extractant used to separate lanthanum from didymium were di-(2-ethylhexyl) phosphoric acid
(D2EHPA), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (P507) and bis(2,4,4-
trimethylpentyl) phosphinic acid (Cyanex 272), provided by Aodachem (China). The diluent used
was commercial kerosene (isoparaffin), provided by Ypiranga (Brazil).
The aqueous feed solution used in the extraction tests was a synthetic solution of La, Pr and Nd with
similar characteristics to a monazite leachate (21.0 g L-1 of La2O3, 4.87 g L-1 of Pr6O11, 17.47 g L-1 of
Nd2O3), and the oxides (99.9% purity) were provided by Pacific Industrial Development Corporation.
2
The total molar concentration of rare earth elements in the feed solution was 0.26 mol L–1. All other
chemicals had analytical grade.
Batch Test
The organophosphorus acids at 0.6 mol L-1 were used in all extraction experiments. The pH value of
the aqueous phase was 3.5 and the acetic acid concentration varied between 0 and 1.5 mol L-1.
The extractant and the feed solution were placed in contact during 15 minutes (initial experiments
showed that equilibrium was achieved within 5 min). After mixing the phases, they were separated
in a separatory funnel the concentrations of rare earth metals in the aqueous phase were determined.
The extraction experiments were performed at room temperature and in triplicate. The standard
deviations of all variables were calculated.
In the extraction tests with Cyanex 272, it was necessary to dilute the feed liquor due to the
emulsification of the aqueous solution during the extraction process. The feed solution in the
extraction tests with Cyanex 272 had the following composition: La 1.8 g L -1, Pr 0.41 g L-1 and Nd 1.5
g L-1.
Chemical analysis
It were determined the Pr and Nd concentrations in aqueous phase by UV-Vis spectrometry (HACH
DR 6000 spectrophotometer) and the total REE concentration by complexometric titration with EDTA
and xylenol orange as indicator. The La concentration was calculated by the difference between the
total concentration of REEs and Pr + Nd concentrations.
Parameter Equations
The accumulated extraction (%EM) of the REEs was calculated from equation 1; as well as the metal
concentrations in the loaded organic phase (equation 2). The distribution ratio of each element (D) is
the ratio of the concentration of metal in the organic phase and aqueous phase at equilibrium
(equation 3). The separation factor (β) indicates the degree of separation of two elements and was
calculated from the distribution coefficient of two different metals (equation 4). Finally, the
didymium purity in the loaded organic phase was determined by equations 5.
[M]feed−[M]N(a)
EM = [M]feed
× 100
(1)
[𝑀]𝑙𝑜𝑎𝑑𝑒𝑑(𝑜) = [𝑀]𝑓𝑜𝑜𝑑 − [𝑀]𝑟𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒 (2)
[𝑀]
D = [𝑀] 𝑙𝑜𝑎𝑑𝑒𝑑(𝑜) (3)
𝑟𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒
DM1
βM1/M2 = (4)
DM2
[Pr]loaded(o) +[Nd]loaded(o)
%𝐷𝑖𝑑𝑦𝑚𝑖𝑢𝑚 𝑝𝑢𝑟𝑖𝑡𝑦 = × 100 (5)
[Pr]loaded(o) +[Nd]loaded(o)+[La]loaded(o)
3
In these equations, [M]feed represents the REE concentration in the feed solution, [M]raffinate is the REE
concentration in the aqueous solution after extraction, [M]loaded(o) is the REE concentration in the
loaded organic solution.

Figure 1 shows the extraction of the REEs in function of acetic acid concentration for the extractants
D2EHPA, P507 and Cyanex 272.
4
Figure 1 REE extraction values in function of the acetic acid concentration obtained with the extractants
D2EHPA, P507 and Cyanex 272 with initial feed pH of 3.5.
It can be noted that for the same element and same extraction conditions, the extraction percentages
obtained with D2EHPA were higher than those obtained with P507 and that the percentages obtained
with P507 were higher than those obtained with Cyanex 272.
It can also be observed that under the conditions studied, there was greater extraction of neodymium
in relation to praseodymium and of the latter in relation to lanthanum, demonstrating the extractant’s
preference for heavier REEs. Besides this, the addition of acetic acid caused an increase in the REE
extraction percentages.
The preference of organophosphorus acids for heavier elements and the better extraction with
D2EHPA in relation to P507 and of the latter in relation to Cyanex272 can be explained by Pearson’s
theory of hard and soft acids and bases (Pearson, 1963). According to this theory, hard bases have
greater affinity with hard acids than soft acids, and soft bases have greater affinity for soft acids than
hard acids. The hard species are less polarizable and have higher charge states and smaller size, while
the species that are more polarizable, with smaller charge and larger size, are considered soft.
The trivalent ions of the REEs and the conjugate bases of the extractant acids are considered hard
acids and bases, respectively. The trivalent ions of the REEs are hard acids due to their high charge,
while the extractants are hard bases for having oxygen atoms in their composition. The conjugate
base of D2EHPA is considered to be the hardest base of all the extractants for having four oxygen
atoms bound to the phosphorus, while P507, which has three oxygen atoms, is less hard than
Cyanex272, which has two oxygen atoms. With relation to the metals, neodymium has a smaller
radius than praseodymium, which in turn has a smaller radius than lanthanum, so that Nd is harder
and La is softer.
Since according the Pearson scheme the acids can be ordered according to their hardness as Nd > Pr
> La, the affinity between these and the extractants has the following order from weaker to stronger
affinity: Nd > Pr > La. This order of affinity explains the order of extraction levels of Nd > Pr > La
observed in the experiments. On the other hand, since the Pearson order of hardness of the bases is
D2EHPA > P507 > Cyanex272, the extraction of the REEs with D2EHPA should be greater than that of
P507, with both of these being greater than Cyanex272, as confirmed experimentally.
The increase of extraction with higher acetic acid concentration can be explained by the greater
concentration of acetate ions (Ac-) in aqueous solution as the acetic acid concentration in the feed
solution rises. The process of ionization of acetic acid (HAc) can be represented by equation (4). The
extraction reaction consists of a cationic exchange between the hydrogen ions of the extractant and
the cations of the REE (equation 5). The H+ released in equation (5) to the aqueous phase reacts with
the acetate (Ac-), as shown in reaction (6), again forming acetic acid molecules. The higher the
concentration of acetate ions in aqueous phase, the lower will be the decline in the aqueous solution’s
pH and the more extensive the extraction will be.
HAc(aq) = H+(aq) + Ac-(aq) (4)

REE 3+(aq) + 3H2A2(o) = REE(HA2)3(o) + 3H +(aq) (5)
H+(aq) + Ac-(aq) = HAc(aq) (6)
5
Figure 2 shows the praseodymium-lanthanum separation factor and didymium purity in organic
phase in function of the concentration of acetic acid, for the extractants D2EHPA, P507 and
Cyanex272.
Figure 2 Praseodymium-lanthanum separation factor and didymium purity in organic phase in function of
the concentration of acetic acid, for the extractants D2EHPA, P507 and Cyanex272 .
It can be noted that the addition of acetic acid favored the separation of lanthanum and
praseodymium slightly in comparison to the reaction without addition of acetic acid. A substantial
Pr/La = 21.2 ± 3.8) was achieved only when Cyanex 272 and acetic acid 0.3
mol L-1 were used. This reaction produced didymium with the greatest purity (95% ± 4%). Under the
rest of the conditions studied, didymium was obtained with greater purity using P507 as the
extractant.
6
CONCLUSION
In this study, we investigated the effect of adding acetic acid to the rare earth feed liquor on the
separation of didymium and lanthanum using the liquid-liquid extraction technique. We observed
that, for any of the elements and under the same conditions, the extraction with D2EHPA was greater
than with P507, which in turn was greater than extraction with Cyanex 272. Likewise, we observed
the preference of the organophosphorus extractants for the heavier REEs. Besides this, we noted that
the addition of acetic acid enhanced the REE extraction percentages, and slightly increased the Pr-La
separation factor. The best separation was obtained with Cyanex 272 and 0.3 mo L -1 of acetic acid
added in the feed liquor.
REFERENCES
Pearson, R. G. (1963). Hard and Soft Acids and Bases. Journal of the American Chemical Society,
vol. 85 (22): pp. 3533–3539.
Sun X, Wang Y, Li D. (2006). Selective separation of yttrium by CA-100 in the presence of a
complexing agent. Journal of Alloys and Compounds, vol. 408–412; pp. 999–1002.
Yin S, Wu W, Bian X, Zhang F. (2013). Effect of complexing agent lactic acid on the extraction and
separation of Pr(III)/Ce(III)with di-(2-ethylhexyl) phosphoric acid. Hydrometallurgy, vol. 131–132, pp.
133–137.
7
Nitronium Ion Inhibition in Aqueous Solution: the
Ultimate Answer to Oxime Nitration in SX
Rodrigo Zambra1, David Acevedo1, José Becerra1, Matthew Soderstrom2 and Laurent
Cohen2
1. Solvay, Chile
2. Solvay, USA
ABSTRACT
The phenomenon of nitration of oxime-based solvent extractant reagents is a long-standing, well-
recognized issue in the copper hydrometallurgical industry. This is especially true in northern
Chile, where nitrates can be naturally present in the ore deposits. Local producers are usually
familiar with this mechanism of degradation of their organic phase, and even more so with the
negative impact it can have on copper transfer. The development of nitration resistant reagent
formulations based on sacrificial additives has significantly assisted the industry by enabling
processing of pregnant leach solutions (PLS) with low to medium nitrating potential. However,
operations which have highly aggressive conditions (i.e., substantial formation or presence of
nitronium ions) still suffer from higher costs, poor quality in the cathode and production capacity
issues.
The following paper is a progress update on the use of sulfamic acid (H 3NSO3) as a potential
method to inhibit nitration for operations with highly aggressive nitrating conditions. It gives
background information on the mechanism of oxime nitration, and presents results from both
laboratory and pilot testing, which show that sulfamic acid is highly efficient in preventing
nitration. Its use, in combination with a nitration resistant formulation (ACORGA NR series), may
permit the treatment of minerals with higher nitrate content and/or the leaching of sulfide ores with
nitric acid (highly aggressive conditions).
INTRODUCTION
The nitration phenomenon in Chile has been an on-going concern for solvent extraction (SX) plants
because of the aggressiveness of the phenomenon, the associated operational problems, the costs
involved and the potential impact on production. It is a chemical reaction by substitution that
occurs between the oxime and nitronium ions (NO2+) present in the electrolyte or PLS solutions. The
nitrated oxime and the copper molecules form a stable organic-metallic complex that is not readily
stripped using electrolyte solution (Soderstrom: 2009). Due to the impact of this phenomenon in a
good number of Chilean operations, it has been studied for more than 17 years and several
developments have been presented to the industry. Among them, one of the most important has
been the development of extractant formulations which are resistant to nitration. These
formulations use an additional organic compound which reacts preferentially with nitronium so
that the nitronium ion is consumed and nitration of the oxime is prevented. In order for the
sacrificial additive or protector to work efficiently the requirements are that i) the protector nitrates
at a faster rate than the oxime, and ii) there is a sufficient concentration of protector to consume all
the nitronium ions that form. These nitration resistant formulations have been used successfully
under conditions of low to medium aggressiveness. However, under highly aggressive nitration
conditions the sacrificial organic compounds are quickly consumed, leaving the oxime exposed to
react with the leftover nitronium ions. The use of nitration resistant formulations is not sufficient
under two plant scenarios: 1.) High aggressiveness of nitration in the aqueous solution. 2.)
Insufficient make-up of the extractant, which allows all the protector to be consumed.
To address conditions of high aggressiveness, Solvay (Cytec at the time) proposed a solution in
2016 based on the reaction of the nitronium ion with sulfamic acid in the aqueous phase before
contacting it with the organic phase. Sulfamic acid was proposed as an effective reagent to consume
the nitronium ion (Soderstrom: 1999; Zambra: 2016).
This work presents a continuation of this study: a process to inhibit nitration by treating the
aqueous phase with sulfamic acid, thus reducing the formation of the nitronium ion prior to the SX
process, and thereby reducing oxime nitration.
BACKGROUND INFORMATION
The nitration reaction will directly depend on the nitrate concentration existing in the aqueous
solutions of the plant and the acidity level, but it is also affected by the variables of temperature,
redox potential, interfacial tension and the reactivity of the aqueous and organic phases (Menacho:
2003). Depending on each of these variables, the nitration conditions will be more or less
aggressive.
OH OH OH
OH N OH N OH N
O 2N O 2N
R1 + NO + R1 R1
2
H +
R2 R2 R2
Where R1 = H or CH3 (aldoxime or ketoxime)
R2 = C9H19 or C12H25 (nonylaldoxime or dodecylaldoxime)
Figure 1 Oxime Nitration mechanism
As known, oxime nitration may produce diverse problems in the normal operation of the SX plant,
resulting in a poor production, high operational instability and significant increase in operational
costs. However, industry suppliers and specialists with extensive experience dealing with nitration
can now suggest to plant operators various changes in operating philosophy and/or design of the
operation that will allow them to run their SX plants with reduced risk.
As previously defined, nitration is a chemical reaction produced between the oxime and the
nitronium ion present in the electrolyte or PLS solutions. Nitronium ions are formed when nitrate
ions (present in the copper ores) react with sulfuric acid as shown below in reactions (1) and (2):
NO3- + H2SO4  HNO3 + HSO4- (1)

HNO3 + H2SO4  NO2+ + H2O + HSO4- (2)
The formation of the nitronium ion depends on the concentration levels of nitrate and acid;
however, the redox potential and the temperature will also influence the reaction rate. On the other
hand, the presence of other metals, colloidal silica, and clay, may also catalyze the formation of
nitronium ions, thus generating high aggressiveness in the solution. (Inanaga: 2012; Holzapfel:
1998; Laszlo: 1986).
A high concentration of nitronium ion in solution (regardless of how it is formed) will lead to a
high consumption of the anti-nitration protectors in the extractant formulation, increasing the
possibilities of oxime nitration. This can be effectively solved by consuming any nitronium ion in
the aqueous media, before entering the SX plant, thus eliminating the possibility of reaction with
the compounds of the organic phase.
Equation (3) below shows the proposed chemical reaction occurring between the sulfamic acid and
the nitronium ion. The products of this reaction (nitrogen, water, sulfuric acid) are inert to the SX
process (Zambra: 2016).
NO2+ + H2NSO3H -> N2O + H2SO4 + H+ (3)
The process of using sulfamic acid to react with nitronium was validated at the lab level by the
Tert-Amyl-Phenol (TAP) test methodology developed by Cytec/Solvay (Zambra: 2013).
TAP may be used to detect the presence of nitronium ions due to its high reactivity, as the benzene
ring contains only half of the OH-activator, and high solubility in the aqueous solution due to the
short alkyl chain. Depending on the aggressiveness of the aqueous solution to be analyzed, the TAP
dissolved in an appropriate solvent is partially or completely nitrated (2-nitro-4-tertamyl phenol) if
mixed with a solution containing nitronium ions. This methodology was used to conduct validation
tests of the effectiveness of sulfamic acid to consume nitronium ions.
The conditions of the synthetic electrolyte used were: 30 gpl Cu, 200 gpl H2SO4, 200 ppm of NO3-,
50°C, O/A ratio 1:5, 2 mM of TAP in heptane, 600 rpm. The test with sulfamic acid was conducted
with a concentration of 0.05mM (stoichiometric dosage calculated from the nitro TAP tests). In
order to ensure the nitration level was adequate, concentrated sulfuric acid was added to the
aqueous phase just prior to contact with the TAP organic phase. The addition of concentrated
sulphuric acid to a solution containing nitrate salts promotes formation of nitronium ions, likely
due to the formation of a hot spot that increases the temperature and redox potential. Gas
chromatography results are shown in figure 2 with and without the addition of sulfamic acid.
Additionally, different tests were conducted using this methodology modifying the variables of
redox potential, temperature, acid concentration and impurities (Cl, Mn and Fe) to make the
solution more aggressive. However, when applying the sulfamic acid, the consumption of the
nitronium ion was effective and it did not generate the nitro TAP compound.
TAP test without Sulphamic Acid

TAP test without sulfamic acid
Nitro TAP 0.25mM
TAP 1.75mM
TAPTAP
testtest
withwith sulfamic acid
Sulphamic 0.05mM
Acid 0,05mM
TAP 2.0mM
Figure 2 Gas chromatography, sulfamic acid validation by TAP test
ANALYSIS AND RESULTS

The continuation of the study consisted of additional lab-based tests with oxime, pilot plant test
studies with real solutions under nitration conditions and a preliminary trial to demonstrate that
sulfamic acid could be successfully utilized in the context of an aggressive nitric acid leach
flowsheet.
Validation with Oxime

Tests with oxime were completed to validate the effectiveness of the sulfamic acid, under
aggressive nitrating conditions. The conditions used were: 30 gpl Cu, 200 gpl H2SO4, 1000 ppm NO3-
, 50°C, O/A ratio 1:10, 5% aldoxime in heptane, 10 contacts of 15 min each, 600 rpm. A
stoichiometric dosage of sulfamic acid was used (0.4mM as determined in previous tests). The
results are shown in Table 1 and Figure 3.
Table 1 Validation sulfamic acid with aldoxime.
Aldoxime Nitrate Sulfamic Acid Residual Cu Nitro Aldoxime Nitronium (mM)

(%) (ppm) (mM) (ppm) (mM)
1 5 0 0 4.28 0.13 0.01
1 5 0 0 5.52 0.17 0.02
2 5 1000 0 126.0 3.97 0.40
2 5 1000 0 98.0 3.09 0.31
3 5 1000 0.40 5.08 0.16 0.02
3 5 1000 0.40 7.28 0.23 0.02
The results show that addition of sulfamic acid to the aqueous phase prior to contact with the
organic fully prevents nitration of the oxime.
Blank Aldoxime
1000 ppm NO3- Aldoxime

Aldehído Nitro Aldoxime
Without sulfamic acid
1000 ppm NO3- Aldoxime

With 0,4 mM sulfamic acid
Time
Figure 3 Nitration reduction w/o Sulfamic acid with aldoxime
Pilot Plant Test Validation

Pilot tests were carried out with real solutions that are known to generate nitration in the industrial
plant setting. Prior to the test, the plant solutions were dosed with sulfuric acid to further increase
the aggressive conditions (catalyzing nitronium ion formation) and fully demonstrate the ability of
sulfamic acid to prevent nitration. Two pilot plants were operated in parallel to evaluate the impact
of the sulfamic acid. Conditions were: Configuration 1E + 1S, all with fresh Organic (30vol% reagent
free of protector):
• Plant 1: had addition of H2SO4 in the PLS and Spent
• Plant 2: had addition of both H2SO4 + 0.05 mM sulfamic acid in the PLS / spent.
The characterization of the solutions was:

Table 2 PLS and spent characterizations
Cu pH/[H+] Cl Fe T NO3 - Mn Redox

gpl -/gpl gpl gpl gpl gpl mV (ENH)
PLS 2.23 2.24 6.8 9.50 7.32 5.84 618
Spent 56.5 199.6 0.056 3.37 0.310 0.176 721
Note: The PLS was set at 200 gpl and Spent at 220 gpl of sulphuric acid, in order to increase the
aggressiveness of the solution prior to contact with the organic phases.
The amounts of nitrated oxime, measured through “residual copper” (copper detected after
complete discharge of non-nitrated organics under standard laboratory conditions, directly
proportional to the amount of nitrated oxime) appear in Figure 4 below. They show the
effectiveness of the sulfamic acid in consuming the nitronium ion before the solutions entered the
SX plant, avoiding the nitration of the oxime (and increase in residual copper).
Figure 4 Pilot plant test in real solutions, validation.
Trial with Nitric Acid

Based on the successful validation tests, sulfamic acid was finally tested on an even more
aggressive leach solution: one resulting from leaching of ore with nitric acid. Preliminary tests were
performed for both sulfide ore (SL) and copper sulfide concentrate (CL) leach solutions. The
solutions obtained from these leaching tests had the following properties:
- PLS Leach sulfide ore: Cu 1.6 gpl; pH 1.46; NO3- 8.8 gpl.
- PLS sulfides concentrate leach: Cu 5.48 gpl; pH 1.55; NO3- 30 gpl.
The conditions used in the test were: 50°C, O/A ratio 1:10, 5% aldoxime in heptane, 3 contacts of 15
min each and 600 rpm. The stoichiometric dosage of sulfamic acid was 0.35mM for the concentrate
leach and 0.10 mM for the sulfide leach (as determined in previous tests). The results appear in
Table 4 below.
Table 4 Test oxime with PLS nitric acid w/o sulfamic acid
Aldoxime Nitrate Sulfamic Acid Cu residual Nitro Aldoxime Nitronium

(%) (gpl) (mM) (ppm) (mM) (mM)
SL 5 8.80 0 23.30 0.73 0.070
SL 5 8.80 0 24.40 0.77 0.080
SL 5 8.80 0.10 1.28 0.04 0.004
SL 5 8.80 0.10 1.49 0.04 0.004
CL 5 30.0 0 90.50 2.85 0.290
CL 5 30.0 0 114.0 3.60 0.360
CL 5 30.0 0.35 1.31 0.04 0.004
CL 5 30.0 0.35 1.76 0.06 0.006
Preliminary tests performed in nitric medium indicate that the sulfamic acid allowed the use of
nitric acid as a leaching agent, reducing the risk of oxime nitration. This appears clearly in Table 4,
where we observe that when sulfamic acid is applied, the nitronium ion is efficiently consumed in
both solutions, decreasing the possibility of nitration of the oxime.
CONCLUSION
Based on the results and analysis of this study, the application of sulfamic acid to copper solvent
extraction developed by Solvay may be the breakthrough solution to the nitration phenomenon.
When applied correctly, the addition of sulfamic acid to an SX feed solution prior to contact with
the organic phase proved to be a highly reliable technique, which will allow copper SX plants to
operate under highly aggressive nitration conditions.
Validated in the laboratory, in pilot plant setting and through a preliminary trial, this technology
has the potential to enable mining projects and mining sites to treat ores with high nitrate content,
which due to the risks associated with nitration, would have been considered as non-exploitable
resources previously.
The preliminary tests conducted in the nitric media show that sulfamic acid is a valid solution for
leaching of copper sulfides ores with nitric acid, or with nitric/sulfuric acid mixtures, expanding the
field of application of the technology and reducing the risks associated with nitration in the organic
phase to new families of lixiviants.
For optimal results, Solvay recommends the use of a nitration-resistant formulation, such as
ACORGA® NR, in addition to the sulfamic acid, which offers a second layer of protection for
aggressive leach conditions. Solvay provides this application to all its customers as part of the
technical service delivered with the use of ACORGA® reagents.
REFERENCES
– Laszlo P, Cornélis A, Pennetreau P. Nitration of Estrone into 2-Nitroestrone by Clay-Supported
Ferric Nitrate. Publication American Chemical Society Vol. 48. (1983). University of Liege,
Belgium.
– Inanaga J, Onitsuka S, Jin Y, Shaik A, Foruno H. Silica Gel-mediated Organic reactions under
Organic Solvent-Free Conditions. Publication Journal Molecules, Vol. 17 (2012), Japan.
– Holzapfel W and Dwyer C. The Nitration of Electron-Rich Aromatics, Publication Tetrahedron
Journal. Rand Afrikaans University (2006), South Africa.
– Laszlo P. Catalysis of Organic Reactions by Inorganic Solids. American Chemical Society, Vol. 19
(1986). University of Liege, Belgium.
– Zambra R, Quilodran A, Castro O. Cytec Chile Ltda. The Phenomenon of Nitration in the
Chilean Copper Hydrometallurgy. Copper (2013), Santiago-Chile.
– Soderstrom M, Yáñez H, Soto A. Bednarski T., Nitration in copper SX? Cytec ACORGA provides
a new reagent, Hydrocopper 2009, Antofagasta, Chile 332-341.
– Hurtado-Guzmán, C. & Menacho, J. (2003).Oxime degradation chemistry in copper solvent
extraction plants, Copper 2003. The Canadian Institute of Mining, Metallurgy and Petroleum,
Montreal, Quebec, Canada, 719 – 734.
– Zambra R, Quilodran A, Rivera G, Castro O. Cytec Chile ltda. Use of NR® reagents in presence
of nitrate ion in SX: A Revision of the Present Moment. Hydroprocess (2013). Santiago- Chile.
– Zambra R, Laval M, Acevedo D, Soderstrom M, Cytec Solvay group. New Alternatives to the
Treatment of Nitrating Solutions in SX (2016). Santiago- Chile.
A New Phase Dispersion and Superior Phase Separation
System
Daniel Ernt
MineXTech, USA
ABSTRACT
New dispersion/separation system improves both the mass transfer of metals in hydrometallurgical
extraction applications and improves phase separation using a new concept in liquid-liquid centrifuges. The
new dispersion device is able to disperse one phase into a second phase independent of flow ratio. This new
patented dispersion and mixing device creates distinct and uniform droplet sizes. Producing distinct and
uniform droplet sizes allows for optimization of mass transfer and phase separation. A unique patented
manufacturing process results in substantially lower cost for the centrifuge separator, producing an
economically viable alternative to current phase separation systems. Mass transfer, higher stage efficiencies,
low hold-up, low residence time, low diluent inventory and usage, lower separator cost and high turn down
ratio are several advantages the overall system application has over existing SX process equipment. The
overall system is completely closed reducing air entrainment. Reduced air entrainment lowers reagent
degradation and enhances phase separation. Additionally, the closed system reduces VOC emissions (air
pollution) ad lessens organic loss. This new system delivers market changing improvements in comparison
to existing centrifugal extraction systems.
Page 1 of 10
1.0 INTRODUCTION
This paper discusses two technical advances that provide important operating improvements to increase
mass transfer and phase separation while reducing cost in hydrometallurgical solvent extraction operations.
The first technical advance is a unique micro dispersion device (MDD). The MDD provides the design,
engineering and operations personnel the capability to increase mass transfer, which in turn improves stage
efficiency. The MDD creates specific droplet sizes for the dispersed phase and thus an optimum droplet size
is determined for a specific application. Optimum droplet sizes are determined that maximize mass transfer
as well as enhancing phase separation (SX Kinetics, 2008). In a given solvent extraction system, smaller
droplet sizes tend to improve mass transfer and hence stage efficiency. However, smaller droplet sizes
reduce phase disengagement efficiency. The MDD allows the design and operating engineers to test various
droplet sizes to optimize these competing objectives, that is, determining the best droplet size that results in
the optimal mass transfer as well as the best phase disengagement,
The MDD also allows the dispersion of a specific phase independent of phase volume or flow ratio. Thus, in
a system where the organic to aqueous (O/A) ratio is 4:1, the organic phase can be dispersed using the MDD
without having to recycle the aqueous phase.
Finally, the MDD produces a more uniform distribution of droplet sizes within the continuous phase
compared to any existing phase mixing devices.
The second device is the GES separator. The GES is a patented centrifuge, which allows high phase
separation efficiency due to the high ‘g’ force created in the rotating bowl. The GES has a lower cost
compared to other centrifugal extractors and separators. The patented economical design and
manufacturing techniques allows the use of a centrifugal separator in hydrometallurgical SX operations.
Other centrifugal contactors and separators are too costly and are uneconomical to use in most SX
operations. The GES offers the advantages over other conventional process equipment such as low hold-up,
low residence time, and low organic inventory.
Together these two new inventions, strategically combined, significantly improve mass transfer and stage
efficiency. They also improve separation and reduce entrainment losses while realizing significant cost
reductions in comparison to other SX systems and existing centrifuge systems.
An important design characteristic in the MDD/GES system is the creation of a closed system. This design
feature minimizes volatile organic content (VOC) emissions – thus reducing organic losses and air pollution.
This closed system design is also important in that air entrainment in the liquids is essentially eliminated. In
order to have the best possible separation and reduce entrainment to the lowest level possible, the system
design must avoid or reduce air induction into the fluids. This fact is borne out in the following: A study
sponsored by the American Institute of Chemical Engineers (AIChE) Hydrometallurgical Symposium in
cooperation with Nchanga Consolidated Copper Mines Limited of Zambia concluded the following for an
aqueous dispersed, organic continuous system: “If air is excluded from the dispersion in the mixer, then
organic in aqueous entrainment is minimized and aqueous in organic entrainment reduced to undetectable
levels”.
Page 2 of 10
2.0 SYSTEM DESCRIPTION
2.1 Mirco dispersion (mdd) description

The unique design of the MDD allows for efficient phase mixing/blending for such operations as extraction,
washing or reaction applications. This allows a combination mixing/separation process to be optimized for
the best mass transfer (accomplished in the MDD) and the best separation (little or no contamination of one
phase in the other) in subsequent phase separation steps. The capability of the MDD to create a specific
droplet size and uniform droplet size creates an efficient mixing and blending system.
The MDD provides improved methods and devices for dispersing droplets or bubbles of a first liquid into a
second liquid. The MDD includes a permeable body, which allows the first liquid to pass through creating a
distinct droplet size. The MDD element is placed within a pipe. The second liquid flows around and past
the MDD. The second liquid is flowing in a turbulent condition. The first liquid exits the permeable MDD
element in droplets of uniform size, which are swept away by the turbulent flow of the second liquid past
the low-pressure side of the permeable MDD body. The turbulent flow conditions of the continuous second
liquid phase allows the droplets of the first liquid to be quickly dispersed before having an opportunity
to coalesce.
Figure 1 Schematic of MDD
The MDD causes the first liquid to be dispersed as individual droplets in the second liquid, resulting in
more efficient transfer of the metal or solute. The MDD can create one phase as the dispersed phase
independent of flow. The dispersed phase is always the phase that passes through the MDD element. The
continuous phase is always the phase flowing around the permeable MDD element. In other mixing systems
the continuous phase is almost always the phase with greater flow volume
Processes can be optimized resulting in maximum mass transfer and minimum entrainment after separation.
In general, good results are obtained by using a permeable body, which has pores, most of which have an
equivalent diameter between about 20 microns and about 200 microns. Figure 1 shows a schematic of the
MDD.
2.2 Centrifugal Separator (GES Unit)

The patented GES centrifugal separator is similar to other liquid-liquid centrifuges in the manner of how the
two phases separate in the bowl but offers unique design differences, which not only improves separation
efficiency but also reduces the cost of the centrifugal separator.
Page 3 of 10
The GES is designed to work with or without the MDD. For situations used exclusive for separating two
liquids of
different densities, the MDD is not used. For hydrometallurgical applications, the MDD provides the mixing
step prior to separation using the GES. This new system disconnects the mixing component from the phase
separation component. This is an important difference between the MDD/GES system compared to existing
centrifugal systems. In other centrifugal extraction equipment, the mixing step and the separation step are
interconnected (Meikrantz, D (1998).
Each GES centrifuge unit includes an inlet chamber, outer housing, rotor or bowl, a drive motor connected to
the rotor by a flexible coupling, and a motor controller for precise control of the motor speed. The lower part
of the housing contains a single inlet for the dispersion to be separated. The upper part of the housing
contains the heavy and light phase discharge ports. The light phase exit port is positioned at the center axis
for maximum liquid residence time and maximum distance from the liquid-liquid interface. The position of
the liquid-liquid interface is determined by the selection of the heavy phase outlet port position. The heavy
phase exits through outlet holes at the top of the rotor, collects in the annulus space between the rotor and
the outer housing before exiting out the top. (Figure 2 is a cutaway of the GES unit).
Figure 2 Cutaway of GES Unit
The liquid feed entering the central orifice, gets deflected towards the wall by a horizontal deflecting baffle
near the entrance. This deflecting disk forces the feed into four identical quadrants separated by vertical
vanes. The dispersion is directed to the rotor or bowl by a series of radial bottom vanes, which create four
chambers or quadrants (see Figure 2). The inner surface of the rotating liquid has almost a vertical shape
because of high ‘g’, except a small parabolic portion at the bottom (see Figure 2). The dispersion entering at
the bottom gets separated as it moves upwards. The rate of separation depends upon the droplet size
distribution, droplet settling velocities under the centrifugal action (r ω 2 -- where r is the bowl radius and
ω is the rotational speed, RPM), densities, viscosities and coalescing behavior of the two phases.
Separation occurs inside the bowl by application of centrifugal force on the mixed liquid phases. Forces in
the range of 100 to 1000 “g” are typical at the rotor wall. In each quadrant, the heavier phase collects at the
rotor or bowl wall. As the lighter phase begins to separate, it collects closer to the centerline of the bowl.
After separation, the overflow outlet ports are provided in such a way that, very clean light and heavy
phases exit the GES. The size and location of the outlet ports are provided in the hardware according to the
relative flow rates of heavy and light phases and the density ratio of the two phases.
Page 4 of 10
In the GES Unit, liquids occupy the complete bowl volume, which results in more residence time, and more
residence time results in higher separation efficiency. In other centrifuge systems, the air entrainment
results in formation of three distinct phases within the bowl – air (or gas), light liquid phase and heavy
liquid phase. Research has shown that air introduced in the mixing and subsequent separation step reduces
phase separation efficiency. If air is excluded from the dispersion in the mixer, then organic in aqueous
entrainment is minimized and aqueous in organic entrainment reduced to undetectable levels (Godfrey, J.C.
1978).
Changing the heavy phase outlet port position varies the position of the liquid-liquid interface in the bowl.
Varying the liquid phase interface position changes the volumes occupied by the two phases in the bowl.
The optimum position of the interface is determined primarily by the density difference between the light
and heavy phases. Figure 3 shows an Interphase Position Diagram for the GES 18 unit.
The efficiency of phase separation in the GES is controlled using three process parameters (Law, Jack ,
2011):
1. Rotational speed (RPM) of the rotating chamber or bowl
2. Residence time in the bowl
3. Volume of each phase within the bowl.
3.0 PILOT TEST
3.1 Equipment and procedures

A two (2) Extract (2E) x 1 strip (1S) MDD/GES pilot plant was installed at a secondary copper recovery SX
operation. The MDD/GES pilot plant operated in parallel with the commercial SX plant. The PLS and lean
electrolyte used were the same solutions processed through the commercial SX system. Raffinate and rich
electrolyte generated by the pilot plant were transferred to the commercial SX plant. The commercial plant is
a conventional mixer-settler operation.
Page 5 of 10
Figure 3 Interphase position diagram for GES 18
The commercial SX plant uses a modified aldoxime as the copper reagent. The MDD/GES pilot plant used
Mextral 5774, which is a modified aldoxime reagent.
The centrifuges used in the three pilot plant stages were GES18 units. The centrifuge bowl or chamber for
the GES18 unit has a volume of 92 liters. Nominal capacity is about 380 lpm (22.8 m3/hr).
Operating parameters for the MDD/GES pilot system and commercial system are listed in Table 1.
3.2 Results
The MDD/GES pilot plant and commercial SX plant operated 24 hours per day. The duration of the
comparison was 34 days. Samples from both the MDD/GES pilot system and the commercial SX plant were
taken every two hours. The results for each 24 hour period (12 samples each 24 hour period) were averaged
over each 24 hour period. The daily average results for each operating parameter were then averaged for the
34 day test period. The daily average results are listed in Table 2
Page 6 of 10
4.0 ECONOMICS OF MDD/GES SYSTEM
Two engineering and design firms experienced in
designing copper SX plants were engaged to develop
budgetary cost estimates for a 20000 MT/yr cathode
copper plant. Two cost estimates were developed for
the SX portion (no leaching or EW). One cost estimate
was using the MDD/GES system and the second cost
estimate was developed using conventional mixer-
settlers.
Initial organic fill volume and cost was also estimated.
Lastly, estimates on annual organic make-up were
estimated. For the conventional SX plant, an annual
make-up equal to 30% of organic inventory was used
by the engineering firms. The annual organic makeup
for the MDD/GES based design was estimated using
makeup quantities recorded during the pilot test
discussed in Section 4. During the thirty-four (34) day
test period, organic makeup, as a percentage of the
total organic inventory, measured ten (10%) percent. In other words, the total makeup added to the
MDD/GES system during the thirty (34) day period was ten (10%) of the total organic inventory.
4.1 Basic design criteria:

Design criteria used for the cost estimates are listed in Table 3
4.2 Installation cost and organic cost comparisons are shown in Tables 4 and 5.
5.0 DISCUSSION AND CONCLUSIONS

TABLE 2
COMPARISON RESULTS DRURING TEST PERIOD
E1 E2 Copper S1
System A in O O in A A in O O in A Recovery A in O O in A
ppm ppm ppm ppm % ppm ppm
MDD/GES 21.9 12.4 23.1 13.8 98.2 26.1 26.8
Commercial Plt 42 24 45 26 90.1 46 52
Above results are averages over the 24 day test period
 Side-by-side operation (parallel operation) of the MDD/GES with a conventional mixer-settler SX

operation over a thirty-four (34) day period produced the following results:
The copper recovery was nine (9%) percentage points higher for the MDD/GES compared to the mixer
settler operation. This is due to higher mass transfer. The higher mass transfer is the result of the MDD
Page 7 of 10
Table 3
DEISGN PARAMTERS FOR COST COMPARISONS
Parameter Value Parameter Value
generating distinct droplet size (100 micron) and a more
PLS flow: 1000 M3/hr Lean electrolyte Cu: 33 g/l
2.8 g/l 45 g/l
narrow range of droplet size compared to the
PLS copper: Rich electrolyte Cu:
Copper recovery: 95% Strip O/A ratio: 4.6:1 conventional agitator based mixers used in the
Extract O/A 1.0 Cu cathode production: 200000 MT/yr commercial SX system. Mass transfer rates across liquid
Electrolyte flow: 218 M3/hr Reagent concentration: 10% boundaries depend in part on the droplet size
distribution, i.e., the interfacial surface area of the dispersed phase. The MDD systems allows for testing to
determine optimum droplet size. Thus, the MDD allows a system design to optimize between mass transfer
and adequate phase disengagement – resulting in minimal entrainment while maximizing mass transfer.
 The entrainment values in the MDD/GES were approximately half of the entrainment values
generated by the conventional SX system. This was observed in all stages and also observed in both
aqueous entrainment in organic and organic entrainment in aqueous. These results were due to three main
factors (Miller, Graeme, 2003):
1. The more uniform droplet size produced by the MDD results in more efficient phase separation.
2. The closed system design of the MDD/GES system results in less air entrainment in the liquid
solutions. Less air results in better phase separation.
3. The higher g force produced by the GES separatory results in better phase disengagement. In
comparing separators designed for separating two liquids of different densities, a useful parameter is g 
Seconds. This represents the product of the g Force multiplied by the residence time in the separator. The
GES units in this pilot study operated at a g force of 245. The residence time in the centrifuge bowl was 15
seconds. Thus, the g Second factor for the GES was 3675. The g  second factor for the settlers used in the
commercial plant was 900 (1 g force multiplied by a 15 minute residence time). As seen, the g second factor
for the GES unit was four (4) times that of the conventional settler equipment. The higher g second factor in
the GES improves phase separation.
 The MDD/GES SX system required a smaller amount of organic makeup over the thirty-four (34)
day test period. The organic losses were factored to take into account the larger size of the commercial plant.
Organic makeup was measured as a percentage of the total organic inventory in each system. Using this
parameter as a comparison measurement showed the organic makeup for the MDD/GES system was one-
third (1/3) compared to the make-up required for the commercial system at the same operating conditions
(flow rates, electrolyte quality, PLS quality and temperature). The main reason for these reduction in
organic loss is due to the closed design used by the MDD/GES system. This results in lower organic losses.
This means lower operating costs and also less VOC emissions (air pollution) from the SX system.
 Based on the pilot plant results, the MDD/GES produces the following benefits compared to existing
SX systems and centrifugal contactors:
The MDD controls which solution phase is dispersed and which solution phase is continuous
Page 8 of 10
Table 4 Organic cost for each system
Initial Fill Plus Annual Makeup
Mixer-settler Centrifuge Conventional mixers do not control the dispersed or
Diluent volume, M3 810 270 continuous phase but rather the solution flow to the mixer
Diluent cost, USD 1,215,000 405,000
controls this parameter. It follows that regardless of which
solution has the overall larger volume, the MDD does not
Reagent volume, M3 90 30 require the larger solution volume (or a recycle of the lower
Reagent cost, USD 810,000 270,000 solution volume) to ensure a continuous phase for the mixer.
This provides the plant with more operational flexibility and
Total org volume,M3 900 300
avoids the costs of recycling the lower volume solution, where
Total org cost, USD 2,025,000 675,000
the lower flow volume is designed to be the continuous phase.
Annual Makeup  The MDD ensures the optimum droplet size is created
Diluent volume,M3 243 40.5 for the dispersed phase which leads to improved mass transfer
Diluent cost, USD 364,500 60,750 and improved stage efficiency.
 The MDD ensures a uniform droplet size, which
Reagent volume,M3 27 4.5
improves phase separation in the downstream separator (GES
Reagent cost, USD 243,000 40,500 unit).
Total org volume,M3 270 45  The MDD/GES is a closed system, which lessens air
Total organic cost, USD 607,500 101,250 entrainment into the system. This reduces the formation of a
third (air) phase into the centrifuge and thus improves phase
5 year period separation. Additionally, the reduction or elimination of air in
Diluent volume,M3 1,215 203 the system reduces organic degradation as well as lowering
Diluent cost, USD 1,822,500 303,750 organic losses.
 Based on cost estimates from two experienced
Reagent volume,M3 135 23
engineering firms, a system using the MDD/GES technology
Reagent cost, USD 1,215,000 202,500 has a lower installation and organic fill cost compared to
Total org volume.M3 1,350 225 conventional mixer-settler based system. Also, annual organic
Total organic cost, USD 3,037,500 506,250 make-up costs are reduced.
Unit Diluent cost , USD/kg 1.50 1.5

Unit Reagent cost, USD/kg 9.00 9.00
Annual makeup (% of organic inventory) 30% 15%
Table 5 System Installed Cost Plus Organic Cost

Mixer-settlers vs. MDD/GES (all values in USD)
Mixer-Settlers MDD/GES
Cost Factors
Installed 25,000,000 19,000,000
Organic Fill 2,025,000 675,000
Make-up (5 year period) 3,037,500 506,250
Total Cost Over a 5 Year Period 30,062,500 20,181,250
Page 9 of 10
REFERENCES
SX Kinetics Internal Research, (2008) “Why O/A ratios and phase continuity are important for efficient SX
plant operation”, 2008, Ontario, Canada
Godfrey, J.C., Hanson, Carl, Slater, M.J. (1978), “Studies of Entrainment in Mixer Settlers”, AIChE
Symposium Series, Vol 74, , 1978, pp 127 – 133
Meikrantz, D (1998) “Continuous liquid-liquid extraction via an improved centrifugal contactor”, AIChe
Symposium. 1998, pp 1-13
Law, Jack L. and .Todd, Terry A. of the Idaho (USA) National Laboratory, “Comparison of Mixer-settler,
pulsed column and centrifugal contactors”, Advanced Separation Techniques for Nuclear Fuel Reprocessing and
Radioactive Waste Treatment, p 160, 2011
Miller, Graeme and Readett, David. 2003 “Solvent Extraction Entrainment Control Needs and Strategies”
ALTA SX/IX Conference 2003, Perth, Australia, p. 12
Page 10 of 10
Aqueous Two-Phase System of Poly (Ethylene
Glycol) 4000 and Ferric Sulphate at 323.15 K
Islamán Villalobos, Yahaira Barrueto, Katiuska Garnica and Yecid Jimenez
Universidad de Antofagasta, Chile
ABSTRACT
From previous studies in the hydrometallurgical field, where the solvent extraction stage uses highly
volatile and polluting organic solvents, aqueous two-phase systems (ATPS) arise as an alternative to
replace these organic solvents. ATPS have many advantages such as low cost, low viscosity, short
process time, low energy consumption, and environmental friendliness.
ATPS are usually formed by combining polymer/polymer, polymer/salt or salt/salt dissolved in
water. These systems have been previously studied in the extraction of biological material such as
proteins and cells, the recovery of biomolecules, and in the extraction of inorganic salts and metal
ions.
Liquid-liquid equilibrium (LLE) data for the Fe2(SO4)3 + polyethylene glycol 4000 (PEG 4000) + H2O
system were determined experimentally at T = 323.15 K. Additionally, experimental density, sound
velocity, refractive index, and viscosity data were also reported at T = 323.15 K. In the future, the
liquid-liquid equilibrium (LLE) data and the physical properties reported herein could allow metal
ion separation processes to be planned.
The Chen-NRTL model and the Othmer-Tobias equation were used to correlate the experimental tie-
line data, obtaining a good representation of the equilibrium. The results show that the quality of
fitting is better with the Chen-NRTL model.
1
INTRODUCTION
From previous studies in the hydrometallurgical field, where the solvent extraction stage uses highly
volatile and polluting organic solvents, aqueous two-phase systems (ATPS) arise as an alternative for
replacing these organic solvents, since ATPS have many advantages such as low cost, low viscosity,
short process time, low energy consumption, and environmental friendliness (Raghavarao et al.,
2003).
Systems containing two aqueous liquid phases at certain concentrations are very useful to extract and
recover many types of molecules and ions. These systems are usually formed by combining
polymer/polymer, polymer/salt or salt/salt dissolved in water (Zaslavsky, 1994).
One of the most common polymers used to form ATPSs is poly(ethylene glycol) (PEG), which is a
hydrophilic polymer. This polymer is mixed with a kosmotropic (water structuring) salt to form an
ATPS. This type of ATPS can be applied to separate, concentrate or fractionate biological solutes and
particles, such as cells and proteins (Perumalsamy & Murugesan, 2007; Wongmongkol & Prichanont,
2006; Singh & Verma, 2010). ATPSs can also be applied to selectively separate metal ion species
(Bulgariu & Bulgariu, 2007).
As a continuation of previous work, the liquid-liquid equilibrium data for the ATPS formed by
Fe2(SO4)3 + PEG 4000 + H2O at 323.15 K are reported. The physical properties including density, sound
velocity, refractive index, and kinematic viscosity of both phases were also measured. In the future,
the liquid-liquid equilibrium (LLE) data and the physical properties reported herein could allow
metal-ion separation processes to be planned.
The experimental data of the tie-lines were correlated by Chen-NRTL model and with the Othmer-
Tobias equation (Jimenez & Galleguillos, 2011; Othmer & Tobias, 1942).
METHODOLOGY
Chemicals
Synthesis grade PEG with an average molar mass of 4000 (3500-4500) was procured by Merck and
ferric sulfate hydrate with a purity of >0.985 was procured by Winkler, both reagents were used
without further purification. Deionized water was used in all experiments (Milli-Q, Millipore, κ =
0.055 S·cm-1)
Apparatus and procedure

The binodal curves were determined by the turbidimetric method (Jimenez & Galleguillos, 2010); this
procedure consisted in adding small amount of PEG or Fe 2(SO4)3.nH2O (typically 0.001 g) to the
respective aqueous solution. Later, the solution was shaken and put in a thermostatic bath at constant
temperature ( 0.1 K) for some minutes. The procedure was repeated until a change in the turbidity
appeared, thereby indicating the formation of a second liquid phase.
The tie-lines were determined at constant temperature for mixtures of known overall composition
(typically 60 g), which were agitated for 48 h in a rotatory bath, whose temperature was controlled
within ±0.1 K. The biphasic solutions obtained were allowed to settle for 24 h at constant temperature,
and extending the time periods of agitation and sedimentation did not affect the results, this last was
verified in previous tests, where five solutions with the same composition were prepared and carried
2
to the equilibrium, to verify the equilibrium time the density of the top and bottom phases were
measured at different times. After reaching equilibrium, triplicate samples were taken from top and
bottom phases to determine the composition of each phase and measure the physical properties
(density, sound velocity, refractive index and kinematic viscosity).
All solutions were prepared by mass using a Mettler Toledo analytical balance (model AX-204) with
a precision ± 0.1 mg.
The densities and sound velocities of the solutions were measured in a density and sound velocity
meter (Anton Paar: DSA 5000M). The equipment was calibrated using distilled deionized water and
air as reference substances.
A refractometer (Anton Paar Abbemat 550) was used to measure refractive indices. A calibrated
micro-Ostwald viscometer was used to measure the kinematic viscosities. This viscometer is
constituted by a Schott-Gerate automatic measuring unit (model AVS 310) equipped with a
thermostat (Schott-Gerate, model CT 52) in which the temperature was regulated to within ± 0.05 K.
The concentration of Fe2(SO4)3 was determined by analyzing the iron content using atomic absorption
spectroscopy (AAS). The AAS measurements were performed using a Varian Atomic Absorption
Spectrophotometer, model 220. The uncertainty of these measurements was ±0.5%. The PEG
concentration was determined using the Merchuk equation (Merchuk, Andrews & Asenjo, 1998),
which related the concentrations of ferric sulfate and PEG, and the water content is given by the
difference between the iron and PEG concentrations.
The amount of water molecules of ferric sulfate (Fe2(SO4)3.nH2O) were determined by analyzing the
weight loss of the sample. This weight loss was measured in a Thermogravimeter TGA/DSC1, STARe
System (Mettler Toledo), with a heating rate of 10°C/min, in a flowing inert nitrogen atmosphere with
a flux of 25ml/min, using an alumina crucible of 70 µL. The registered descent corresponds to nine
water molecules (Figure A1).
Thermodynamic framework
The excess Gibbs energy, GE, for the Chen-NRTL model is calculated as a sum of three contributions:
𝐺 𝐸 = 𝐺𝐸,Comb + 𝐺𝐸,LR + 𝐺𝐸,SR , (1)
where GE,Comb, GE,LR and GE,SR are the combinatorial contribution, the long-range interaction
contribution and the short-range interaction contribution, respectively.
Thus, the expression for the activity coefficient of component I (polymer, ions, water) also consists of
the sum of three contributions:
ln𝛾𝐼 = ln𝛾𝐼Comb + ln𝛾𝐼LR + ln𝛾𝐼SR . (2)
To calculate GE,Comb, GE,LR and GE,SR, the Flory-Huggins expression (Flory, 1942), the Pitzer-Debye-
Hückel equation (PDH) (Pitzer, 1980) and the Chen-NRTL model (Zafarani-Moattar & Sadeghi, 2002)
were used respectively.
3
Binodal curve
The equilibrium compositions of the aqueous two-phase system, Fe2(SO4)3 + PEG 4000 + water at
323.15 K were obtained experimentally. The experimental data of the binodal curves are shown in
tables 1.
Table 1 Binodal curve data of the Fe2(SO4)3 (ca) + PEG 4000 (p) + H2O (w) system at 323.15 K
wca wp wca wp
T = 323.15 K
0.4082 0.0111 0.2061 0.1023
0.3407 0.0142 0.1971 0.1144
0.3150 0.0202 0.1892 0.1267
0.2971 0.0245 0.1808 0.1380
0.2839 0.0280 0.1747 0.1469
0.2723 0.0332 0.1660 0.1606
0.2638 0.0381 0.1577 0.1754
0.2550 0.0446 0.1493 0.1912
0.2390 0.0638 0.1413 0.2072
0.2299 0.0739 0.1284 0.2630
0.2205 0.0849 0.1208 0.2911
0.2131 0.0942 0.1145 0.3079
Tie-lines and physico-chemical properties

The tie-lines data are given in table 2. Additionally, density, sound velocity, refractive index and
kinematic viscosity data of each one of the phases are reported. Figures 1 shows the tie-lines for this
system.
4
Table 2 Experimental phase equilibrium compositions for the Fe2(SO4)3 (ca) + PEG 4000 (p) + H2O (w) system, viscosity (ν), refractive index (nD),
density (ρ) and sound velocity (s) at 323.15 K.
Total system Top Phase Bottom Phase
s/(m∙s-
wca wp wca wp ν /(mm2·s-1) nD ρ/(g∙cm-3) s/(m∙s-1) wca wp ν /(mm2·s-1) nD ρ/(g∙cm-3) 1)
T = 323.15 K
0.2311 0.0987 0.1424 0.2276 11.552 1.3953 1.17313 1657.72 0.2872 0.0308 2.641 1.3982 1.29083 1631.70
0.2016 0.1628 0.1196 0.2806 31.988 1.4108 1.18044 1686.47 0.3019 0.0285 3.540 1.4204 1.40765 1677.78
0.2381 0.1208 0.1251 0.2848 18.086 1.4008 1.16768 1670.15 0.3201 0.0178 2.707 1.4056 1.33084 1643.40
0.2100 0.1745 0.1068 0.3141 19.405 1.4162 1.19120 1690.24 0.3219 0.0172 5.380 1.4301 1.44113 1693.69
0.2451 0.1362 0.1247 0.3073 21.072 1.4033 1.17150 1678.69 0.3320 0.0223 2.066 1.4158 1.36612 1657.59
0,35
0,3
0,25
0,2
WP
0,15
0,1
0,05
0
0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45
Wca
Figure 1 Liquid-liquid equilibrium of the Fe2(SO4)3 + PEG 4000 +H2O system at 323.15: () Binodal curve,
(∙∙●∙∙) Tie-lines, (—) Merchuk equation and (–×–) Chen-NRTL model
Table 2 shows that at constant temperature and different system global compositions, the salt
concentration in the bottom phase always exceeds that in the top phase. Thus, the density of the
bottom phase also exceeds the density of the other phase. It also shows that the refractive index of
the bottom phase exceeds that of the top phase because the molecules are more tightly packed
(Muruchi, Galleguillos & Jimenez, 2016). The viscosity values of the top phase always exceed that of
the other phase because the PEG concentration is higher in the top phase. Similar behavior was
observed for the sound velocity.
Correlations
The binodal curve data were fitted according to the empirical equation developed by Merchuk
(Merchuk, Andrews & Asenjo, 1998):
0.5 3 )
𝑤𝑝 = 𝑐𝑒𝑥𝑝⁡(𝑑𝑤𝑐𝑎 − 𝑓𝑤𝑐𝑎 (3)
where wp and wca are the polymer and salt concentrations, respectively. c, d, and f are fitting
parameters. Table 3 shows these calculated parameters using least square regression.
Table 3 Parameters of the Merchuk and Othmer-Tobias equations for the Fe2(SO4)3 (ca) + PEG 4000
(p) + H2O (w) system at 323.15 K
T = 323.15 K AAD%a
Merchuck c 4.4603 0.3910

d -7.7437
f 34.8926
Othmer- 0.5836
k 0.5167
Tobias
n 2.0234
𝑒𝑥𝑝
∑|𝑤𝑖 −𝑤𝑖𝑐𝑎𝑙 |
a 𝐴𝐴𝐷 = 100, where N is the data number used to the correlation
𝑁
According to the obtained absolute average deviations, the Merchuk equation can be used to
reproduce the binodal curves at 323.15 K. Figure 1 shows the calculated binodal curve at 323.15 K.
The tie-line data were correlated with the Othmer-Tobias (Othmer & Tobias, 1942) equation:
𝑇 𝐵 𝑛
1−𝑤𝑝 1−𝑤𝑐𝑎
( 𝑇 ) = 𝑘( 𝐵 ) (4)
𝑤𝑝 𝑤𝑐𝑎
where, k and n are fitting parameters. wca, wp and ww are the mass fractions of the salt, polymer and
water, respectively. The superscripts “T” and “B” refer to the top and bottom phases, respectively.
Table 3 also shows the determined parameters.
The obtained absolute average deviations (AAD%) show that the Othmer-Tobias equation
satisfactorily correlate the tie-line data.
Also, Chen-NRTL model (Jimenez & Galleguillos, 2010; Zafarani-Moattar & Sadeghi, 2002) was used
to correlate the experimental data. The minimized objective function is defined by:
𝑇 𝑇 𝐵 𝐵 2 2
𝐹𝑜𝑏 = ∑𝑢=1 ∑𝑣=1 {(𝑤𝑢,𝑣,𝑒𝑥𝑝 − 𝑤𝑢,𝑣,𝑐𝑎𝑙 ) − (𝑤𝑢,𝑣,𝑒𝑥𝑝 − 𝑤𝑢,𝑣,𝑐𝑎𝑙 ) } (5)
where wu,v is the mass fraction of the component “u” for the vth tie-line and the subscripts ‘‘exp” and
‘‘cal” refer to the experimental and calculated values, respectively. The superscripts “T” and “B” refer
to the top and bottom phases, respectively. The experimental data were also correlated considering
the following equilibrium condition:
(𝑥𝐼 𝛾𝐼 )𝑇 = (𝑥𝐼 𝛾𝐼 )𝐵 (6)
Table 4 shows the calculated interaction parameters with the corresponding deviations.
Table 4 Interaction parameters of the Chen-NRTL model for the Fe2(SO4)3 (ca) + PEG 4000 (p) +
H2O (w) system at 323.15 K
Chen-NRTL model
𝑎ca,𝑝 𝑎𝑝,ca 𝑎ca,𝑤 𝑎𝑤,ca 𝑎𝑝,𝑤 𝑎𝑤,𝑝 AAD%a
-361.679 -28852.618 -3991.906 -31565.594 6101.349 -887.411 0.010

𝑒𝑥𝑝
∑𝑛
𝑖 |𝑤𝑖 −𝑤𝑖𝑐𝑎𝑙 |
a 𝐴𝐴𝐷 = 100, where N is the data number used to the correlation.
𝑁
The obtained standard deviation shows that the Chen-NRTL model correlates satisfactorily the
experimental data. As an example to show the reliability of the Chen-NRTL model a comparison
between the experimental and correlated tie-lines is also shown in Figure 1. It is also important
mentioned that the PDH equation gives the Chen-NRTL model better accuracy.
CONCLUSIONS
Liquid–liquid equilibrium data for the Fe2(SO4)3 + PEG 4000 + H2O system were obtained at 323.15 K.
As part of the study, binodal curve, tie-lines and the properties of density, sound velocity, refractive
index and viscosity of both phases for the studied tie-lines were reported. As a consequence of the
comparison of the data reported by Villalobos et al. (Villalobos et al. 2016) and the informed data is
concluded that the biphasic area increase with the temperature, so the ferric sulfate has higher
capacity to induce the phase separation as temperature increases, because at high temperatures the
free electrolyte amount in the bulk solution increases.
The Othmer-Tobias equation and the Chen-NRTL model were used to correlate the equilibrium
results. The results show that the quality of fitting is better with the Chen-NRTL model.
REFERENCES
L. Bulgariu, D. Bulgariu, Sep. Sci. Technol. 42 (2007) 1093-1106.
P.J. Flory, J. Chem. Phys. 10 (1942) pp. 51–61.
Y.P. Jimenez, H.R. Galleguillos, J. Chem. Thermodyn., 42 (2010) pp. 419-424.
Y.P. Jimenez, H.R. Galleguillos, J. Chem. Thermodyn., 43 (2011) pp. 1573-1578.
J.C. Merchuk, B.A. Andrews, J.A. Asenjo, J. Chromatogr. B, 711 (1998) pp. 285-293.
L. Muruchi, H.R. Galleguillos, Y.P. Jimenez, Fluid Phase Equilib. 412 (2016) pp. 29-38
D. Othmer, P. Tobias, Ind. Eng. Chem., 34 (1942) pp. 693-696.
M. Perumalsamy, T. Murugesan, Sep. Sci. Technol. 42 (2007) pp. 2049-2065.
K.S. Pitzer, J. Am. Chem. Soc. 102 (1980) pp. 2902–2906.
K.S.M.S. Raghavarao, T.V. Ranganathan, N.D. Srinivas, R.S. Barhate, Clean Techn. Environ. Policy, 5
(2003) pp. 136-141.
J. Singh, N. Verma, Braz Arch. Biol. Techn. 53 (2010) 1051-1056
I. Villalobos, Y. Barrueto, K. Garnica, Y.P. Jimenez, V Seminario de Difusión de la Investigación en la
Facultad de Ingeniería-Universidad de Antofagasta. (2016)
N. Wongmongkol, S. Prichanont, Korean J. Chem. Eng. 23 (2006) 71-76.
M.T. Zafarani-Moattar, R. Sadeghi, Fluid Phase Equilib. 203 (2002) pp. 177–191.
B.Y. Zaslavsky, Aqueous Two-phase Partitioning: Physical Chemistry and Bioanalytical
Applications, CRC Press, 1994
APPENDIX
Figure A1 Thermal decomposition curve of Fe2(SO4)3.nH2O to determine the water molecules

The Mith of Aromatic Compounds in Metallurgical
Grade Kerosenes
Guillermo Stephens, Sergio Valladares and David Belmar
Axxa Chemicals, Chile
ABSTRACT
The metallurgical grade kerosenes used in the solvent extraction process must comply with certain
characteristics in order to be cost effective, and at the same time to be an efficient means of
dissolving and transporting the organic extractant throughout the different stages of the process (1)
The characteristics the kerosene must fulfill have largely been described in the specialized
literature, and in numerous papers and technical lectures (2). Basically they are:
 Must have a high Flash Point (not lower than 80°C)
 Be insoluble in water
 Have a low viscosity
 Have relatively low density
 Be capable of diluting the organic extractant
 Must maintain the copper – extractant complex in solution
 Have a short phase disengagement time from the aqueous solution
 Be available at relatively low cost
No mention is made on any requirement on the chemical composition; specifically on whether the
kerosene has to be fully aliphatic, or it can contain aromatic compounds.
The solvent extraction plants today have access to kerosenes that range in composition from no
aromatics to those with up to about 20% aromatics.
Plant operators usually make judgements based on preconceived ideas on the aliphatic or aromatic
character of a certain diluent that are not based on experimentally obtained data.
1
THE MITHS SURROUNDING AROMATICS CONTENTS IN A DILUENT
We as suppliers of the metallurgical grade kerosene Solvex (r), whose formulation contains about
20% aromatics, repeatedly come across some preconceived ideas on the performance of such a
diluent basically, they are two:
 Diluents which contain aromatics in their formulation evaporate faster than those which are
fully aliphatic.
 Aromatics contained in the diluent constitute a health hazard because some light aromatic
compounds are described in the literature as carcinogenic.
BENEFITS OF USING A DILUENT WITH AROMATICS IN ITS FORMULATION

Diluents which contain aromatics have a better capacity to dissolve the copper – extractant complex
(3). This fact has been evidenced at plants that use a high reagent concentration, where under
certain circumstances the organic extractant drops out of the organic phase, having a big negative
impact both in copper recovery, and in losses due to O in A entrainment.
Evidence has also been obtained that shows that the aromatics in the diluent shield the oxime and
reduce the oxidation effect produced by nitrates present in the PLS. In the case of one plant in
northern Chile, the presence of nitrates in the PLS led to a massive loss of extractant due to
degradation by nitration. This problem was solved by applying a certain ratio of aldoxime to
ketoxime, and by means of making use of a kerosene that contains aromatics.
EVAPORATION RATE OF A DILUENT

A study was done to determine the factors that are most relevant in influencing the evaporation
rate of kerosenes (4). The variables studied were aromatics contents and the temperature at which
the distillation process is started in the fractioning column.
The analysis carried out consists in comparing the resulting evaporation losses for the different
diluents involved in the study by weighing the samples under controlled pressure and temperature
conditions.
The testwork was divided into two series; the first of them determines the evaporation rates as a
function of the aromatics contents of the different diluents, being the other variables constant; the
other evaluates the evaporation rate as a function of the initial boiling temperature of the diluents.
Samples description
Ten samples, prepared according to ASTM standards, were used for the study which differed in
their aromatics contents, and in the initial boiling temperature. Table I gives a description of the
different samples used in the study.
2
Table 1 Physical Characteristics (Variation of the aromatics contents)
Result
Test Method Unit
Sample A Sample B Sample C Sample D Sample E
Distillation IBP ASTM D 86 °C 199 199 199 199 199
Distillation FBP ASTM D 86 °C 230 232 235 233 231
Flash point ASTM D 56 °C 78 78 78 78 76
Aromatics Content ASTM D 6379 %w 0 13 21 25 40
IBP: Initial boiling point; FBP: Final boiling point
Table 2 Physical Characteristics (Variation of IBP)
Result
Test Method Unit
Sample F Sample G Sample H Sample I Sample J
Distillation IBP ASTM D 86 °C 197 205 210 215 220
Distillation FBP ASTM D 86 °C 245 245 245 245 245
Flash point ASTM D 56 °C 78 84 87 89 92
Aromatics Content ASTM D 6379 % masa 21 21 21 21 21
N° 1 Series: Variation of the aromatics contents

The evaporation rates obtained for the samples with varying aromatics contents and equal Initial
Boiling Point (IBP), show that there is a direct relationship between the evaporation losses and the
aromatics contents.
Figs. 1 and 2 show the influence the aromatics content has on the losses due to evaporation for the
different diluents as a function of time.
The aromatics content was increased stepwise in 5 percentage units, the evaporation rate increases
in 0.104 kgs/day/m2, and a weight loss of 3.11% between sample A and sample E which
respectively show the lowest and the highest weight loss due to evaporation in the testwork.
As can be seen in Fig. 1, the weight loss is kept almost constant at 0.3% of the mass for an aromatics
content that varies from 0% to 20% (samples A, B, and C). Over this value there is an increase of
weight loss, reaching 0.83% for sample D, which has a 25% by weight of aromatics, and a loss of
1.68% for sample E, which has 40% by weight of aromatics.
3
25,0
20,0
Weight loss %w/w

15,0 Sample A
Sample B
10,0 Sample C
Sample D
5,0 Sample E
0,0
1 2 3 4 5 6 7 8 9 10 11 12 13
Day
Figure 1 Weight loss variation of the aromatics contents (%w)
It can be concluded from the weight loss data that the evaporation rates will follow a similar
pattern, i.e. the higher the aromatics contents, the higher the evaporation losses will be. This pattern
can be seen in Fig. 2, where the evaporation rate difference between samples A and E is 0.1
kg/day/m2. For the intermediate samples, the evaporation rates do not exceed 0.03 kg/day/m2.
0,700
0,600
Evaporation Kg/day*m2
0,500
Sample A
0,400
Sample B
0,300
Sample C
0,200 Sample D
0,100 Sample E
0,000
1 2 3 4 5 6 7 8 9 10 11 12 13
Day
Figure 2 Evaporation rate variation of the aromatics contents (kg/day/m2)
4
N°2 Series: Variation of the Initial Boiling Point
The evaporation rate for the samples with a constant aromatics content (21%), is inversely
proportional to the Initial Boiling Point (IBP), i.e. the higher the IBP, the lower the evaporation rate
of the diluent, as can be seen in Fig. 3.
Figure 3 Weight loss variation v/s IBP (%w)
As can be observed in Fig. 3, the weight loss decreases in approximately 8.4 percentage points (from
23.9% down to 15.44% weight loss) when the Initial Boiling Temperature increases in 8°C, from
197°C up to 205°C. From the study it was also concluded that for Initial Boiling Temperatures
above 210°C the same weight loss pattern is valid, but the difference in weight loss does not exceed
a value of 4% by weight.
The variation in evaporation rates for samples A and B, whose IBPs are 197°C and 205°C
respectively, reaches a difference of 0.167 kg/day/m2, while the difference between samples B and E
is 0.077 kg/day/m2, decreasing to 0.04 kg/day/m2 for samples B and C, to then remain constant at
0.02 kg/day/m2 for the rest of the samples as can be seen in Fig. 4.
kg/day/m2, decreasing to 0.04 kg/day/m2 for samples B and C, to then remain constant at 0.02
kg/day/m2 As can be observed in Fig. 3, the weight loss decreases in approximately 8,4 percentage
points (from 23.9% down to 15.44% weight loss) when the Initial Boiling Temperature increases in
8°C, from 197°C up to 205°C. From the study it was also concluded that for Initial Boiling
Temperatures above 210°C the same weight loss pattern is valid, but the difference in weight loss
does not exceed a value of 4% by weight.
The variation in evaporation rates for samples A and B, whose IBPs are 197°C and 205°C
respectively, reaches a difference of 0.167 kg/day/m2, while the difference between samples B and E
is 0.077 for the rest of the samples as can be seen in Fig. 4.
5
1,300
1,100
Evaporation Kg/day*m2
0,900
Sample F
0,700
Sample G
0,500 Sample H
Sample I
0,300
Sample J
0,100
-0,100 1 2 3 4 5 6 7 8 9 10 11 12 13
Day
Figure 4 Evaporation rate variation v/s IBP (kg/day/m2)
The results of the study show that even though the aromatics contents has a certain influence in the
loss of diluent due to evaporation, such losses are not relevant when compared to the losses as a
function of the Initial Boiling Point used in the production of the specific diluent, therefore making
this parameter more relevant when making an evaluation analysis of different options of diluents.
A different study was made at Axxa Chemicals to determine the evaporation losses of all the
diluents currently available in Chile. The results obtained are the following evaluation carried out
in Santiago for a period of 12 days.
Table 3 Evaporation rate (Kg/(day*m2))
Days
Product
0 1 2 3 4 5 6 7 8 9 10 11 12
Solvex Mineria 0.00 0.34 0.33 0.29 0.28 0.27 0.25 0.25 0.23 0.21 0.20 0.20 0.19
Fluid A 0.00 0.43 0.43 0.39 0.37 0.36 0.34 0.33 0.30 0.28 0.26 0.26 0.26
Fluid B 0.00 0.49 0.45 0.41 0.40 0.39 0.37 0.35 0.33 0.30 0.28 0.28 0.27
Fluid C 0.00 0.52 0.54 0.49 0.47 0.47 0.44 0.42 0.39 0.36 0.34 0.34 0.33
6
Figure 5 Evaporation rate variation v/s competitive fluid (kg/day/m2)
Fig.5 shows the evaporation rate for the different diluents evaluated for a period of 12 days. The
graph shows a high evaporation rate during the first day for all the diluents, to then start
declaining. Solvex shows the lowest evaporation rate throughout the 12 days period; the diluent
identified as C has the highest evaporation rate. The diluents identified as A and B show similar
evaporation rates, and are situated between those of Solvex and diluent C.
Table 4 Average evaporation rate
Evaporation
% aromatics
Diluent IBP °C rate
(maximum)
(Kg/hr/m2)
Solvex 23 208 0.23
Fluid A 18 206.5 0.31
Fluid B 20 204.5 0.33
Fluid C <0.5 200.5 0.39
The results show that Solvex, at 20% aromatics, has the lowest evaporation rate of the currently
commercially available solvents. This is the consequence of a higher Initial Boiling Point applied in
the distillation process, thus demonstrating what was explained before, that the aromatics contents
in a solvent is not necessarily what determines its evaporation rate.
This fact has also been confirmed at some of the plants currently operating with Solvex, some of
which are located at a high altitude above sea level.
Light Aromatics
Light aromatics, also referred to as BTX, comprise the species benzene, toluene, and xylene, which
reportedly constitute a health hazard, are sometimes believed to be present in the aromatics
formulated diluents. The following table shows some of the physical characteristics of these
compounds (5)
7
Table 5 Typical Aromatics Data
Vapor
Carbon Boiling temp. Flash Point,
Aromatic compound Pressure kPa
atoms N° °C °C
at 25°C
Benzene 6 80 -11 12.7
Toluene 7 111 4 3.8
Xylene 8 144 27 1
Butyl Benzene 10 183 58 0.13
Methyl Naphthalene 12 245 94 0.002
The distillation process to produce the Solvex diluent starts at 205°C, therefore of all the
compounds mentioned above, only methyl naphthalene might be present in the final product.
CONCLUSIONS
The aromatics compounds present in the metallurgical grade kerosenes do not impact their
evaporation rates in such a way to make them less attractive in terms of their contribution to the
production cost of a given plant. On the contrary, the diluents with aromatics in their formulation
should be viewed in terms of the benefits they have in terms of the higher solubility they show for
the copper – extractant complex, and the protection they give the oximes when faced with the
possible presence of nitrates in the PLS.
In view that the distillation process of the diluent Solvex starts at 205°C, the presence of compounds
of the BTX type is ruled out.
REFERENCES.
1. Rydeberg J. “Solvent Extraction Principles and Practice”, Chapter 7&8. 2 nd Edition. Marcel
Dekker
2004.
2. Bishop M.,et al. “Thechnical Developments leading to modern Solvente Extraction Diluents” ,
SME, Inc. 1998.
3. Domic E. “Hidrometalurgia, fundamentos, procesos y aplicaciones” Editorial Andros Ltda. 2001.
4. Belmar D, et al,: “Determination of the Relevant Factors that influence the evaporation rate of
Metallurgical Grade Kerosenes. Hydroprocess 2015.
5. CRC, Handbook of Chemistry and Physics. W.M. Haynes ( Editor). 93 rd Edition 2012-2013.
8
CHAPTER 6
Leaching and Solvent

Extraction in Chloride
Medium
Leaching of Primary Copper Sulfides in Chloride-
Ferrous Medium
Karina Salinas1, Juan Alvarez1, Cynthia Torres2, Camila Córdova3 and Osvaldo Herreros3
1. Compañía Minera Zaldíva, Chile.
2. Universidad Católica del Norte, Chile
3. Universidad de Antofagasta, Chile
ABSTRACT
This work is about the kinetic behaviour of the leaching primary sulfide ore of Minera Zaldívar
Company (CMZ), located in Antofagasta Chile, in a chloride-ferrous medium treatment. The effects
of chloride and ferrous concentrations, as well as temperature on copper extraction have been
studied. The ranges of these variables have been considered keeping in mind the costs involved and
whether the results would allow application in the company's industrial process. The leaching was
carried out in PVC columns of 1.5 cm high by 18 cm diameter, loaded with approximately 50 kg of
P (80) of 11.5 mm granulometry previously agglomerated, rested for 14 days and treated for 89 days
of irrigation. The best extractions of total copper, 50.23%, were achieved with the conditions of 32.9
°C, addition of 0.6 kg sulfuric acid, 0.525 kg of NaCl and 0.5 kg of FeSO4 in the agglomerate. The
most significant effects were temperature and the addition of NaCl in the agglomerate.
The dissolution reactions of copper sulfur and / or pyrite species occur essentially in the curing
step, where the reactions would be favored by a low percentage of humidity, which implies to have
more concentration of the reagents in the leach solution. In addition, it should be considered that in
the curing step, the heat generated as the result of the dissolution of concentrated sulfuric acid
makes the reactions thermodynamically favourable.
1
INTRODUCTION
It is known that as mineral deposits are deeper, the law of mineral diminishes and mineralogical
species become more complex. CMZ does not escape this reality and from the year 2019 the
extracted ore will increase its content of chalcopyrite. The current CMZ leaching process involves
the curing step of sulfuric acid per ton of ore and a determined amount of IPLS (Intermediate
Pregnant Leach Solution). The ore is transported and agglomerated by transferring conveyor belts
to form a heap leach. Once the heap leach is ready, the irrigation begins with a leaching cycle of
approximately 300 days. The modification would consist of adding together with the acid, reagents
such as sodium chloride and ferrous sulfate in the agglomerate stage and carrying out the leaching
process at a temperature of approximately 30 °C, to increase the percentage of copper extraction in
the leach mineral type primary sulfide.
The main objective of this work was to determine the effect of the modification in the curing
process and the temperature in the copper leaching kinetics of the sulfide-type mineral of CMZ,
which has a mineralogical composition of chalcopyrite, covellite and chalcocite.
It should be mentioned that many studies have been conducted on the leaching of chalcopyrite with
reagents such as ferric sulfate, ferric chloride, sodium nitrate-sulfuric acid, hydrochloric acid and
sodium chloride-sulfuric acid mixtures, among others (Senanayake, 2009).
On the other hand, the slow copper dissolution of chalcopyrite has been attributed to the formation
of a passivation layer on the mineral surface. This phenomenon has been widely studied, with no
consensus regarding about causes or how to avoid its formation (Watling, 2006; Klauber, 2008;
Debernardi & Carlesi, 2013).
Recent studies have shown that passivation of chalcopyrite depends on redox potential (Eh), since
high redox potentials (high concentration of ferric ions) promote the passivation of chalcopyrite
(Hiroyoshi et al., 1997), and that (Hiroyoshi et al., 1997; Hiroyoshi et al., 1999; Kametani & Aoki,
1985).
METHODOLOGY
Mineral
For the leaching tests, 500 kg of ore containing primary sulfide contents were obtained from a mine
stockpile. The ore was reduced in size, homogenized and graded to obtain fractions with a grain
size profile of ¾ "mesh up to -200 # with a P (80) of 11.5 mm. A general sample of the homogenized
mineral was taken for chemical analysis, mineralogical and scanning electron microscopy in
conjunction with X-ray diffraction (SEM-EDX).
The mineralogical composition of the mineral base, shown tabulated in TABLE 1, indicates that the
mineral has contents of magnetite (0.63%), chalcopyrite (0.55%), pyrite (0.28%) and covellite
(0.15%).
2
Table 1 Mineralogical composition
% Mineral Composition
%
Mineral Base
Chalcocite 0.04
Covellite 0.15
Chalcopyrite 0.55
Bornite 0.01
Pyrite 0.28
Hematite 0.02
Magnetite 0.63
Ilmenite 0.03
Rutile 0.01
Gange 98.29
TOTAL 100.00
Original mineral SEM-EDX analysis

SEM-EDX analysis of the original ore sample was performed. The elemental composition of the
original mineral sample indicated that it contained mostly oxygen, aluminum and silica, so it could
be concluded that the mineral has a large amount of aluminosilicates such as aluminum oxide
(Al2O3) and silica (SiO2). In the sample it was possible to detect the presence of chalcopyrite.
Chemical analysis of the original mineral

By incremental division a sample of the mineral head was drawn for each column for chemical
analysis and the law of the mineral was determined through the sequential method of copper. This
analysis allows knowing the degree of solubility of the mineral in solutions of sulfuric acid and
cyanide. The sulfuric acid digestion yields the copper content as acid soluble oxide, in the solid
residue of the same sample and after adjustment of pH and by digestion with a solution with
cyanide, the copper contained in the secondary sulphides and the bornite. Finally, the above
analytical residue is called residual copper, which corresponds to the copper present in the
chalcopyrite.
The chemical analysis for each sample of head according to column is detailed in TABLE 2 and it
can be seen that the mineral used has the highest amount of copper in the form of chalcopyrite.
Table 2 Chemical analysis of ore head per column, showing percentage of soluble copper (CuS);
Cyanurable copper (CNsCu) and Residual copper (Cur)
Column Column Column Column Column Column Column Column Column
1 2 3 4 5 6 7 8 9
Total copper 0.35 0.38 0.43 0.36 0.47 0.38 0.37 0.41 0.45
Soluble copper 0.04 0.04 0.04 0.04 0.04 0.06 0.04 0.04 0.05
Cyan. copper 0.13 0.14 0.16 0.14 0.19 0.14 0.13 0.15 0.17
Residual copper 0.18 0.20 0.23 0.18 0.24 0.18 0.20 0.22 0.23
Total iron 4.88 4.95 4.90 4.82 4.97 4.94 4.64 4.87 4.67
3
The curing and agglomeration stage was performed on a HDPE binder by pouring the
corresponding acid solution per column onto the mineral. The curing solution contains 12 kg of
sulfuric acid per tonne of ore and the corresponding reagents.
Once the ore was agglomerated, it was loaded into the columns and left to stand for 2 weeks under
two different conditions: from column 1 to 6 the rest was in a temperate (container with an electric
hot air generator) and column 7 to 9 at room temperature. In each of them a Tiny-tag temperature
recorder was installed on the mineral bed. The temperature recorders were configured to measure
the temperature every two hours.
The leaching was carried out in 9 columns (C1-C9) of PVC of 1.5 m high by 18 cm in diameter. Each
of the columns was loaded with 50 kg of ore. Leaching was performed with IPLS (Intermediate
Pregnant Leach Solution) at an irrigation rate of 8 L/m 2h and, subsequently, with refining at an
irrigation rate of 5 L/m2h in an open circuit system using peristaltic pumps resistant to the action of
acid contained in the IPLS and raffinate. For the control of the leaching process, daily samples of the
incoming solution and the percolation of the columns were made for the determination of copper,
total iron, iron II and acidity.
The irrigation time for columns 1 through 6 was 89 days, and columns 7, 8 and 9 were 47 days,
because they reached the stationary phase in the copper extraction.
Leach temperature
An average temperature of 32.9 °C was recorded in the columns heated with an electric hot air
generator (columns 1 to 6) and 14.5 °C in the columns kept at room temperature (columns 7, 8 and
9).
Figures 1 and 2 show the temperature profiles as a function of the leaching time.
Figure 1 Columns temperature 1 to 6
4
Figure 2 Temperature register of columns 7 to 9
Redox Potential of leaching solutions

Figure 3 shows that the output solutions were maintained at a potential near 600 mV (vs SHE) in all
columns with no major variations.
Figure 3 Potential solutions of exit of the columns as a function of the ratio leaching (RL)
On the other hand, when the leaching is carried out at room temperature, the consumption of acid
by the mineral increases, accelerating the kinetics. The maximum consumption achieved in the tests
was approximately 36.5 kg acid/mineral tonnes for the heated columns at 32.9 °C and 20 kg
acid/mineral tonnes for the columns at room temperature.
5
Copper extraction from solutions
Chemical analysis of mineral residue

The results of the chemical analysis of gravel collected from each column are detailed in TABLE 3,
based on this information, the copper extraction calculation of the mineral was carried out,
comparing the copper grade and the gangue grade at the end of the test period.
Table 3 Chemical analysis of mineral residue per column
C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9

Total Copper 0.23 0.24 0.29 0.20 0.23 0.19 0.34 0.36 0.40
Soluble copper 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.03
Cyanurable copper 0.06 0.07 0.08 0.05 0.04 0.04 0.12 0.13 0.16
Residual copper 0.15 0.16 0.19 0.14 0.17 0.13 0.20 0.21 0.21
Total iron 4.6 4.77 4.65 4.79 4.91 4.97 4.74 4.71 4.68
Extraction of copper from the mineral

TABLE 4 shows the percentage of total copper extraction, with its respective percentages of
extraction from copper oxides and sulfides in each of the columns, considering the analysis of head
and the gangue of the columns. The use of the reagents NaCl and FeSO4 in the leaching carried out
at 32.9 °C produce a remarkable increase in the extraction of copper sulfides and a slight increase in
the extraction of oxides. However, the use of these reagents in leaching at room temperature
produces low extractions of copper sulfides.
Table 4 Extractions of copper in percentage from oxides and sulfides of copper
C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9

Extraction of total copper 35.4% 35.8% 33.7% 44.2% 51.9% 50.3% 9.9% 13.0% 12.4%
Extraction of oxide copper 57.5% 57.5% 62.5% 62.5% 60.0% 71.7% 45.0% 50.0% 50.0%
Extraction of sulfide copper 32.6% 33.2% 30.8% 41.9% 51.2% 46.3% 5.7% 9.1% 7.7%
TABLE 5 summarizes the percentage of total copper extraction obtained in each column, with
respect to its agglomerate condition and leach temperature
6
Table 5 Extractions of total copper per column, agglomeration and leaching temperature
Column Extraction Agglomeration Temperature
1 35.4% 0.6 kg H2SO4 32.9°C

2 35.8% 0.6 kg H2SO4 + 0.5 kg FeSO4 32.9°C
3 33.7% 0.6 kg H2SO4 + 1 kg FeSO4 32.9°C
4 44.2% 0.6 kg H2SO4 + 0.525 kg NaCl 32.9°C
5 51.9% 0.6 kg H2SO4 + 0.525 kg NaCl+0.5 kg FeSO4 32.9°C
6 50.3% 0.6 kg H2SO4 + 0.525 kg NaCl+ 1 kg FeSO4 32.9°C
7 9.9% 0.6 kg H2SO4 14.5°C
8 13.0% 0.6 kg H2SO4 + 0.525 kg NaCl 14.5°C
9 12.4% 0.6 kg H2SO4 + 0.525 kg NaCl+0.5 kg FeSO4 14.5°C
According to the results of TABLE 5, a higher copper extraction was observed in columns 5 and 6
that were agglomerated with NaCl and additions of FeSO4 at 1% and 2% w/w respectively.
To explain the dissolution of primary copper sulfides, it is generally accepted that the leaching of
chalcopyrite is produced by the action of ferric chloride according to the reaction (Hauk & Maurice
(1998), Dutrizac (1981):
CuFeS2 + 4FeCl3 → CuCl2 + 5FeCl2 + 2S (1)
Using HSC version 6 software, reaction 1 has a Gibbs free energy, ΔG 0 = -39.04 kcal/mol at 14.5 °C
and -39.24 kcal/mol at 32.5 °C.
However, in the system used in this research it is unlikely that FeCl 3 will be formed "in situ" as a
leachant, according to:
Fe3+ + 3Cl- = FeCl3 (2)
Since this reaction has a positive ΔG0, so that reaction 2 would not occur. However, it is possible to
raise the following reaction (Blacksmiths 2014):
CuFeS2 + 4Fe3+ +Cl- = CuCl+ + 5Fe2 + + 2S (3)
Reaction 3 has a Gibbs free energy, ΔG0 = - 31.3 kcal/mol at 14.5 ° C and - 33.2 kcal/mol at 32.5 °C.
This would possibly be the reaction that would make feasible the dissolution of chalcopyrite in this
leach system.
This reaction reveals the importance of the presence of the chloride ion in the leaching system as a
facilitator of the chalcopyrite dissolution.
7
On the other hand, the action of ferrous ion in the system is a redox potential "stabilizer" and
probably an agent that would prevent the formation of some surface intermediate solid in the
chalcopyrite particle.
CONCLUSION
In the column tests carried out, the largest copper extractions were achieved in the columns at 32.9
°C. As the temperature increases and the same agglomeration conditions are assumed, the
extraction result can be up to five times that of the columns leached at 14.5 °C.
The highest copper extraction was obtained in column 5 (agglomerated with H 2SO4, NaCl and 1%
w/w FeSO4), in which an extraction of 50.23% of copper was achieved and in column 6
(agglomerated with H2SO4, NaCl and 2% w/w FeSO4), which reached a 48.5% extraction. The next
highest extraction was column 4 (agglomerated with H2SO4 and NaCl), which reached an extraction
of 41.84%.
Extractions of copper in columns agglomerated with H2SO4 or with H2SO4 and FeSO4 at 1% w/w or
2% w/w did not present extractions higher than 32% (columns 1, 2 and 3 respectively).
Copper extractions in the columns leached at room temperature did not exceed 15% of copper
extraction, despite the addition of NaCl and FeSO4 reagents.
ACKNOWLEDGEMENTS
The authors are grateful to Compañía Minera Zaldívar for the financing to carry out the present
study and also their authorization to publish the results that are framed in the Chilean patent
application 2238-2014.
REFERENCES
Debernardi, G. & Carlesi, C. 2013. Chemical-electrochemical approaches to the study passivation of
chalcopyrite. Miner.Process.Extr.Metall.Rev.34:10-41.
Dutrizac, J.E. 1981. The dissolution of chalcopyrite in ferric sulfate and ferric chloride media.
Metallurgical Transactions 12B:371-378.
Hawk, J.A. & Maurice, D. 1998. “Ferric chloride leaching of mechanically activated chalcopyrite”.
Hydrometallurgy, 49: 103 – 123.
Herreros, O., Personal comunication.
Hiroyoshi, N., Hirota, M., Hirajima, T., Tsunekawa, M. 1997. A case of ferrous sulfate addition
enhancing chalcopyrite leaching. Hydrometallurgy 47, 37-45.
Hiroyoshi, N., Miki, H., Hirajima, T., Tsunekawa, M. 2000. A model for ferrous promoted
chalcopyrite leaching. Hydrometallurgy 57:31-38.
Hiroyoshi, N., Maeda, H., Miki, H., Hirajima, T., Tsunekawa, M. 2001. Enhancement of chalcopyrite
leaching by ferrous ions in acidic ferric sulfate solutions. Hydrometallurgy 60:185-197.
Kametani, H.& Aoki, A. 1985.Effect of suspension potential on the oxidation rate of copper
concentrate in a sulfuric acid solution. Metallurgical Trans 16, 695-705.
8
Klauber, C. 2008. A critical review of the surface chemistry of acidic ferric sulfate dissolution of
chalcopyrite with regards to hindered dissolution. Int. J. Miner.Process.86: 1-17.
Senanayake, G., 2009, A review of chloride assisted copper sulfide leaching by oxygenated sulfuric
acid and mechanistic considerations, Hydrometallurgy 98, 21-32.
9
In Situ Acid Generation: a Potential Option for
Copper Oxide Heap Leaching Process
Felipe Hilário, Barbara Cardoso, Danielly Couto, Geysa Pereira and Rogério Ribeiro
Vale, Brazil
ABSTRACT
Heap leaching technology has successfully been used for copper recovery of oxide ores as well as
secondary sulphide ores (containing mainly chalcocite) for a number of decades. The acid-reactive
gangue minerals consume sulphuric acid from the percolating liquid, thus reducing the final acid
concentration in the PLS exiting the heap. This results in a pH profile in the heap, where the solution
pH is low at the top of the heap, while the solution pH is higher at the bottom.
After copper recovery, the acid consumption property of the ore is the most significant factor
influencing the economics of heap leaching and its reduction will therefore have a significant impact
on a project economics. The concept of the technology is to achieve a homogeneous pH profile in the
heap by the use of aerobic microbial oxidation of the elemental sulphur. The hypothesis is that In-
Situ Acid Generation (ISAG) can achieve this within the heap. The process is driven by firstly
agglomerating the ore with elemental sulphur prior to the stacking of the heap. Importantly, the acid
is generated at the agglomerate surface and within the heap where it is required and without surface
application and percolation from the top of the heap. The rationale is that less acid will be required
throughout the heap because the pH only needs to be brought to within the target pH range, rather
than below the target range. A key consideration is whether the system could be sufficiently
controlled within the targeted process pH range. Fortunately, such acid bio-generation systems seem
to be self buffering within the range pH 1.5-2.0. Using a copper oxide ore from northern region of
Brazil, experiments using 1m and 6m columns has demonstrated the concept of the technology. A
comparison between ISAG columns and a convention acid heap leaching is also presented.
1
Saline Tailings: AMD Production, Microbial Changes
and the Effect of Washing with LAR-2® as
Remediation Strategy
Cristián Pugh1,2, Bernardo González1,2, Juan Rivadeneira1,2,3, Hector Ayala3, Raimundo
Bordagorry3,4, and Gustavo Rodríguez1,2,3
1. Center of Applied Ecology and Sustainability (CAPES), Chile
3. Laboratorio de Investigación Aplicada, Chile
4. Universidad Diego Portales, Chile
ABSTRACT
The large amounts of water used to process sulfide copper minerals have led to put the attention on
the use of seawater, thus mitigating the overexploitation of fresh water. However, flotation processes
using seawater produce saline tailings, of which very little is known about its chemical stability and
the microbial processes involved in tailings stabilization. In this work, the effect of salinity on acid
mine drainage (AMD) production were studied using tailing dump material coming from the San
José flotation plant, also evaluating how the LAR-2 reagent (mainly composed by tricarboxylic acids)
could improve the tailing stability processes. A sample of tailing was subjected to salinization and
subsequent one kilogram of both, saline tailing and the native (non-saline) tailing, were placed in to
micro-columns. Wash treatments were assayed using LAR-2 solutions, rainfalls were simulated to
study AMD generation, and the changes in the composition of bacterial communities were analyzed.
Results indicated that saline tailings produced more acidic solutions and with a greater conductivity
than the non-saline tailings, producing higher dissolution of metals. Bacterial communities present
in saline and non-saline tailings increased in abundance as they underwent successive rainfall
regimes, although diversity remained relatively constant, but bacterial communities shown a
tendency to resemble each other at the end of rainfall simulation. LAR-2 treatment over tailings
produced a significant increase in metal dissolution as well as significant changes in the composition
of bacterial communities. Thus, LAR-2 application could induce the mobility of metals in both, saline
and non-saline tailings; therefore it may be used as leaching solution to recover metal values from
tailings, chemically stabilizing them. However its application as a tailing washing agent can have
deleterious effects on the environment if percolation solutions are not adequately controlled.
1
INTRODUCTION
The main economic activity in Chile is the mining industry, mainly copper-focused, which
contributed with the 11.99% of the country's GDP in 2014. Copper mineral extraction is mostly
exploited in the northern of Chile, in places that often do not have enough available water to carry
out their operations (Gajardo & Vivallo, 2009). This problem is more relevant because of the
decreasing of copper laws found in mineral deposits, which makes it necessary to increase the
amount of rock material processed to obtain the same amount of ore, thus producing an increase in
the amount of water needed to operate (Gunson et al., 2012). In order to solve the problem of water
scarcity, innovations have been made such as the use of seawater in copper mining processes, such
as in flotation (Castro, 2012).
Mining tailings are the main residue of copper mining processing, which are exposed to
environmental conditions, as wind, humidity and rainfall. The last two may generate acid mine
drainages (AMD), which correspond to the acidic and metal containing solution that percolate
through the soil layers and contaminate the underground water, altering their composition (Akcil &
Koldas, 2006), thus affecting both their microbiology and the macro fauna that use it (Kaushal et al,
2005).
The use of seawater in the flotation processes would have the effect of generating tailings with high
salt concentration. This creates a new problem since the chemical and microbiological properties of
these new tailings are unknown, as well as how they could affect the environment through the
generation of AMD.
Currently there are several methods for AMD control, although none of them have, so far, shown to
be completely effective for both drainage control (persistence over time) and economic feasibility. A
chemical method that is under study is the use of organic acids such as citric acid to form keloids
within the tail (Rodríguez, 2015), constraining the interaction water-air-tailing, thus reducing the
potential of AMD generation.
In this work, the chemical and biological properties of artificially salinized tailing column
microcosms were studied and compared with the same tailing column microcosms in its native form
(non-salinized). We also addressed how both types of tailings react to a washing treatment with the
compound LAR-2, which is composed mainly by tricarboxylic acids (Rodriguez, 2015).
METHODOLOGY
Sample salinization and column microcosms set up

Twenty kilograms of tailing were obtained from San José flotation plant from the Pucobre S.A. mining
company, Copiapo, Atacama region, Chile (27° 29′ S, 70° 18′ W). Four samples of one kilogram of
tailing were mixed with 40 g of Sea Salts (Sigma-Aldrich). This mixture was then wetted adding 100
mL of Sea Salt medium (20 g / L of salt) and mixed manually until a homogeneous mixture was
obtained. Four samples of one kilogram of non-salinized tailings were just wetted adding 100 mL of
distilled water.
To study AMD generation in salinized and non salinized tailings, four column microcosms were
filled, two with 1 kg of salinized tailing and two with 1 kg of non-salinized tailing (duplicate). Before
2
testing AMD production in salinized and non-salinized tailings, they were allowed to rest for a week
in order that the tailing material could better settle into the column.
To study the effect of LAR-2 over AMD generation in salinized and non-salinized tailings, four
column microcosms were filled, two with 1 kg of salinized tailing and two with 1 kg of non-salinized
tailing (duplicate). Before LAR-2 treatment and testing AMD production in salinized and non-
salinized tailings treated with LAR-2, they were allowed to rest for a week in order that the tailing
material could better settle into the column.
LAR-2 treatment, rainfall simulation and AMD generation in saline and non-saline
tailings
Four column microcosms, two salinized and two non-salinized were treated adding 200 mL of LAR-
2 (10 g/L) using a peristaltic pump at an irrigation rate of 0.2 mL per minute. One week after LAR-2
treatment all the eight columns (four salinized and four non-salinized) were watered by aspersion
with 30 mL of distilled water, once a week for four weeks, in order to simulate a rainfall of 9.041 mm
per week, accumulating an annual rainfall of 36.164 mm, to asses the normal to intensive precipitation
in the northern of Chile.
Percolate solutions corresponded to the drainages generated after each simulated rain. Those
solutions were recovered every week and analyzed for pH, conductivity, sulfate concentration (using
the "Sulfate assay kit" following the supplier's instructions, Sigma-Aldrich, 2016), chloride
concentration (using the titration method), and total Cu and Fe concentration by AAS (Atomic
absorption spectrometry). Also two samples of tailing from 3 cm depths were taken and metagenomic
DNA (total DNA from the sample) was extracted using the "FastDNA spin kit for soil" (MP
Biomedicals, Santa Ana, California, USA); to then amplify the 16S ribosomal gene of bacteria using
the forward primer 27F labeled with a fluorochrome 6-FAM and reverse primer 1492R. Applying the
technique of Terminal of Restriction Fragment Length Polymorphisms (TRFLP), using the MspI
endonuclease, relative abundances of the most abundant taxa of bacteria within the samples obtained
from tailings were determined.
RESULTS
AMD generation in saline and non-saline tailings

Both salinized and non-salinized tailing retained the first 30 mL of simulated rain, then it was not
possible to obtain drainage from untreated with LAR-2 tailings, in the first week. Drainages from the
simulated rainfall were inspected by naked eye and a salt precipitate was observed in those coming
from salinized tailings, while those from the non-salinized tailings did not present salt precipitate.
The drainages obtained exhibited variation in the pH depending on whether or not they were treated
with LAR-2. For tailings treated with LAR-2, pH of those salinized tailing material were higher than
those of the non-salinized ones (Figure 1, top-left panel). Unlike, drainages from tailings non-treated
with LAR-2, pH from salinized ones tend to be lower than the pH of the drainage from the non-
salinized tailings (Figure 1, top-right panel).
In tailings treated with LAR-2, conductivity of the drainage from the salinized tailings far exceeded
that obtained from the drains of the non-salinized tailings; however; the values of this parameter
decreased over time (Figure 1, bottom-left panel). On the other hand, without LAR-2 treatment,
3
conductivity of the drainage from the salinized-tailing was eight times greater than the non-salinized
one. However, unlike of what was observed in tailing treated with LAR-2, the conductivity remained
constant over time in both, salinized and non-salinized tailing drainages (Figure 1, bottom-right
panel).
With LAR-2 treatment Without LAR-2treatment
Non-Salinized
pH
Salinized
Conduc vity
Non-Salinized
Salinized
Figure 1 Levels of pH (top panel) and conductivity (bottom panel) in percolation drainages from salinized and
non-salinized tailings, when treated with LAR-2 (left panel), and without LAR-2 treatment (right panel).
For the LAR-2 treated tailings drainage, the chlorides in both drainages (from salinized and non-
salinized tailings) showed a high decrease over time, reaching a final concentration close to zero
mol/L (Figure 2, top-left panel). On the other hand, the drainages of tailings not treated with LAR-2,
the release of chlorides maintained constant values in non-salinized tailings and slightly decrease in
time in salinized tailing drainages (Figure 2, top-right panel).
For tailings treated with LAR-2, it was observed that the concentration of sulfates found in drainage
decayed over time for both types of tailings (salinized and non-salinized). It was also observed that
the drainage from the saline tailing had a lower concentration than those from the tailings that were
not salinized (Figure 2, bottom-left panel). Regarding the tailings non-treated with LAR-2, the release
of sulfates in the drainage decreased in time in salinized tailings drainage and increased in the non-
salinized tailings drainage.
4
With LAR-2 treatment Without LAR-2treatment
4,5 6
4
5
3,5
Cl- concentrataion (mol/L)
Cl- concentrataion (mol/L)

3 4
Chloride
2,5
Serie2 Non-Salinized
No Salino
3
2
Serie1 Salinized
Salino
1,5
2
1
0,5 1
0
1 2 3 4 0
2 3 4
0,09 0,084
0,08
0,083
SO4 concentrataion (mol/L)
0,07
SO4 concentrataion (mol/L)

0,082
0,06
Sulfate
0,05 0,081
Serie2 Non-Salinized
No Salino
0,04 0,08 Salinized
Salino
Serie1
0,03
0,079
0,02
0,078
0,01
0 0,077
1 2 3 4 2 3 4
Figure 2 Levels of chloride (top panel) and sulfate (bottom panel) in percolation solutions from salinized and
non-salinized tailings, when treated with LAR-2 (left panel), and without the treatment (right panel).
The release of copper from the LAR-2 treated tailings, proceeded in an accelerated manner, reaching
about 1 g / L concentration in the salinized tailing drainages and 0.85 g / L in the non-salinized tailing
drainages, during the first two applications of simulated rainfall. However, the successive
applications of rainfall caused an increase in Cu mobilization but then decreased after the fourth
application, in the case of the salinized tailings; whereas the non-salinized tailings presented a
decrease of copper release in drainage starting in the third rainfall application (Figure 3, top-left
panel). For tailings not treated with LAR-2, the release of Cu was much lower than that of those
treated with LAR-2, of the order of 2.7 mg / L for the drainage of the non-saline tailings and 1.6 mg /
L in those salinized tailings drainages, during the first two applications of simulated rainfall, but the
following simulated rains generated even less release of Cu from the tailings (Figure 3 top-right
panel).
The release of Fe from the tailings treated with LAR-2, proceeded much more slowly than Cu release,
with a tendency to increase Fe concentration over time, up to levels of 1.2 g / L Fe in drainages from
salinized tailings and 0.25 g / L Fe in non-salinized tailing drainages (Figure 3, bottom-left panel). In
the case of those tailings not treated with LAR-2, as observed for copper, the release of Fe was much
lower than when those tailings were treated with LAR-2, however, the trend to increase the release
of Fe since the first simulated rainfalls, stabilized at values around 4 mg / L, in the case of salinized
tailings, or decreased from 7 mg / L to 3 mg / L, in the case of those non-salinized tailings (Figure 3,
bottom- right panel).
5
Figure 3 Levels of Cu (top panel) and Fe (bottom panel) in percolation solutions from salinized and non-
salinized tailings, when treated with LAR-2 (left panel), and without the treatment (right panel)
Bacterial community changes in saline and non-saline tailings

In general terms, bacterial communities were affected by treatment with LAR-2. Non metric.
multidimensional scaling analysis (NMDS) clearly reflected these differences, establishing three
groups (Figure 4, left panel), two of which represented bacterial communities from tailings samples
not treated with LAR- 2 and a group represented by bacterial communities from tailings treated with
LAR-2 (Figure 4, left panel), indicating that treated tailings with LAR-2 produced less differences in
the composition of the communities than in the absence of LAR-2.
In agreement with that was observed in the non-salinized tailings, the salinized ones showed a
similar differentiation took place on the bacterial communities depending on if they were or not
treated with LAR-2. But in this case, two groups corresponded to communities belonging to tailings
treated with LAR-2, which in turn differed according to the time of exposure to simulated rainfall,
and one group corresponded to communities of tailings not treated with LAR -2. They were
differentiated by the exposure time to the simulated rains, but with a lower level of dissimilarity
between the communities (Figure 4, right panel).
6
Figure 4 Bacterial community ordination according to Bray-Curtis similarity from non-salinized tailing
communities (Left panel) and the salinized ones (right panel). Green triangles: non-treated tailings communities
(Control); Blue triangles: LAR-2 treated tailings communities (LAR).
DISCUSSION
Tailing residues from the sulfide copper mining flotation processes have the potential to generate
AMD (Akcil & Koldas, 2006); however this potential depends on multiple variables such as sulfur
and iron contents and the pH, as well as the environmental variables, mainly the rainfall of the place
where these are located (Akcil & Koldas, 2006). In addition, the microbial communities that inhabit
the tailings can modify their physicochemical properties, increasing the potential for them to generate
AMD (Korehi et al., 2013).
In this work, the potential to generate AMD by a copper mining tailing was evaluated when the
tailing was salinized. Also, we used a tricarboxylic acid as a treatment to mitigate the potential of
AMD generation, assuming that this acid acts as a chelating agent of metals, thus avoiding metal
release.
Although results showed that the drainage from the saline tailings mobilized less metals and sulfates
(Figures 2 and 3), they tend to acidify the percolated solutions (Figure 1) and increased the chloride
concentration (Figure 2), with a concomitant increase in conductivity (Figure 1). Therefore, the
potential of AMD generation increase, but with different consequences, from that of normal (non-
salinized) tailings. Although they do not contribute to a greater amount of metals to the solutions,
they increase their salinity with deleterious consequences for the environment (Jan, et al., 2015;
Kaushal, et al, 2005). For example, saline water can be propagated a substantial distance trough
superficial and ground water aquifers, leading to more widespread effects on water quality and can
have lethal and sublethal effects on aquatic plants and invertebrates (Kaushal, et al, 2005). Salinity
reduces the diversity and abundance of aquatic plant and invertebrate communities and having
immediate effects on plants that are not adapted to salt including leaf drop, leaf burn, stunted growth,
poor seed germination and tree death. Thus, saline tailings may offer additional difficulties to fito-
estabilize or fito-remediate them, because the constraint imposed by salinity over undapted plants.
7
The treatment with LAR-2 on salinized and non-salinized tailings produced an stabilizing effect,
which is reflected in smaller differences in the chemical parameters measured between the two types
of tailing drainages (compare panels left and right in Figures 1 and 2), particularly when increasing
the rainfall regime. However, there are strong differences in the release of metals between the
salinized and non-salinized tailings treated with LAR-2. The latter indicates that LAR-2 has a greater
synergistic effect with the salt in the dissolution and mobilization of metals from salinized tailings
(Figure 3, left panel), although independent of salinity, LAR-2 washing stimulates the release of
metals from the tailings (compare left and right panels of Figure 3).
On the other hand, the treatment of tailings with LAR-2, both salinized and non-salinized, has an
effect on the composition of bacterial communities present in tailings (Figure 4). The compositional
changes detected on bacterial communities are probably due to the fact that this compound is easily
metabolized by bacteria; so some species will be favored by the presence of this compound in the
tailings, increasing their abundance in relation to those obligate lithotrophic bacteria. It is also
possible that the metal leaching effect detected when using LAR-2 as a washing solution (Figure 3) is
due to this enhancement of the development of bacterial species with metal dissolving abilities,
however these hypotheses must be tested by additional experimentation.
CONCLUSION
Saline tailings, on contact with high rainfall, produce drainage with a high ionic charge, which can
cause environmental problems associated with this characteristic. In addition they are mobilized
more metals than in those non-saline, so that their drainage has a high complexity that makes it
difficult to their stabilization.
LAR-2 exerts a chemically stabilizing effect on the tailings, promoting the mobility of the metals, but
decreasing the release of sulfates and chlorides, so its use is recommended for the recovery of metals
from tailings prior to final disposal, stabilizing them chemically.
ACKNOWLEDGEMENTS
This work has been funded by the CONICYT grant to CAPES FB-0002-2014, and the CORFO grant
15ITE2-46476. The help of Luis Aghemio, from Prokumet Lab, is greatly appreciated.
REFERENCES
Akcil, A., & Koldas, S. (2006) Acid Mine Drainage (AMD): causes, treatment and case studies, Journal
of Cleaner Production, 14(12), pp 1139-1145.
Castro, S. (2012) Challenges in flotation of Cu-Mo sulfide ores in sea water, In Water in Mineral
Processing–Proc, of the First International Symposium (Ed. J. Drelich), SME, Chapter 2 (pp. 29-40).
Gajardo, M., & Vivallo, W. (2009) Evolución de las reservas y recursos de cobre, molibdeno, oro, plata,
nitrato y yodo en Chile 2001-2007, Servicio Nacional de Geología y Minería - Chile, Subdirección de
Geología.
Gunson, A. J., Klein, B., Veiga, M., & Dunbar, S. (2012) Reducing mine water requirements, Journal of
Cleaner Production, 21(1), pp 71-82.
8
Jan, S. u., Kubra, G., Naz, M., Shafqat, I., Shahzad, M. A., Afzal, F. and Kazi, A. G. (2016)
Biotechnological applications to improve salinity stress in wheat, in Plant-Environment Interaction:
Responses and Approaches to Mitigate Stress (Eds. M. M. Azooz and P. Ahmad), John Wiley & Sons, Ltd,
Chichester, UK, Chapter 1, pp 1-27.
Kaushal, S. S., Groffman, P. M., Likens, G. E., Belt, K. T., Stack, W. P., Kelly, V. R., Band, L.E., & Fisher,
G. T. (2005) Increased salinization of fresh water in the northeastern United States. Proceedings of the
National Academy of Sciences of the United States of America, 102(38), 13517-13520.
Korehi, H., Blothe, M., Sitnikova, M. A., Dold, B., & Schippers, A. (2013) Metal mobilization by iron-
and sulfur-oxidizing bacteria in a multiple extreme mine tailings in the Atacama Desert,
Chile. Environmental science & technology, 47(5), 2189-2196.
Rodríguez, L. A. (2015) Method for leaching copper oxide, replacing sulfuric acid with a non-
polluting organic leaching agent Patent No. 13992376. Estados Unidos.
9
SX Operation under High Chloride Content
Conditions
Rodrigo Zambra1, Mauricio Morales1, Matthew Soderstrom2 and Laurent Cohen2
1. Solvay, Chile
2. Solvay, USA
ABSTRACT
Copper solvent extraction (SX) plants have seen a trend of increasing chloride content in their feed
solutions due to shortage of fresh water (and use of sea water) and/or intentional addition of
chloride to aid in the leaching process. The high chloride content of the pregnant leach solution
(PLS) presents some challenges as it can affect the SX process with higher acidity, higher aqueous
viscosity, and greater sensitivity to aqueous-in-organic (A/O) entrainment. Low pH and high
viscosity of the PLS can impact the metallurgical performance (stage efficiency and Cu recovery).
The sensitivity to A/O entrainment requires additional considerations such as optimization of the
wash stage(s), use of coalescers, as well as monitoring and improving the physical quality of the
organic phase.
The following study presents the results of a complete review of the metallurgical behavior of the
SX plant when utilizing PLS with high chloride content. The study reinforces the importance of
maintaining a high organic quality through efficient clay treatment. It also demonstrates the
advantages of using modified aldoximes (over ketoxime based formulations) to maintain extraction
capacity at low pH, taking advantage of the faster kinetics to offset the drop in stage efficiency due
to higher aqueous viscosity.
INTRODUCTION
New leaching techniques involving the addition of chloride salts to improve copper recovery from
oxidized or secondary sulfide minerals, are generating leaching solutions with chloride
concentration in the PLS above 50 gpl, in some cases up to 100 gpl. Additionally, there is an
increasing trend in the industry to use sea water, because of the scarcity of fresh water available for
mining or due to the economic advantage for operations in geographical proximity to the Pacific
coast. As a result, the number of plants with high contents of chloride (i.e., above 50 gpl) has
increased significantly, forcing the industry to study all the possible effects of operating with high
concentrations of chloride ions. This holds true both for existing SX operations, in order to
implement the necessary changes, and for design considerations of future projects.
Historically, the chloride ion has been considered a typical impurity in the SX operations in Chile
due to the local ore mineralogy (Atacamita), with levels in the PLS typically between 0 and 10 gpl of
chloride. Some plants however, have had to cope with more elevated chloride levels due to the use
of sea water. Since their inception these plants have successfully operated with chloride
concentrations above 50 gpl (see Figure 1) by putting in place additional equipment for aqueous-in-
organic (A/O) entrainment contention (double wash stage and/or coalescers equipment) to avoid
chloride contamination in the electrolyte to EW, thus preventing the stainless steel cathode plates
from corrosion by pitting.
Mineralogy Sea water Leaching technology

•Mantos Blancos (65 gpl) •Tocopilla (50 gpl) •Michilla (65 gpl) (Cuproclor®)
•Pampa Camarones (62 gpl) •Michilla (65 gpl)
•Mantos de la Luna (60 gpl)
•Pampa Camarones (62 gpl)
•El Salado (60 gpl)
Figure 1 SX operations with high levels of Chloride in PLS
The following work presents a summary of the change of conditions in the PLS to be processed, due
to the high presence of chloride ions in relation to the metallurgic, chemical stability and physical
response of the solvent extraction process.
BACKGROUND INFORMATION
The presence of high chloride in PLS immediately leads us to review the behavior of the SX plant
from the metallurgical, chemical (organic stability) and physical aspects (A/O entrainments).
Metallurgical Review:
The presence of chloride ion in an acid aqueous solution increases the proton activity (H+), which
causes a reduction in the pH of the solution (See Figure 2).
Figure 2 PLS pH depending on the chloride level for 1 gpl H2SO4 (use NaCl)
Operations utilizing sea water with a chloride concentration of 20 gpl have reached an equilibrium
chloride concentration in the leach solution of 50 to 60 gpl. As shown in Figure 2, this amount of
chloride would result in a pH reduction from 1.92 to 1.6 assuming a constant value of 1 gpl H2SO4
in the aqueous solution. If this acid concentration increases due to different conditions of the
leaching process, the reduction in the pH will be even higher.
The pH reduction in the solvent extraction plant has a direct effect on the extraction efficiency and
consequently the transfer of Cu to electrowinning (EW). Therefore, the variables affecting the Cu
recovery must be adjusted in order to compensate for the reduction in copper transfer. However,
most variables are constrained by the operating conditions of the SX plant. As a result, one of the
main variables that can effectively be adjusted is the formulation of the extractant.
With PLS of low pH it is preferable to use formulations of strong extractants. The utilization of an
aldoxime as a base extractant gets better results in Cu recovery at low pH, as can be observed in
Figure 3. However, straight aldoxime is rarely used on its own as it is difficult to strip. The strength
of the formulation can be altered with modifiers to achieve the optimum strength. The correct
choice of modifier can also improve the chemical stability of the formulation.
Plants operating with sea water in their leaching process tend to show a high viscosity in their
aqueous solutions, typically above 5 cP (Yáñez-Soto: 2009). This can be explained by the high ionic
strength of the solution. However, in leaching conditions where chloride salt is added, this effect is
not observed.
Figure 3 Oxime behavior according to pH
The increase of viscosity in the aqueous solution often results in a reduction of the stage efficiency
in SX, affecting the transfer of Cu to EW (see Figure 4). Due to this, an increase is required in the
agitation or in the extraction capacity by increasing the percentage of extractant to accomplish the
recovery objectives.
Figure 4 Effect of viscosity on the stage efficiency and Cu Recovery
Similarly to the impact of lower pH, a revision of the extractant formulation may be required in
order to mitigate the effect of viscosity in the metallurgic performance of the plant. To this purpose,
it is advisable to use an extractant with fast kinetics to enable the mass transfer in spite of the
greater viscosity. Different studies have demonstrated the higher reaction kinetics (and subsequent
stage efficiency) of nonyl aldoxime over other aldoximes and ketoximes (See Table 1).
Table 1 Stage efficiency vs base extractant formulation.
Extractant formulation (20 vol %) Stage efficiency

C9 Aldoxime 90%
C12 Aldoxime 79%
Ketoxime 72%
Chemical Stability Review:

Previous studies have shown a possible negative effect on the hydrolytic stability of oximes in the
presence of a high concentration of chloride. This possible effect may be due to an increase in
potential ENH and/or higher proton activity. Although, industrial experience has shown that oxime
based formulations are quite stable under these leach conditions, this effect has been evaluated.
Physical Review:
On the other hand, the physical condition of the plant organic (organic quality) must be maintained
under high chloride conditions so that it generates lower levels of A/O entrainment. The quality of
the organic phase should allow the continuous operation, without deviations or non-compliances in
the production, quality or cost of the hydrometallurgical plant. Maintenance of the organic quality
will result in good coalescence between the aqueous and organic phases, minimizing A/O
entrainment. Therefore, in order to maintain good physical quality of the organic phase, clay
treatment is of critical importance to obtain the best physical conditions of the organic inventory.
Maintenance of organic quality via clay treatment has been discussed in more detail in separate
papers (Quilodran: 2015), but should be seriously considered for any operation treating a high Cl
tenor PLS. For a similar level of entrainment (A/O), an increase in the concentration of chloride in
PLS, will increase the mass of chloride transferred to the thankhouse. This can generate significant
problems in the process (pitting of blanks) or increasing the electrolyte bleed requirement. The
effect of clay treatment on the physical performance of the organic phases is shown in Figure 5.
Figure 5 Clay treatment, effects of Interfacial Tension on phase disengagement
ANALYSIS AND RESULTS

The methodology used for this study was executed under the standard Solvay laboratory
procedures for the construction of isotherms, kinetics, stage efficiency calculation and
determination of chemical stability. In the case of the physical performance, results of pilot studies
are shown.
Metallurgical Review:
The extraction isotherms obtained are shown in Figure 6. It can be observed that the effect of the
chloride ion produces a drop in the equilibrium curves for the different formulations of extractants
evaluated; the least affected being the ester-modified aldoxime due to a better chemical response of
Cu extraction under lower pH conditions. On the other hand, the stripping isotherms used are
shown below (Figure 7) for an extractant percentage of 18 vol% and an electrolyte of 40 gpl of Cu
and 190 gpl of acid.
The impacts of kinetics on stage efficiency are shown in Figure 8. It can be observed that there is
greater stage efficiency for the modified-aldoxime formulation, for both a low viscosity of 2 cP and
a high viscosity of 6 cP (corresponding to sea water conditions). The results also indicate an
improvement in kinetics with higher Cl concentration however, this may be offset by increasing
viscosity in the PLS, which decreases stage efficiency. This effect of high viscosity (6 cP) causes a
drop by approximately 2 pp in relation to the stage efficiency of 2 cP for the different formulations
analyzed.
Figure 6 Extraction isotherms for 0, 50, 100 and 150 gpl Cl concentrations
Figure 7 Stripping isotherms
Figure 8 Stage efficiency for different viscosity and Chloride in PLS

From the isotherms and calculated stage efficiencies, McCabe-Thiele analysis was completed to
estimate the chloride concentration impact on copper recovery for 2E+1S and 2E+2S configuration.
The recovery and Cu Transfer expected for a 1:1 O/A ratio are shown in Figures 9 and 10).
Figure 9 Cu Recovery, high chloride level conditions in PLS, 2E+1S; 2E+2S circuit
As can be observed, there is a negative effect in the copper recoveries and, hence, in the copper
transfer as the level of chloride in the treated PLS increases. This is mainly due to the effect shown
in the drop of the chemical equilibrium (extraction isotherms), because of the pH decrease from the
greater proton activity in presence of high concentrations of chloride in the aqueous phase.
Figure 10 Cu transfer, high chloride level conditions in PLS, 2E+1S; 2E+2S circuit
Chemical Stability Review:

The results of hydrolytic stability are shown below (See Figure 11) for the formulations of pure
aldoxime, ester-modified aldoxime and ketoxime.
Figure 11 Hydrolytic stability in relation to chloride in PLS
As can be observed, the presence of chloride in the PLS had limited impact on the stability of the
formulation under these test conditions. That said, the stabilization of the aldoxime is noticeable
when it is mixed with the ester modifier.
Physical Review:
As previously discussed, one of the main concerns when operating with high levels of chloride in
the PLS is the possible physical entrainment of this impurity to the electrolyte solution. In order to
reduce the possibilities of A/O entrainments, we recommend operating with a good quality organic
phase, reflected by the interface tension of the organic phase measured by the Delta IFT variable
(difference between the Interfacial Tension of a given plant organic and that of the same organic
after being treated with 50 kg/m3 of clay). A higher Delta IFT means a higher level of contamination
with tenso-active species, which leads to coalescence issues and higher A/O entrainments.
Studies carried out by Solvay have demonstrated that a clay treatment, operated in the best possible
conditions (correct clay dosage, elimination of aqueous, correct agitation, etc.) is vitally important
for the reduction of A/O entrainment. Below, we show a study carried out for an SX plant with
Delta IFT delta of 7dynes /cm. Its organic was treated with a dose of 20 kg/m3, reducing the Delta
IFT to 2.7 dynes/cm. The benefits in the improvement of the physical quality in the organic phase,
translated into a significant reduction in A/O entrainment as shown in Figure 12.
Treating the organic phase with clay (as prevention) shows similar benefits to that of operating with
a double wash stage (as remediation). Figure 13 shows the results obtained in an evaluation for an
SX plant using sea water, for a Delta IFT of 4.5 dynes/cm with a clay dosage of 20 kg/m3. The
comparison of chloride removal is made for plant organic treated with 1 wash stage versus
untreated plant organic with a double wash stage.
The correct clay treatment of organic brings similar efficiencies of chloride removal for one wash
stage vs. the double wash stage configuration. Note: Given the ability, two stages of wash would
be preferable to one, but efficiency is clearly related to organic quality and steps should be taken to
avoid contamination of the electrolyte.
Figure 12 Comparison of entrainments with/without clay treatment
Figure 13 Comparison of chloride removal, clay treatment vs double wash stage
CONCLUSION
While chloride has some impact on the SX operation in terms of physical and metallurgical
performance and presents some challenges to the industry, those can and have historically been
managed. The largest challenge remains the control of chloride and preventing its transfer to the
tankhouse. When excess chloride is present in the PLS, copper SX operations must put in place
solutions to prevent chloride contamination of the electrolyte. As such contamination happens
through entrainment, organic quality remains one of the most important variables to consider for
the control and minimization of chloride transfer. Efficient treatment of organic with clay is
fundamental for the SX plants that will operate or are already operating with high chloride
concentration in the PLS.
From the SX standpoint, other considerations/findings include:
 The higher the chloride concentration in the feed, the most benefit the operation will derive
from using stronger aldoxime formulations as they are more resistant to the pH drop.
 Higher chloride in the feed seems to improve the kinetics and consequently stage efficiency.
However this benefit may be offset by the buildup of total dissolved solids leading to
higher aqueous viscosity and therefore lower stage efficiency. Batch stage efficiencies and
kinetics should be considered in the plant evaluations and for design conditions.
 Stability of the oximes under extract conditions with high chloride shows no significant
concerns.
REFERENCES
– Yáñez H, Soto A, Cytec Chile. Viscosidad en las soluciones de lixiviación y su efecto en SX.
Cytec Chile Seminar (2009).
– Soderstrom M, Bednarski T, Villegas E, Cytec Industries. Eficiencia de acercamiento al equilibrio
en planta de SX de cobre. Cytec México Seminar, (2009).
– McCallum T, McCallum A, Bednarski T, SX impurities transfer and wash stage considerations.
SME conference (2015), Phoenix USA.
– Zambra R, Monsalve N, Cytec Solvay Group. Aspectos relevantes en la operación de SX bajo
condiciones de alto contenido de cloruro. CopperClor 2016. Santiago Chile.
– Quilodran A, Zambra R, Soderstrom M. Cytec Solvay Group. Organic phase quality and
optimization of the clay treatment process. Hydroprocess 2015. Santiago Chile.
CHAPTER 7
Design and Operation

of Solvent Extraction
and Electrowinning
Circuits
Measurements in Intercell Bus Bar with Four Contact
Points for Copper Electrowinning Plant
Chi Zhang1 and Junyi Wu2
1. Peking Brotech Company, China
2. Sanmen Sanyou Technology, China
ABSTRACT
With the demand of refined copper, the popularity of hydrometallurgy for copper refining has been
increasing in China. To improve energy efficiency and productivity in copper electrowinning (EW)
process, an intercell bus bar with four contact points has been used in many plants. In order to
evaluate its benefits, industrial tests were performed in a copper electrowinning plant and specific
measurements including cell voltage, cell current, voltages between anode and cathode at different
locations, changes in electrolytic solutions and temperature were obtained in a tankhouse during
two production cycles of total twenty-five continuous days.
Compared to conventional intercell bar, the benefits include: more stable cell voltage and cell
current as well as an even distribution of operating current between anode and cathode. It is also
observed that the temperature variations in the inter-cell bus bar with four contact points are less
than that in the conventional intercell bar. These observations have resulted improvements in the
testing cells and demonstrated clearly the potential of the intercell bus bar with four contact points
for copper production with electrowinning process.
1
INTRODUCTION
After entering 20th century, the growing demands and dilution on copper resource are increasing in
the same time. To recover copper from low grade ore and tailings economically and effectively,
hydrometallurgy process has become the main process in more and more copper mines.
The modern hydrometallurgy process generally includes Leaching - Solvent Extraction –
Electrowinning processes. When increasing efficiency of hydroprocess becomes a subject, leaching
and SX is related to the detail ore conditions of mines, (Fan, X. Peng, J. Huang, M. Zang, S. Zhang, L.
2005) while electrowinning process is similar in different refineries, which the efficiency is affected
by equipment’s function closely. As the main equipment in tankhouses, the anodes, cathodes and
intercell bus bars in tankhouses are studied and improved by many companies and researchers.
(Zhang, C. Wu, J.Y. 2015) (Zhang, C. Wu, J.Y. 2016) (Dufresne, R. 2016)
The copper quality and productivity in electrowinning plant are decided by many factors, such as
stability of cell voltage, composition and concentration of electrolyte solution, current distribution,
and operation management in tankhouse. The study in this article is about measurements in
intercell bus bar with four contact points, which is a capping board designed by Sanmen Sanyou
Technology Inc, also widely used in copper refineries in China and Africa, to improve their
efficiency in electrowinning plants. In this study, the data including cell voltage, cell current,
voltages between anode and cathode at different locations, changes in electrolytic solutions and
temperature were obtained in a tank house in Dexing Copper Refinery in China.
In tankhouse with the conventional intercell bars, the cells are connected in series by intercell bars.
Each anode or each cathode has only one end to be contacted to intercell bar, and the other end is
contacted to insulator. The four contact points bus bar as the capping board between tank cells, is
named because all four contact points of one pair of anode and cathode are connected to the bus bar.
It means both two ends of each anode (or cathode) will be linked together achieving homopolarity.
Each piece of anode (or cathode) with two contact points is apparently more conductive than
conventional one contact point design. Another theoretical advantage is all anode (or cathode) of
one cell can be connected together, through their hanger bar and four contact points bus bars, as a
parallel circuit, to decrease the electric resistance of all contact points.
The diagrammatic sketch about the basic
structure of intercell bus bar with four
contact points is as below:
2
(a) A cell using intercell bus bar with four contact points
(b) Diagram of four contact points (c) The structure of intercell bus bar with four contact points
Figure 1 Sketch about structure of intercell bus bar with four contact points
The users in China who have installed intercell bus bars with four contact points reported the
advantages of solving broken circuit problems and increasing current efficiency. The propose of
the measurement in this article is mainly to study the detail effect on actual operations by intercell
bus bars with four contact points in electrowinning plant.
METHODOLOGY
Layout of test cell

The intercell bus bars with four contact points were installed in Dexing Copper Refinery as Fig.2
below. There are two rows of tanks, twelve tanks per row, as Fig.2(a). Two neighbouring tanks
were selected to install three intercell bus bars around as test tanks, which named A and B; the
other two tanks with conventional intercell bars were monitored as contrast tanks, which named C
and D. There are 30 pieces of anodes and 29 pieces of cathodes per tank, as Fig.2(b). The
installation is as Fig.3.
Fig.2(a) Layout of tankhouse, totally

24 tanks; A & B used 3 intercell bus
bar with 4 contact points, C & D used
conventional intercell bars.
Fig.2(a) Single cell sketch
Figure 2 Layout of tankhouse
3
(a) Installation of insulated bottom layer (b) Finished capping board
(c) Contact points connected to anode and cathode (d) Tank cell installed with intercell bus bar
Figure 3 Installation of intercell bus bars
Measurement method
The installation of intercell bus bars with four contact points was finished in the beginning of July,
the practical measurements started from July 28th to August 25 th. August 5th – 8th was harvest
operation with open circuit. Besides the continuous improvement on measuring devices and
method, the data below from measurements was recorded:
 Input voltage in tankhouse;
 Input current in tankhouse;
 Temperature changes in the selected tanks;
 Cathode copper output;
 Concentration of solution;
 The measuring points are set at several positions in every pair of anode and cathode in
selected tanks, as Fig.4 and Fig.5 (a). 1# is electric voltage drop from one end of anode
hanger bar to the other end of cathode hanger bar; 2# is electric voltage drop between the
same ends of anode and cathode; 3# is electric voltage drop in opposite direction;
 Electric current value measured at each end of every anode and cathode, as Fig.5 (b);
4
Figure 4 Sketch of measurements in intercell bus bar
(a) How operators measured electric voltages (b) Electric current measurements
Figure 5 Measurements in intercell bus bar
Input electric current and voltage

The input electric current and voltage of whole tankhouse were recorded during measurements, by
frequency of twice per day. Fig.6 shows the values, which the current before August 9th is between
6,000A and 6,100A, while voltage is steadily at 16 V. Then in the complete harvest period, the
electric current keeps at 7,000A – 7,100A level, and voltage decrease to 15V. Input electric voltage
and current was relatively stable in the same harvest period.
5
Figure 6 The input electric current and voltage of whole tankhouse during measurement time
Cell Temperature
The temperature changes were monitored in tank A, B, C, and D, by measuring 3 set points at
solution entrance, middle part, and exit of each tank. The results showed all measured temperature
changes of set points are basically stable. All temperature value is lower than 400C, which matches
the electrowinning process happened at room temperature. Table 1 below provide the average
values of the measured temperatures, A, C, and D have similar temperature level, except B is a little
lower. As Fig.2 (a) showed above, tank A is neighbouring to tank B, so there should not be big
difference between A and B. It is considered that the existing apparent difference in Table 1 could
be caused by the practical operation conditions.
Table 1 Average values of electrolytic solution in selected tanks (0C)
Set point A B C D
Entrance 37.28 36.3 37.27 37.41
Middle 37.25 36.39 37.49 37.58
Exit 37.13 36.43 37.78 37.76
Fig.7 below provides the curves which stands for the difference changes of entrance temperature
minus exit temperature of tank A, C, D. In case of Tank C and D, the difference values are mostly
negative numbers, which means the exit temperature is higher than entrance temperature. Tank C
6
and D had a trend that the temperature is increasing along the solution flow direction in the cell.
The different values of tank A were mostly positive number or close to zero, which means the
temperatures at two ends of tank cell didn’t change much.
Figure 7 Difference of entrance temperature minus exit temperature of tank A, C, D
Due to the limited measurement condition, the trend in Fig.7 is not very distinct, but the
temperature difference in the same tank cell is remarkable. The temperature in tank A didn’t
increase along the solution flow direction. It is considered the intercell bus bars with four contact
points even the current distribution in tank cell, that lead the whole connection system to be not
sensitive against the factors which cause tank C and D to have a temperature increasing trend.
Cell voltage between anode and cathode
(a) Cell voltages between intercell bars besides tank B & D (b)1# voltage measured from tank B & D
7
(c) 2# voltage measured from tank B & D (b) 3# voltage measured from tank B & D
Figure 8 Comparison of average values of measured cell voltage from tank B and D
As described in methodology above, cell voltage value between neighbouring intercell bars, 1#, 2#,
3# voltage value of each pair of anode and cathode, and cell current are measured. The results of
tank B and D was listed as Fig.8, to be analysed and discussed. The same scales are used at Y-axis
in Fig.8 (a)(b)(c)(d), in order to compare the different voltage values.
Regarding Fig.8, the average values of measured voltage from tank B and D showed quite similar
change trend during the measurements, especially in the complete harvest period after August 9th.
Not only the average values of cell voltage and 1#, 2#, 3# voltage from tank B and D are at similar
level, but also the change trend in every day during the measurements in tank B and D had
remarkable consistency. Although the electrowinning process in tank B and D has no direct
relationship due to the apparent distance between them as the plant layout in Fig.2(a).
Variance of measured voltage values from different tanks

The average values of measured voltages per day from tank B and D are similar, but the average
values are calculated from the measured voltages at 29 pairs of anode and cathode in one tank cell,
which means the average values cannot reflect variance among each single value.
The detail working condition around 29 pairs of anode and cathode could be different inside tank
cell, which is uneven due to many reasons such as equipment performance, measurer deviation,
and so on. The average value comparison can only stand for a part of true performance of tank
cells, therefore it is necessary to calculate and analyse the variance of the measured voltage of tank
B and D by days. The variances, as Fig.9, show how big difference is among the measured voltage
values in one day, as well as the curves show how the uneven level changes every day.
In Fig.9(a), tank B and D have close variances of cell voltage values in whole measurements period.
Generally absolute value of the variances of cell voltage of two tanks are relatively low, and in 2 nd
half of the complete harvest period, two tanks have quite the same curve of variance changes.
The variances of 1#, 2#, 3# voltage values show very different results in Fig.9(b)(c)(d) to Fig.9(a).
Firstly from Aug.9th to 14th, which was the beginning of complete harvest period, the variances of
voltage values in tank D have noticeable fluctuation, and then tend to stabilized in the left days.
Meanwhile the variances in tank B keep almost the same level in the whole measurements period;
Secondly the variances of 1#, 2#, 3# voltage values in tank D are basically lower than in tank B in the
complete harvest period.
8
The higher absolute value of variance is caused by the more complicated difference among the
voltage values measured from 29 pairs of anode and cathode. The difference degree means the
local operating condition is various because of local electrolytic solution flow, resistance changes of
solution, electric current distribution, contact points condition, etc. This kind of variance is
logistical in the practical daily operations in tankhouses, which the heterogeneity in one tank cell
certainly affect the electrowinning process and cathode copper quality. Per Fig.9, the high stability
of variances of all measured voltage values in tank B, compared to in tank D with the same working
condition, shows the tank cell with intercell bus bars with four contact points could have higher
ability to eliminate or resist changes in external conditions.
(a) variance of cell voltage values of tank B & D (b) variance of 1# voltage values of tank B & D
(c) variance of 2# voltage values of tank B & D (b) variance of 3# voltage values of tank B & D
Figure 9 Variances of measured cell voltage from tank B and D
Electric current
Due to the limitation of measuring device and difficulties happened in the field, the electric current
was measured only in the complete harvest period. The absolute values of current collected from
tank B and D show no obvious rules or trends. The measured max. value and min. value are
sprinkled very unevenly. The reason behind is related to the connection system provided by
intercell bus bars installed to tank B, which certainly adjusts the current distribution in the tank cell
B, causing current to concentrate on anode and cathode with less resistance.
To check the effect of whole connection system against external condition changes, the variance of
electric current was studied. The variances of tank B and D shows a similar trend, as Fig.10. The
variances of current have increasing trend along the time going, which happens in both tank B and
9
D. In the last days of the measurements period, the change amplitude of variances of current
values from tank B gradually decreases and tends to be stable, meanwhile the change amplitude of
variances from tank D has an increasing tendency.
A noticeable fact is, all the measured electric current value is influenced by the sensitivity of
measuring device, and the measuring condition of touch point on hanger bar of anode or cathode.
In the last days of harvest period in tank cell, the copper sulphate precipitation became more and
more serious around contact points, which is assumed to influence the result of current value much.
Therefore, the result of current and its variance in this study is constrained by objective conditions.
Figure 10 Variances of measured current value in anode hanger bars from tank B and D
CONCLUSION
The electrowinning process is a complicated process continuously contributed by many
equipment’s performance and multiple working condition influence. Intercell bus bars with four
contact points is only a part of function in the whole connection system, which is difficult to cut its
effect discussion apart from other factors. The principle of this study is trying to collect as more
data as possible, to check how the whole connection system can be improved by adding this kind of
capping board.
The measurements lasted 25 days, which a complete harvest period was from August 9th to 25th.
About 900-1000 values was measured every day, so the total data number reaches 25,000 level, and
even increases over 40,000 after rough calculation and analysis. The tendency about how the whole
connection system of tank cell faces external factors change have been shown as the data analysis
and discussion above. During the measurements period, also the copper harvest period, the
temperature changes, the variances of measured voltage values change, and the variances of
current values change, the data pool shows the tank cell with intercell bus bar with four contact
points, have higher ability to eliminate or resist changes in external condition along the time going.
10
Due to the limitation of manual work, the collected data may be not more enough, however, the
result proves the direction of data analysis in this study. The next step of research work could be
automatization of measuring devices in the tank cell for copper electrowinning.
ACKNOWLEDGEMENTS
Dexing Copper Refinery.
Dexing Copper Refinery is built in Dexing Copper Mine in Jiangxi province China, which was
founded in 1960s. There was a period Dexing Copper Mine had the biggest output in Asia, also the
2nd biggest output worldwide following Escondida in Chile. The hydrometallury process in
Dexing was installed after 1997. Dexing Copper Refinery has been an aged electrowinning plant
already, which mainly refines tailings now. This study acknowledges their willings on analyzing
and improving working performance.
REFERENCES
Fan, X. Peng, J. Huang, M. Zang, S. Zhang, L. (2005) “Study on innovative process of leaching of
chalcopyrite,” Journal Mining and Metallurgical Engineering, 25 (3), pp. 58 - 62.
Zhang, C. Wu, J.Y. (2015) Application of Permanent Stainless Steel Cathode Plate in Copper
Refining, Energy Saving of Nonferrous Metallurgy, ISSN 1008-5122, pp. 8 – 11.
Zhang, C. Wu, J.Y. (2015) Selection of Stainless Steel for Cathode Plate in Hydrometallurgical
Process, World Journal of Engineering and Technology, pp. 348 – 353.
Zhang, C. Wu, J.Y. (2016) EXPERIENCES OF USING PERMANENT STAINLESS STEEL CATHODE
PLATES IN CHINA, Hydroprocess 2016, Santiago, pp. 178 – 188.
Dufresne, R. (2016) Energy Saving and Increase in Efficiencies for Bus Bar Insulators, Hydroprocess
2016, Santiago, pp. 189 – 198.
11
Development of a Low Resistance, Low Corrosion
Cathode Plate for Electrowinning and Electrorefining
Nigel Aslin, Christian Pasten, Addin Pranowo and Graham Heferen
Glencore Technology, Australia
ABSTRACT
For nearly 40 years Glencore Technology (formerly Mount Isa Mines Copper Refineries) has been the
mainstay supplier of permanent cathode plates to the copper industry with its ISA PROCESS and
KIDD PROCESS cathode plates. Improvement to the cathode plate design remains a key area for
research, and on-going developments by Glencore Technology have led to the commercialisation of
a new design. The ISAKIDD cathode plate is universally suited to both electro-refining and electro-
winning bringing major cost efficiencies to the operations through improvements in hanger bar
strength, corrosion resistance and electrical conductivity. A variation of the this design uses a ‘steer-
horn’ shaped hanger bar to lower the resistance path across the cathode plate giving significant tank-
house power savings in electrowinning refineries. Technical aspects and results of commercial trials
of the ISAKIDD and ‘HP’ cathode plate are discussed in this paper. A novel new contact system
which allows shorting frames to be used with Stainless Steel hanger bars will also be tested. Trial
results will demonstrate savings in a typical EW tankhouse of up to 720k USD per year in power costs
alone, with further savings in maintenance costs and operational efficiencies.
1
INTRODUCTION
Glencore Technology were the pioneers of Permanent cathode technology for copper and remain
committed to continuous improvement and innovation of the technology forty years later. The latest
design hanger bar represents the most significant advance in cathode technology offered by Glencore
Technology since the introduction of the Duplex cathode blades ten years ago.
The ISAKIDD hanger bar was jointly developed by Glencore Technology and their manufacturing
partners Bendtech. It provides a range of operational advantages over current designs, including
electrical efficiency, mechanical strength, corrosion resistance, cost of supply and life-cycle cost of
maintenance.
The hanger bar consists of a Stainless Steel tubular bar with high conductivity copper core
encapsulated inside the bar. The copper core is exposed at each end of the bar to form contacts and a
patented weld is used to form a non-corroding and air-tight seal between the copper contacts and
Stainless Steel bar (Figure 1 below).
Figure 1 ISAKIDD hanger bar construction details
A mechanical bond between the copper core and Stainless Steel tube provides an efficient and robust
electrical connection from blade to hanger bar. All exposed surfaces of the bar are resilient to
corrosion from the tankhouse environment including acid mist, chlorides and electrolyte salts. The
copper / stainless steel electrical joint is fully enclosed inside the bar and protected from corrosion.
The Stainless Steel tubular bar provides mechanical strength superior to that of a solid copper bar
and will not bend or sag when exposed to high temperature shorting. A homogeneous weld between
the Stainless Steel blade and Stainless Steel hanger bar avoids the galvanic corrosion issues that are
common with many conventional alternative designs2.
The ISAKIDD hanger bar is equally suited to both Electro-refining and Electro-winning, however the
greatest benefits will be seen in EW plants with aggressive corrosion conditions, such as cells with
ventilation hoods.
The hanger bar can be manufactured as either a conventional straight bar, or a novel new ‘Steerhorn’
design with significantly lower power consumption. The fundamental principal of the Steerhorn
2
design is to reduce the high resistance pathway from electrolyte to the hanger bar. Resistivity of
Stainless Steel is approximately forty times higher than copper so minimising the ‘freeboard’ distance
from electrolyte to hanger bar has a major benefit in reducing voltage drop across the cathode and
ultimately reducing tankhouse power costs3,4.
This paper presents the results of a commercial trial carried out with the Steerhorn version of the
ISAKIDD hanger bar.
A second hanger bar type included in the trials is a traditional KIDD HP cathode hanger bar modified
to a Steerhorn configuration for still-lower power consumption. This design consists of a solid copper
bar welded to Stainless Steel blade, with a wrap-around Stainless Steel sheath protecting the weld
from corrosion. The void between the sheath and copper bar is sealed internally with a resin which
also prevents ingress of electrolyte and acid mist to the interior of the bar.
Figure 2 ISAKIDD Steerhorn Cathodes in service
METHODOLOGY
Trials were carried out during normal operations at an EW plant in Chile, using two commercial cells.
One cell was installed with KIDD HP Steerhorn cathodes and the other with ISAKIDD Steerhorn
cathodes. Plate performance was monitored over one cathode cycle (6 days) with particular focus on
current distribution, power consumption, ease of handling in the overhead crane and Cathode
Stripping Machine. A shorting frame test was also carried out to assess the functionality of the plates
under full current load during a simulated maintenance activity.
Test Conditions;
Current density 360 A/m2

Electrodes per cell 61 cathodes / 62 anodes
Anode type conventional lead/calcium/tin alloy
Cathode pitch 100mm
Test duration 6 days (one cathode cycle)
Cathode deposit weight (avg) 110 kg per cathode (55kg per side)
Cathode deposit type enveloped (KIDD Process)
Ventilation type fan-forced cross ventilation (no hoods)
3
Measurements / observations during the test;
 Internal plate resistance; calculated from measured plate voltage and measured plate
currents. Plate voltage was measured from solution line to copper contact using a DC volt-
meter and plate current was measured using a DC clampmeter placed around hanger bars.
 Current distribution – measured individual plate currents during normal operation and
shorting frame operation
 Compatibility with cranes and CSM – observation during washing and stripping operations
 Compatibility with shorting frames (old and new type) – checking current distribution and
plate / contact temperatures during operation of the shorting frame.
 Two cells adjacent to test cells were used as a reference to assess comparative performance.
RESULTS / DISCUSSION
Internal Plate Resistance / Power Consumption

In a typical EW cell, internal plate resistance accounts for 2-3% of overall cell voltage1. The majority
of cathode plate resistance occurs within the stainless steel ‘free-board’ zone between electrolyte
solution line and hanger bar. A much smaller resistance exists in the hanger bar itself.
Steerhorn shaped hanger bar results in much shorter current path across the stainless steel blade,
therefore reducing voltage drop and DC power consumption. The bar is cranked downwards in the
centre to minimise the high resistance path from electrolyte to hanger bar.
Also important is the ability of the cathode plate to maintain low resistance over the full duration of
its life. Conventional design cathodes use a copper weld between the solid copper hanger bar and
Stainless Steel blade, which is highly vulnerable to galvanic corrosion and deterioration over time.
This leads to increasing plate voltage and higher power consumption over time and on-going cycle
of weld repairs every 5-8 years2. Inconsistent corrosion from plate to plate can also impact current
distribution within a cell particularly when new plates are intermixed with older plates. ISAKIDD
hanger bars have no corrodible parts exposed to the outside environment and are designed to achieve
stable performance over the full life of the plate.
In the demonstration trials, Ohmic resistance of the plates was determined by calculation R = V / I
(Ohm’s Law) where V = measured voltage drop from electrolyte to copper contact and I = individual
plate current measured with a clamp meter.
Results of the test are shown in Figure 3 below. KIDD HP plates demonstrate a large reduction in
plate voltage, averaging 30µΩ per plate, approximately 60% lower than the Reference plates.
ISAKIDD Steerhorn plates averaged 67µΩ, or 12% less than the Reference plates.
Figure 3 Internal Plate Resistance Comparison, Trial plates versus Reference plates
4
Power Savings
In the following hypothetical example the power savings of the HP Steerhorn plate (HPSH) is
calculated, based on the plate resistance measured during the trial. The following typical EW
parameters are used to demonstrate the expected savings in operating cost;
Table 1 Typical parameters and power savings, 150 ktpa EW tankhouse using HPSH cathodes
plant capacity (tpy) 150,000

current density (A/m2) 350
current efficiency (%) 92
plate area (m /plate)
2 2
no. plates 20,328
plates/cell 66
no. cells 308
average cell voltage (mV/cell) 2,100
rectifier current (kA) 51
power consumption (MWhr/yr) 78,154
power consumption (kWhr/TCu) 1,862
power cost (USD/kWhr) 0.15
Reduction in plate resistance, HP Steerhorn vs Conventional = 46 µΩ

Equivalent voltage saving Vplate = Iplate x Rplate
= 51,000/66 x 46 x 10-6
= 35.4 mV (per cell)
For typical cell voltage 2,100mV this represents 1.7% reduction in total tankhouse power
consumption, an annual saving of 728,000 US$ per year, for the example given above (equivalent to
36 US$/plate/yr).
Table 2 Power Consumption data, Steerhorn plates versus Conventional
Current Distribution
5
Current distribution was measured for the trial plates and two reference cells containing standard
cathode plates. Current densities were measured for each cathode and plotted as a histogram (Figure
4 below).
20 Control Cells data set combined

18 trial plates data set combined
16 BENCHMARK = normal dstn 8% relative std dev
14
% frequency
12
10
8
6
4
2
0
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
520
-2
CD (A/m2)
Figure 4 Current Distribution Trial versus Control plates
The trial plates had significantly less variation than the Reference cells as shown in the table above.
Relative Standard Deviation (RSD)* of plate current density was 11% for the trial plates combined,
and 19% for the Reference Plates. Ideally the data should follow a Normal Distribution with RSD less
than 10%, in a ‘best practice’ operation (shown in Figure 4 for comparison). Major factors affecting
current distribution are, in order of importance;
 inter-electrode spacing (alignment of anode to cathode)
 cathode plate internal resistance, and
 contact resistance (between hanger bar and intermediate busbar)
* standard deviation divided by average current density
Handling Equipment compatibility

The Steerhorn plates were designed to be easily integrated into the existing tankhouse and
completely interchangeable with the existing cathode plates, in terms of handling in the Cathode
Stripping Machine and Overhead Cranes.
Manual overhead cranes were employed at the test site to transport the plates to and from the
Cathode Stripping Machine. Handling of the SH plates was via Stainless Steel hooks welded to the
top of the hanger bars, in the same fashion as the windows used in the existing plates. No handling
issues were observed with the cranes throughout the trials.
Test site uses a KIDD ‘Carousel’ type Cathode Stripping Machine with the following steps carried
out in sequence; flexing, hammering (if required), stripping and removal of copper deposit. The
plates are handled via the lugs in the CSM feed conveyor system and transfer to the carousel. The
standard chisel system used by these machines is compatible with the Steerhorn design plates
without modification. The chisels were found to work efficiently with only 30mm freeboard (distance
from electrolyte level to hanger bar) on the Steerhorn plate (reduced from 180mm standard plate). A
6
small modification was made to one of the sensors on the feed-in conveyor to accommodate the
different hanger bar shape, otherwise no issues were observed with the operation of the CSM during
the trial.
Shorting Frame Compatibility

A shortcoming of hanger bar designs using full stainless steel encapsulation is they are incompatible
with shorting frames which are commonly used to bridge out cells during maintenance and cleaning
operations. The ISAKIDD hanger bar incorporates two secondary copper contacts on the topside of
the bar which allow the use of a standard shorting frame (Figure 5 below). Shorting frame operation
was tested during the trials with two different shorting frame designs.
The first frame tested was an older style frame with rigid bridging bar. Thin sheets of copper cathode
were laid between the bridging bar and copper hanger bars to help distribute current across all the
hanger bars, per normal operating practice. A repeat test was carried out using a more contemporary
design shorting frame with spring contacts that apply even pressure to all hanger bars and
compensate for small variations in hanger bar height across the cell (Figure 6 below).
Figure 5 ISAKIDD Steerhorn Cathode Figure 6 Spring-contact shorting frame in

with top-mounted shorting frame contacts operation with IK cathode bars employing
secondary contact
During the test, rectifier current was ramped from zero to full operating current (45kA) at the rate of
5kA per minute, while monitoring the current distribution and temperature of the plates using an
infrared thermal camera (Figure 8 below). Steady state temperature distribution of the cathode plates
was stable and well within the safe working temperature of the plates. Figure 7 below shows the
steady-state current distribution at maximum current 45kA with normal distribution (one plate not
making contact).
7
8
7
6
no. cathode plates

5
4
3
2
1
0
720
460
480
500
520
540
560
580
600
620
640
660
680
700
740
760
780
800
820
More
Plate Current, Amps
Figure 7 Current Distribution during Shorting Frame Operation
Figure 8 Infrared testing of contact temperatures during shorting frame operation
CONCLUSIONS
 Trials were successfully completed with two new hanger bar designs using a novel
‘Steerhorn’ shaped hanger bar.
 Major reduction in DC power consumption was demonstrated with KIDD HP Steerhorn
cathode - up to 720k USD per year based on a typical tankhouse scenario.
 New design ISAKIDD cathodes offer superior mechanical strength and anti-corrosion
properties to existing designs, significantly reducing repair costs over the life-cycle of the plate.
 Secondary contacts on the ISAKIDD cathodes allow use of shorting frames despite utilising
a full stainless steel exterior for corrosion protection.
 Steerhorn plates were shown to be fully compatible with the cells, cranes, CSM and shorting
frames, and interchangeable existing conventional cathode plates in existing operations.
8
REFERENCES
1. N.J Aslin, D.Stone, W.Webb, ‘Current distribution in modern copper refining’, Aug 2005,
conference paper
2. J.Weston, W.Webb, ‘The link between operational practice and maximising the life of stainless
steel electrodes in electrowinning and electrorefining’
3. K.L Eastwood, G.W Whebell, ‘Developments in permanent stainless steel cathodes within the
copper industry’
4. J.Weston, W.Webb, ‘The development of a “lower resistance” permanent cathode’
9
New Electrolytic Process for Copper Electrowinning
and Simultaneous Generation of Ferric Ion for
Sulfide Leaching
Jaime Simpson and Víctor Araya
Protech, Chile
ABSTRACT
We modified an electrolytic cell using an ion exchange membrane to separate the anodic and
cathodic solutions and studied alternatives to produce high-purity copper cathodes by
electrowinning the catholyte, while simultaneously producing ferric ions by electro-oxidizing
ferrous ions in the anolyte. The ferric-rich solution produced in the cell can be used to improve
copper recovery in the leaching of secondary sulphide ores.
Research was carried out at the laboratory level using synthetic and real solutions obtained from
different hydrometallurgical processes in a sulfuric environment. The experimental setup consisted
of a two compartment cell, operating continuously in closed circuit, with temperature control (40 to
60 °C) and different current densities (200 A/m2 to 500 A/m2) using DSA anodes (4 cm x 8 cm) and
graphite anodes (4 cm x 8 cm). The cathode was a 316 L stainless steel plate of 32 cm 2. Acid mist
was measured around the laboratory unit. System responses were cell tension, mass of deposited
copper, Fe (II) to Fe (III) conversion, Faradic current efficiency and total energy consumption.
Results show that the process can be carried out with energy consumptions between 960 and 1400
kWh/ton of copper, with current efficiency higher than 94%, copper voltages fluctuating between
0.88 to 1.4 V, and ferric ion conversion stoichiometrically equivalent with deposited copper. A pilot
plant with anodes and cathodes of industrial size has been built and is currently under testing.
1
Elimination of Air Pollution by Acid Mist in Copper
Electrowinning Plants from Copper Oxide Ores©
Víctor Vidaurre
TECMINOMET, Chile
ABSTRACT
This paper describes a method and system for sustained control of acid mist pollution generated
during the electrowinning of copper and other non-ferrous metal. The system positively prevents the
release of gaseous fluid pollutants and/or contaminated process air to the working ambient above
the electrolytic cells, utilizing a “cell by cell” approach providing substantial total abatement of acid
mist, in an effective, efficient and sustainable manner.
As the acid mist is generated, it is continuously captured and confined in each cell just above the
electrolyte with removable anode covers, equipped with double seals forming transversal mini
chambers that enhance coalescence of electrolyte airborne droplets in the mist, growing them in
weight and thereby falling into the electrolyte.
Suction is provided by an extraction turbine system and the extracted (contaminated) gaseous fluid
flow is fed into individual depurators installed on each cell, where it passes through bubblers into
liquid columns capturing 99.9% of liquids. The liquid condensates are recycled back to the cell
while the individual depurated gaseous fluid flows are collected by a manifold and: either
exhausted into outside atmosphere, or to a secondary multistage depurator/condenser with a chiller
to reclaim 99.9 % of the water and sulfuric acid vapors, before discharging to the atmosphere with
innocuous levels of H2SO4.
The continuous operation of this holistic system is governed by a programmable logic controller,
with self-regulation sustained by instantaneous monitoring of process variables.
The “cell by cell” acid mist control system guarantees continuous compliance of zero escape of acid
mist to the working atmosphere, simultaneously with minimum power usage at levels of 100
watts/cell, and innocuous gaseous fluid discharges to atmosphere at levels of orders of magnitude
below present standards.
1
RENACAR SYSTEM FOR PRECLUDING ACID MIST AIR POLLUTION IN COPPER
ELECTRODEPOSITION PLANTS
This document describes a method and a system of concatenated devices for sustainable automatic
and autonomous control of air pollution by acid mist generated in the electrowinning process of
copper and other nonferrous metals, with zero emissions of acid mist to the working environment
over the cells, while recycling 99.9% of the liquid condensates back to the EW process, and
simultaneously, with minimum energy consumption and innocuous levels of contaminants in the
treated gaseous fluid effluent discharged to open atmosphere.
This work crowns 20 years of multidisciplinary developmental effort to update metal electrowinning
electrodeposition technology elementals from Faraday Theory days to the standards of efficiency,
productivity and sustainability required of all industrial processes in the XXI Century; at the same
time, the innovation introduces a PAC control with wireless, instantaneous monitoring of variables
for autonomous operation -including other productivity and quality enhancer systems- that jointly
solve the most challenging remaining problems: effectively protecting people's health and
safeguarding equipment and facilities simultaneously with increased productivity and quality.
RENACAR is an innovative acid mist capture, confinement, recycling and abatement process,
designed to be readily installed in any existing polymer concrete electrolytic cell to provide an
effective, efficient and a finally sustainable solution based on a "cell by cell" strategy to solve the EW
process acid mist environmental problem not yet resolved. RENACAR dramatically downsizes the
scale of the acid mist generation in each cell, and then eliminates by coalescence the electrolyte
aerosols as they are generated, which involves immediate recycling into the electrolyte, taking
advantage of phenomenological occurrences of physical principles that were key in the design of
removable anode covers (RAC), to seal off the electrolyte from working atmosphere.
We shall begin by characterizing the problematic “acid mist” as a two-phase gaseous fluid compound
made up of:
 a continuous gaseous phase consisting of vapors of water and sulfuric acid evaporated
from the electrolyte, at its process operating temperature, composed by:
- oxygen gas, generated at the energized anodes, and released to the electrolyte from the
anodic surfaces in the form of very small bubbles, growing in size and speed as they
ascend to the electrolyte surface (volume of O2 generated is proportional to the direct
current density operated in the cell).
- ambient carrier air, suctioned directly through the removable anode covers (RAC) into
the cell coalescer mini chambers that confine the acid mist in the space below the anode
covers and above the electrolyte in the cell, to enable controlled movement and
extraction of the confined acid mist mass from the cell.
- ambient air for diffusion, suctioned likewise from the plant atmosphere, for soft
agitation of the electrolyte, by homogeneous injection in the form of small bubbles,
directly into each interelectrode space from diffusers installed parallel to the cathodes
just below them, from a horizontal plane above the cell bottom.
- other gases that may be carried diluted in the electrolyte from the prior processes of
copper ores to prepare the copper bearing electrolyte, or by reactions in the electrolyte.
2
 a liquid dispersed phase carried in the continuous gaseous phase, as minute aerosols or
tiny airborne particles or droplets of electrolyte and sulfuric acid, originated by the
explosion - and subsequent collapse - of the interphase liquid film of electrolyte, acid and
water surrounding the gas bubbles upon emerging from the electrolyte surface.
In Chile, the applicable regulation protocols are contained in Ministry of Health Decree MINSAL DS
594 / 2000 that dictates the basic environmental health sanitary conditions in work places, and
establishes permissible LPE´s for various physical and chemical contaminants and other occupational
risks. MINSAL 594 / 2000 mandates that in workplaces located at an altitude higher than 1.000 m
above sea level (m.a.s.l.), the standard LPE of 0.8 mg/m³ limit for a normal day of 8 hours, with total
of 48 hours per week, must be duly adjusted by an altitude correction factor (Article N° 55). For
example, for a plant altitude of 2,500 (m.a.s.l.), with a barometric pressure of 560,3 mm of mercury,
𝑃
Fa =760 (1)
P is the local atmospheric pressure expressed in mm of mercury and 760 is the atmospheric pressure
at sea level.
560,3
Fa = 760 = 0,7372 (2)
LPE= 0,8 * 0,7372 (3)
LPE = 0,590 mg/m³ at 2,500 m.a.s.l. (4)
The design of the RENACAR "cell by cell" system enables a dramatic downsize of the acid mist
problem and is based on full compliance of universally accepted "environmental paradigms" used in
all effective and successful technologies for environmental control and effluent treatment:
 ”Eliminate the sources of contaminant effluents in processes; if this is not possible, decrease the
effluents to a minimum”. In present EW processes using insoluble lead anodes, acid mist
cannot be eliminated. RENACAR provides RAC covers to decrease the amount of effluents
by diminishing the physical volume for restraint/confinement of gaseous fluids in the cell,
generated for any given current density, thus reducing evaporation of liquids.
 "Minimize pollution in effluent flows”. The RAC cover system captures and confines the acid
mist effluent at the emission sources inside each electrolytic cell. Contaminants liquid
aerosols are simultaneously abated as generated, by induced coalescence of the acid mist.
In present art, the mitigation of the harmful effects of the acid mist, considers a dilution strategy with
different barriers that do not assure the full compliance of the legal requirements established by the
Authority of Health and Environment:
 mitigation of acid mist emission, such as plastic spheres.
 inhibition of acid mist formation, such as depressants or suppressants products.
 forced atmospheric air ventilation to dilute/remove the acid mist from the plant
environment inside buildings, with the attendant decrease of ambient temperature in
the EW Plant.
 hood covers placed on each cell to extract -and transport through a ductwork maze-
towards a centralized gaseous fluid effluent treatment system with chimneys in the
exterior of the building. The operational efficiency these systems is difficult to determine
due to the altitude of evacuation (m.a.s.l) of the effluent gases to the atmosphere.
3
 acid mist individual cell capture and extraction in situ to a centralized gaseous fluid
effluent treatment system, which appears to be “best available technology” to date with
capture and extraction of acid mist over the electrolyte by means individual seals attached
to the anodes discharging the slightly diluted acid mist into vacuum channel fiberglass
ducts attached to each cell lateral walls, extraction by suction applied to lateral channels
that remove the acid mist in several points along the lengths of the cells, discharging to the
conventional duct network for transportation of the acid mist to a remote treatment facility
outside the EW plant.
It should be noted that none of the current state of the art acid mist control solutions mentioned
above complies fully with the established LPE in 100% of the monitoring points established DS
594/2000, and therefore, 100% LPE compliance at best is only partial while the metal electrodeposition
process is conducted.
By contrast with the present art, the new RENACAR “cell by cell” system eliminates dilution the acid
mist at each cell volumes of clean air, but quite to the contrary, by dramatically reducing instead the
volume of contaminated effluent generated to a level such that allows optimized operation of the EW
process introducing soft aeration systems to agitate the electrolyte and thereby making it
substantially abated right within the cell that originates it. Consequently RENACAR provides also
minimum energy usage!
This radical departure of RENACAR downsizing strategy from current art and established wisdom,
is accomplished by observing -and taking full advantage- of a quadruple phenomenological
occurrence in each energized cell: (1) a thermal gradient existing between the electrolyte
temperatures relative to the typical ambient air temperatures above the cells, the providential
assistance provided gratis by the natural forces, (2) gravity and (3) atmospheric pressure, and (4)
the continuous application of forced extraction to the confined acid mist from each cell. All four
simultaneously interact within the mini chambers (formed by the removable anode covers -RAC’s-
with double longitudinal flexible seals to separate the electrolyte from the work atmosphere, in each
interelectrode space), to induce and promote abundant coalescence of the fine aerosol droplets of
electrolyte in all the mini chambers, upon cooling and soft swirling contact with the controlled
volume of very slow incoming atmospheric carrier air required for continuous extraction.
Coalescence causes fine droplet growth to larger sizes until their own weight detaches them from the
interior horizontal surfaces of the longitudinal double seals of mini chambers, or from the electrodes
vertical surfaces, dropping downwards into the electrolyte below, in effect, self-recycling themselves!
Simultaneously, the forced extraction suction that is applied either by a single turbine system outside
of the plurality of cells -or by individual mini turbines attached to the external surface of one front
cell wall- pulls the mass of confined acid mist in the mini chambers at each interelectrode space in
each cell, and slowly (i.e., at less than 1 m/s) moves it horizontally towards the lateral cell walls,
turning 90° to swirling merge with the forward moving streams of gaseous fluid flows in the two
longitudinal lateral channels; as a lateral gaseous fluids streams move forward, the mass of the
gaseous fluid grows, until finally discharging into a relatively into the larger volume expansion
chamber provided near the exit point of the cell. The continuously incoming acid mist volume from
the two lateral channels softly compress the confined gaseous global mass in the expansion chamber
to almost a standstill, retarded by the very small rectangular exit cross sections in the extraction rig
provided for the gaseous fluid exhaust.
4
In effect, the confining spaces of the acid mist inside mini chambers in each the cell act as labyrinths
of collision surfaces interposed in the paths which the acid mist gaseous volume strikes on its travel
out of the cell; they enhance collision impact opportunities and friction for the aerosols to coalesce.
Quite surprisingly, more than 90% of the cell’s acid mist volume extracted from each cell is virtually
free of liquid aerosols.
Installed on one outer front wall of each cell, SIRENA system´s first depurator device DEVA “V3”,
receives the acid mist flow extracted from the cell, and immediately passes it through a bubbler
device which operates under a liquid column of controlled height, that effectively catches the
remaining liquid aerosols that were too small to coalesce and recycle to the electrolyte in the cell
where they originated. The first depurator device also separates the gaseous fluid from the
condensate liquid -in a preferred configuration- by interposing a gaseous fluid cooler or chiller device
to condense the vapors in the gaseous fluid, and returns it continuously to the EW process; the treated
gaseous fluid effluent substantially containing traces of water and sulfuric acid vapors is discharged
from the first depurator either to the outside atmosphere, or alternatively, to a secondary depurator
multistage condenser device that repeats the bubbling process against a liquid column of controlled
height, and is further equipped with a secondary gaseous fluid cooler or chiller device interposed
across the global effluent flow for immediate forced condensation of the vapors remaining prior to
discharge to the outside atmosphere.
The most astonishing discovery while materially implementing the strategic “cell by cell” concept of
unitized cell final solution was the unexpected minimum energy needed in the aerosol coalescence
phenomenon. The coalescence process that abates contaminant acid mist aerosols so effectively, is
ad hoc controlled by closely regulating the individual gaseous fluid extraction suction rates of
polluted gaseous fluid effluents at each cell, and further aided by the RAC cover design that supports
coalescence at the same time the acid mist is being generated, by the simple yet very effective
dimensions and tolerances of the dual longitudinal flexible seals!
RENACAR is designed to operate concatenated with a soft electrolyte agitation system(SEAS), built
specifically to provide very soft agitation flow from air diffusers installed parallel to the cathodes in
each interelectrode space (reference Patent CL 44.803/ 2009) that is also easily installed in each cell.
The joint operation of SEAS with RENACAR is strongly recommended. The continuous energy of
the air bubbles streams directed upwards by the vertical hanging electrodes to strike the bottom of
the mini chambers above is a welcome additional enhancement to coalescence.
The critical acid mist extraction rate setting at each cell necessary to generate a slight depression
under the RAC covers in each cell, is concurrently achieved by regulating for the minimum speeds
required for maintaining very slow internal displacements of the polluted gaseous effluent in each
cell. That setting also regulates the minimum admission rate of atmospheric carrier air to enter the
cell through each mini chamber to allow extraction of the entire volume of confined acid mist in each
cell as it is generated plus the required carrier air. The above is a key fact that assures the
impossibility of simultaneous escape of gaseous effluents, or confined acid mist flowing upwards
into the working atmosphere over the cell, 100% of the time while the cell is energized!
The RENACAR control system (including SEAS), is composed of two independent subsystems of
electronic control devices (with no moving parts) installed in series in each cell, and a third
mechanical central extraction system driven by a single turbine with a frequency variator for
instantaneous adjustment of turbine speed required to maintain sustained holistic equilibrium and
concatenation in real time of the relevant variables in the sub processes of the EW process, i.e.,
5
generation of acid mist gaseous fluid effluent, followed by confinement, coalescence, extraction,
condensation and depuration. This complex concatenation of sub processes is achieved by
instantaneous control of two key variables in equilibrium: (1) the sum of the individual “cell by cell”
settings of effluent extraction rates with (2) the effective actual global turbine effluent extraction rate;
all gaseous fluid flows are sensed by robust and certified ad hoc orifice plates, (chosen for their proven
stable accuracy and durable dependability notwithstanding operation in severely aggressive
environments)
The sustained holistic instant concatenation of the above subsystems is sustained by an especially
custom fitted PAC, i.e., programmable automation controller that includes proprietary software for
seamless instant monitoring and two ways wireless transmission of data from the sensors in
RENACAR. The instantaneous states of the variables allow instantly wireless corrections of any
deviations as they may appear in each cell in the RENACAR, thereby achieving sustained autonomous
operation:
 with guaranteed zero emissions of acid mist to the working ambient above the cells, 100%
of the time and in operation, including the time for harvesting the cells,
 simultaneously, assured minimum energy usage (100 to 200W per cell depending on
number of cathodes), for the total abatement and recycling of the acid mist generated by
the EW process.
 guaranteed 99,9% recycling of EW liquid condensates back to the process,
 guaranteed substantial reduction of the original pollutants in the acid mist to innocuous
levels in the gaseous fluid flow finally discharged to the open atmosphere.
The PAC equipment with proprietary software platform package for seamless instant two ways
wireless monitoring of the variables of both sub processes of the EW process completed 9.000 hours
in continuous operation installed in a prototype RENACAR with 4 cells in an EW industrial plant,
logging an astonishing 100% operational availability - 0 hours lost due to electronics!
System 1 Removable Anode Covers (RAC) and Depuration of Extracted Acid Mist from
each cell (SIRENA)
Figure 1 EW Cu cell with RAC covers of RENACAR for “0” emission of acid mist into work ambient
Figure 1 shows in perspective a state of the art polymer composite Cu EW cell (USPTO N°6,572,741
& N°6,730,195) with removable anode covers (RAC’s) installed on the flat section of the hanger bars
of its insoluble anodes. The electrolyte in the electrode free zones at the end of each cell is sealed
with ad-hoc non-removable fixed electrolyte covers N° 1 and 2. Acid mist extraction rig (AEC) is
installed on one external frontal cell wall, receives confined acid mist and discharges a gaseous fluid
6
flow to a first depurator of electrolyte aerosols (DEVA “V3”) that are dragged together with the
gaseous fluid extracted from each cell.
Figure 2 cross section EW cell with RAC/SIRENA systems including Soft Electrolyte Agitation System (SEAS)
Figure 2, displays an elevation longitudinal cross section view of an EW cell in operation with the
RAC anode covers installed on the anodes, sealing the electrolyte in the interelectrode spaces,
including the soft electrolyte agitation system (SEAS) installed under the electrodes for joint
operation with RENACAR. With the configuration of the RAC’s shown in Figure 2, the electric
contacts between each electrode and the current bar remain at all times 100% accessible and visible
(and -now with RENACAR- in an atmosphere completely free of acid mist corrosion!) during the
entire cell operation cycle. Most importantly, the cathodes with electrodeposited copper also remain
immediately accessible to the crane all times. At cell harvest, this eliminates any loss of crane time in
standby while operators remove cell cover devices of present art.
Figure 3 lateral view of single RAC- Removable Anode Cover - with double longitudinal flexible seals
Figure 3, shows a single RAC with the double longitudinal flexible seals installed at the bottom of its
lateral sides; flexible seals are designed to rest their horizontally protruding flexible lips (both), flat
on the adjacent cathodes plate surfaces when RAC’s are installed on each anode, thus forming
parallelepiped mini chambers over the electrolyte in the interelectrode spaces. RAC’s are monoblock
cast with high performance polymer composite (USPTO N°6,143,219) to fit up to twenty anodes for
harvesting sixty cathode cells in three crane trips.
7
Figure 4 perspective view of cell with electrodes and RAC’s (with double longitudinal flexible seals removed)
Figure 4, shows each interelectrode space as seen with the RAC´s installed (with the upper and lower
“roofs” removed from the mini chambers formed by the double longitudinal flexible seals). The
interelectrode spaces are seen as vertical parallel channels open to the working atmosphere. The
frontal flexible seals on both ends of the RAC’s structural bodies, to isolate and seal the electrolyte
over the lateral cell channels, extending lengthwise along the lateral walls of the cell. The animation
shows the continuous sequence of paths of the confined acid mist in the coalescer mini chambers:
first simultaneously in all the interelectrode spaces, moving transversally, and then discharging into
the longitudinal lateral channels with a 90° change in direction; then forward towards expansion
chamber of the gaseous fluid effluent prior to extraction by suction applied from outside of the central
discharge rig (AEC).
Figure 5 detail of mini chambers in adjacent anodes when cathodes are removed at harvest
Figure 5, shows the operation of the sealed coalescence mini chambers taking advantage of the
vertical thermal gradient that exists between the electrolyte and the atmosphere temperature over
the cell, as describe in the text of this paper.
8
Figure 6 photograph of coalesced acid mist aerosols into drops attached to flexible seals with cathode in place
Photo 6 shows coalesced droplets of electrolyte aerosols visible at their maximum growth size prior
to detachment from the underside of the flexible transparent longitudinal lip seal, shown resting on
the adjacent cathode plate surface.
Figure 7 photograph of coalesced acid mist aerosols into drops attached to flexible seals without cathode plate
Photo 7 shows coalesced droplets of electrolyte aerosols visible at their maximum growth size prior
to detachment from the underside of the flexible transparent longitudinal lip seal, shown with the
cathode removed and the lips of the double seals overlapped instantly sealing the mini chamber upon
removal of the cathode for harvesting.
In Figures 6 and 7, the transparency of the flexible double longitudinal seals of the RAC’s allow
observing the dispersed liquid phase droplets already coalesced as drops of visible sizes attached to
the underside faces of the longitudinal seals. The growth of the droplets continues until their size
and weight manage to surpass their adhesion with the seals and fall by gravity self-recycling to the
electrolyte that originates them in the same cell. Figure 6, shows two RAC’s with their corresponding
cathode inserted into an interelectrode space. Figure 7 shows the state of the coalescer mini chamber
volume increased by the removal of the intercalated cathode plate. At the time of harvest the cathode
plates are lifted from the cell and in their vertical travel, the electrodeposits on both sides are swept
by the corresponding flexible seals of each adjacent RAC. When the cathode with electrodeposited
copper leaves the cell, the interference is interrupted and the adjacent longitudinal seals of the RAC
extend overlapping and immediately, forming a new ceiling and increased volume to the
combination of the two mini chamber volumes. The innocuous volume of acid mist emission that
occurs at the instant when the cathode plate detaches from the lip seals -which instantly overlap
maintaining the electrolyte sealed- is perhaps detectable by some still unknown sensor device.
The dimensions and clearances of flexible seals in the RAC are designed with close tolerances to allow
entry of atmospheric acid mist carrier air volume into to the coalescer mini chambers with the
minimum suction applied from one of the front walls of the cell, in order to simultaneously remove
continuously confined acid mist effluent with a flow rate setting that is determined individually “cell
by cell”, just sufficient to maintain a slight pressure depression in the confinement volume of the cell
9
under the RAC’s, and also initiate and sustain the coalescence of the disperses liquid phase acid mist
aerosols in the coalescer mini chambers.
The gaseous fluid flow extraction rate applied to each cell, is of course, designed to be set
individually, and regardless of the other individual extraction flow settings established in each of a
plurality of cells connected to the RENACAR system. The global suction provided be the RENACAR
turbine(s) will instantly satisfy sustained operation in time of each cell with its individual setting for
effluent extraction rate to insure maintaining at least two millibars depression under the RAC, so
that the zero effluent emission objectives can be sustainably guaranteed.
System 2: acid mist depurator and recycling system (SIRENA) (USPTO N°9,498,745)
Figures 1 and 2 show first depurator devices that provide the suction needed to maintain, at all times,
a depression under two millibars (with respect to the working atmosphere) in the confinement
volume for gaseous fluids “cell by cell”.
The SIRENA´s first depurator device DEVA “V3” installed on one external front wall in each cell
receives the acid mist flow extracted from each cell, and passes it through a bubbler under a liquid
column of controlled height to catch the remaining liquid aerosols that were too small to coalesce and
recycle back to the electrolyte where they originated in the cell. The first depurator also separates the
liquid condensate - aided by a chiller device (optional)- and returns it continuously to the EW process,
from the gaseous fluid flow with vapors of water and sulfuric acid that are discharged from the first
depurator: either to the outside atmosphere, or to a subsequent secondary multistage condenser
depurator, equipped with a bubbler device under liquid column of controlled height, and also chiller
interposed across the gaseous fluid effluent flow to cool it down to a temperature where the
contaminated vapor effluents are forced to condense, and the remaining contaminant in the gaseous
fluid effluent prior to its discharge to the outside atmosphere is innocuous.
The SIRENA has a central extractor turbine to perform both the removal of the contaminated gaseous
fluid from each cell and drive it through a manifold collector pipe, either to the atmosphere outside
the plant, or to the second centralized multistage depurator condenser described above.
In SIRENA, two independent systems of devices (no mobile part) are installed connected in series at
each cell, and served by a third mechanical suction system for central global extraction with a
frequency variator instantly adjustable for holistic concatenation of the global operation is done by
means of a programmable automation controller (PAC) that includes a proprietary software platform
for instant monitoring of the instantaneous state of the variables for autonomous operation. The
average contents of pollutant in the final discharge of gaseous fluid from industrial operation of a
prototype RENACAR of 4 cells, running continuously for a week, was certified to average 0,03
mg/m3 in a plant location altitude under one thousand meters above sea level, where the maximum
LPE is 0,8 mg/m3, a result twenty seven times below its LPE! in the global gaseous fluid effluent
prior to discharge into the open atmosphere.
10
Figure 8 detail of subsystems 1 and 2 concatenated in real time through PAC autonomous control system
Figure 8, shows the operation of the global extraction system in the RENACAR prototype with
gaseous fluid effluent passing through the secondary stage of bubbling in the multistage depurator
condenser device with a chiller. Polluted gaseous effluent flow to be discharged through the turbine
is measured with a verifier device to detect contents of sulfur contaminants by averaging the
contaminant content measured in the effluent flow discharged to the atmosphere by a partial flow
derivative line for a given time, and analyzing the contaminant content following the protocol
indicated by pertinent OSHA Stationary Measurement Methodology.
Figure 9 layout diagram of subsystems 1 and 2 concatenated in real time by autonomous PAC
Figure 9, shows the layout configuration of devices installed in the RENACAR 4 cell Prototype PAC,
with monitoring and communication/ recording system, including reports of sequential data of
instantaneous state of process variables to trigger instantly self-regulation of abnormal variations
from established setting, enabling stable continuous and autonomous operation for an indefinite time
(USPTO Application N°15/357,882-(2016)).
11
BENEFITS DEMOSTRATED/MEASURED BY CONTINUOUS OPERATION OF
RENACAR "CELL BY CELL" PROTOTYPE IN AN INDUSTRIAL COPPER EW PLANT
 Zero emissions of acid mist above cells, 100% of the operating time (including harvests)
 Unprecedented (7 days continuous operation) maximum averages ~0,030 mg/m3 of sulfur
pollutant content in gaseous effluent released to open atmosphere
 Measured power for RENACAR+SEAS <300 Watts/cell (60 cat.@ 300 A/m2)
 Recovery 99.9% of liquid effluent condensate and recycled back to the EW process
 In scavenger cells, elimination of plastic spheres that enable automatic organic removal
 Elimination of plastic spheres improves physical appearance of cathode copper sheets
 Maximum decrease of contaminated effluent by coalescence as it was generated by cell
 Elimination of dilution systems for acid mist capture and all ducting network plus remote
treatment facilities altogether
 Elimination of dispersal of electrolyte aerosols in the external environment of the plant
 Elimination of corrosion degradation of EW plant equipment and buildings over time
 Reduction of at least 1° C, thermal loss between temperatures at the electrolyte infeed and
discharge, enabling substantial fuel savings in electrolyte SX-EW loop inventory
 100% operational availability demonstrated by programmable automation controllers
including monitoring of variables in real time with feedback for self-regulation
autonomous continued operation in 8.840 hours on a RENACAR prototype.
The best results of metal electrodeposits in 4 (scavenger) cells in the RENACAR Prototype were
obtained operating two cells (of four cells) with a typical well known Soft Aeration System (SAS)
(Francisco Sánchez P., 2013) to demonstrate concatenation and observe ad record the combined
benefits of a more complex but optimized operation of the EW process. The results are:
 Improved productivity by continuous operation at high current densities (>50% increases)
 Concentration homogeneity in the layer boundary provides improved availability of metal
 Ions from bulk electrolyte and determines uniform thickness of electrodeposited metal
 Uniformity in the mass transfer, viscosity and flow velocity at the cathode surfaces
 Decrease in thickness of the layer boundary
 Significant increase in current efficiency (2 and up to 4 percentage points)
 Noticeable improvement of the physical and chemical metal electrodeposit quality in
significant number of cathode plates
 Substantial decrease in nodules and rugosities and other defects in electrodeposits
 Reduction of specific energy consumption, expressed as kWh/Ton copper
 Lower electrodes requirements by choosing to operate cells at higher current densities (up
to 50% higher) without affecting the quality of the electrodeposits mentioned above.
 Reduced dissipation of thermal energy and corrosion by 100% zero emission above cells
12
Figure 10 SEAS + RENACAR with PAC, precursor of autonomous EW electrochemical reactors of the future?
Figure 10 shows the “duo” SEAS + RENACAR systems installed for joint operation to obtain
enhancement of productivity/quality fitted in existing cells, duly concatenated with a PAC
autonomous control system extended to other variables of the EW process.
CONCLUSIONS AND ONGOING VISION FOR THE FUTURE

The results of the RENACAR prototype and experience gained after continuous operation from
November 2015 to January 2017, convinced us:
 of the robust, precision and reliability of the generic electronic PAC equipment used in the
present severe polluting environment of EW
 of the flexibility to adapt to the precise concatenation requirements to maintain “duo” SEAS
+ RENACAR seamless operation together with continuous untroubled operation and
excellent 100% operational availability in the aggressive industrial environment
Our foremost conclusions from the experiences learned with the RENACAR "cell by cell" seven years
technological development and demonstrations in this presentation
 “Cell by cell” strategy for acid mist abatement and recycling was demonstrated with results
exceeding expectations: elimination of acid mist dilution, downsizing the problem and
introduction of abatement immediately while acid mist is generated are the key aspects in
the success of our final solution exposed.
 overall, the escalation of RENACAR as an industrial final solution to the acid mist problem
of the EW process, applicable immediately to ALL existing EW cells is not possible, without
the formidable and robust demonstration in the PAC flawless electronics and two ways
wireless communication capabilities.
 The “duo” SEAS + RENACAR arrangement with Autonomous PAC to enhance
productivity and quality of EW electrodeposits at high current densities with 100%
elimination of acid mist effluents over the cells is a pioneer concept opening the challenge
of converting present polymer concrete electrolytic cells into autonomous EW
electrochemical reactors in the not too distant future.
13
REFERENCES
Francisco Sánchez P. (2013), “SISTEMA AIREACIÓN SUAVE ELECTROLITO EN CELDAS
DIVISIÓN GABRIELA MISTRAL”, Copper International Conference 2013.
14
Development and Implementation of SELE®
Technology in EW Tank House, Radomiro Tomic
Division
Mario Núñez1, Felipe Lagno1 and Sergio Cortés2
1. Radomiro Tomic Division, Codelco, Chile
2. New Tech Copper, Chile
ABSTRACT
Since its launch in November 1997, Radomiro Tomic has produced more than 5 million of tones of
copper cathodes, becoming one of the largest EW plants in the world.
Historically, the RT electrowinning tank house has had very good chemical quality results, but very
low in physical quality, so much that, on average the physicochemical quality did not exceed 60% of
grade A copper production.
A Cell aeration technology, called “Air Sparging”, was implemented in 2011 with the purpose of to
improve the physical quality of the cathodes. The results in terms of improvement of physical
cathodic quality have been remarkable, however only a 85% grade A could be reached, far from the
design goal of 92%.
In year 2015, working together with a national company, New Tech Copper, several evaluations of
the SELE® technology were carried out. This technology consists in a device that is installed inside
the cells and allows to improve the physical quality of the copper cathodes over 85% grade A and
increases current efficiency, in addition to other benefits.
This presentation shows the development of this technology, the early evaluations, the successes and
challenges, the paradigm changes and the decisions that led Radomiro Tomic to implement the first
648 SELE® devices in it`s EW plant at the end of year 2016.
In these first months of operation, it is possible to appreciate comparative advantages in the quality
of the cathodes produced and in the general operation of the EW tank house. This, project the
cathodes of Radomiro Tomic to become one of the bests of the Corporation.
1
Start-Up Solvent Extraction: Electrowinning
José Miguel Aldana Fuentes
Minera Antucoya, Antofagasta Minerals, Chile
ABSTRACT
In recent years the development of mining has been facing increasingly difficult projects from the
perspective of environmental, social and economic sustainability. At the same time, Antofagasta
Minerals has been a pioneer in low copper ore deposits, making it increasingly important to have
and / or use low-cost capital and operating technologies, making these resources profitable.
Antucoya considers the extraction of the ore through a conventional open pit operation, which
gives rise to three types of material classified according to CuT law present in each of them: upper
grade ore (0.2-0 , 4%), mineral of marginal qualification (0.13 to 0.19 %) and sterile.
Antucoya considers an estimated production of 80 thousand tons per year of fine copper in the
form of cathodes.
This paper presents the achievements and challenges of the Start-up of the Plant Extraction by
Solvent and Electro-Obtainment. The background considers the Operational Model where security,
design scope during engineering, planning in the hiring, advanced equipment, hiring experienced
Operators, Vendors training, What If lifting, elaboration of procedures before the start of COM,
lifting Of operational support contracts in advance are important milestones to consider.
The operational results obtained confirm the feasibility design parameters and, in turn, provide
opportunities for improvement, where operational excellence is key in the systemic and systematic
management of excellence in performance through the use of capacity in processes, Technology and
human talent even more for this type of low-grade minerals.
1
De Nora’s Mixed Metal Oxide Anode (MMO) Self-
Protected Anode Technology Platform for Metal
Electrowinning
Carl Brown 1, Félix Prado2, Piero Casanello1, Luciano Iacopetti3, Michele Perego3,
Giuseppe Faita3, Paolo Perrone3 and Alicia Calderara3
1. De Nora Tech, USA
2. Infotrol, Spain
3. Industrie De Nora, Italy
ABSTRACT
De Nora, a global leader in the development, manufacture and sale of mixed metal oxide (MMO)
anodes for electrochemical processes will discuss advancements in anodes for metal
electrowinning. A staged development approach was undertaken by De Nora and our industrial
copper electrowinning partner to bring to commercial demonstration of our anode technology
package. This MMO technology package provides a long anode life with enhanced operational
performance benefits when compared to lead alloy anodes, and an integrated short detection
system (SDS) providing anode structure protection and reduced operator intervention in Copper
Electrowinning (CuEW).
The development stages of De Nora’s technology advancements can be partitioned into these main
component attributes: anode structure design, catalytic MMO anode coating, and integrated
dendrite short detection system providing electronic self-governess over dendrite shorting damage
to the primary MMO anode meshes.
De Nora’s state-of-the-art technology has incorporated the most advanced attributes of our MMO
anode developments culminating with advancing two technology types: “Self-Protected Anode”
(SPA-R) – Resistor type along with “Self-Protected Anode” (SPA-T) – Thermistor type with
integrated short detection system. The SPA anode incorporates a modular design for discrete
current distribution and uniform copper cathode depositions. SPA-T anodes employ embedded
electronic micro-switches to regulate current flow to the individual MMO anode meshes when
cathode dendrite shorts are encountered, thus preventing any structural catalytic mesh panel
damages or loss of cathodic current efficiency. While the SPA-R anodes utilize internal titanium
resistors to minimize MMO mesh panel damage during short circuit occurrences.
The implemented technology package provides for the following economic benefits:
1. 12 – 15% power savings
2. Cobalt-free electrolyte operations
3. Smoother, uniform cathode deposits generating a 1 -2% improvement in current efficiency
4. Tankhouse operations producing lead-free copper quality cathodes, in addition to
elimination of lead waste for improved operator health and environment.
1
INTRODUCTION
De Nora’s technology development program for primary metals electrowinning took form in 2011,
putting into place a multidisciplinary team of professionals from R&D coating development,
Design and Manufacture engineering and Customer Field Services. With clear development
objectives, the team set out to provide a next generation all-titanium anode with ancillary short
detection technologies to facilitate optimum electrode performance in today’s electrowinning
tankhouse operations. The technology advancements were developed with the availability and
capital investments of in-house laboratory cell test facility, along with a full height reduced width
plating bench cell. These cell configurations allowed for accelerated life testing of coating
formulations characterized by significant voltage reductions compared to standard lead anode
operations. Additional benchmarking of these optimized coating formulations targeted low
electrochemical wear, coating morphologies providing resistance to surface contamination of
electrolyte species such as lead dioxide or manganese dioxides. The R&D coatings development
team set out to provide a coating with best-in-class hours of operational performance per gram of
precious metal catalyst applied to the anode, with commercial cost and sustainability in focus.
The program, having achieved its goals at the laboratory and bench scale levels, now advanced the
anode structures and catalytic anode coatings to commercial demo cell operations, consisting of 3
anodes/4 cathodes of full size and 24/7 operation characterizing key performance attributes such as
voltage and power savings achieved, copper cathode deposit morphology and lead-free product
quality, acid mist generation observations, cobalt-free electrolyte operations, along with short
detection and minimal titanium anode shorting damage methodology. Successful completion of
these activities and knowledge gained provided a path forward into a pre-commercial full cell 64
anodes/63 cathodes evaluation operated at 450 A/m2 with our industrial Chilean electrowinning
partner. Photos depicting the various testing stages facilities are shown below. Figures 1 - 4 below
depict the progression of anode testing from laboratory benchcells to laboratory pilot onto
commercial pilot culminating in commercial cell operation.
Figure 1 Laboratory Benchcell Testing, R&D

Milano, Italy
2 Figure 2 Pilot 1m x 15cm R&D Cell

Operation
Figure 3 Pilot Commercial Demo
Full Size 3 Anodes, 4 Cathodes Operation 24/7
Figure 4 Commercial Chilean 64-MMO anode
Cell Operation @ 450 A/m2

De Nora is developing an engineered “Value Technology Package” consisting of our MMO anode,
optimized mixed metal oxide coating formulated for copper electrowinning in conjunction with an
advanced real-time integrated Short Detection System (SDS)
C
and Self-Protected Anode (SPA). This
paper will provide an update to the pre-commercial operation of the “VTP” being introduced and
operated with our Chilean industrial partners.
Dimensionally Stable MMO Anode Selection

Mixed metal oxide (MMO) titanium anodes have seen broad industrial use, since their introduction
in the 1970’s, encompassing electrochemical industries represented by Chlor-alkali, Metals
Electrowinning, Electrogalvanizing, Copper Foil and Printed Circuit Board manufacture, Water
Treatment and Cathode Protection, to highlight a few. The acceptance and conversion from lead
alloy anodes to titanium MMO anode technology into CuEW has been hampered over the years by
the high initial product cost and the associated titanium damage incurred to the coated anode
structure resulting from copper cathode dendrite shorting during operations. See Figure 5 below of
a damaged titanium coated mesh area as a result of large cathode dendritic formation for reference.
Figure 5 Cathode dendrite shorting damage imparted onto Titanium MMO anode
3
De Nora has listened to our customers and learned from past MMO anode product entries into the
CuEW tankhouse operations and is addressing these primary issues with our “Value Technology
Package (VTP).” The fundamental R&D laboratory development program focused on the
electrocatalytic coating formulation. Optimization of the mixed metal oxide (MMO) coating
formulation considered key attributes including:
1. Reduction in oxygen overpotential.
2. Coating morphology with enhanced resistance to electrolyte impurities from surface
blinding deposits.
3. Economic considerations of hours of operation at operating current density/ grams of
precious metals utilization.
The “VTP” combines an optimized electrocatalytic MMO anode coating which provides good
economic power savings, meets or exceeds the customer performance target of a 5-year operational
coating life, and a mesh structure suitable for sustainable recoats over its lifecycle.
A skeletonized titanium superstructure has been engineered to provide long service lifecycle and
corrosion resistance to the acid mist environment and includes a titanium clad copper steerhorn
associated with the SDS anode system, in addition to the ti-clad vertical conductor bars in the SPA
anode system. Quick turn structure repair ability, when and if required, has been factored in.
Through Finite-Element-Analysis (FEA) the electrode design minimizes structural electrical drops
and provides for uniformity of throwing power for improved copper cathode deposits. The
resulting effort has produced an economical and robust 20-year titanium anode structure, cost
effective long life 5+ year MMO coating and integrated Short Detection System able to protect the
MMO anode investment from cathode shorting damage.
The initial trialed Short Detection System anode is depicted in Figure 6 below. The primary
attributes of the SDS system include;
1. Parallel tensioned outer dendrite contact screen, relative to the MMO active mesh anode
2. Integrally connected contact screen to an individual MCU, a self-powered anode monitor
device located on the hanger bar
3. Wireless monitoring control box located in close proximity to the corresponding cell
4. Control room laptop with monitoring software along with operations email alert capability.
4
Hanger bar with
MCU integrated
monitoring
MMO anode ”heart”
of the package
Dendrite Short
Detection Screen
Protective Steerhorn
Covering
Cathode Guides
Figure 6 Diagram depicting Functionality of Short Detection Anode System with remote monitoring
The SDS meshes are fabricated incorporating a proprietary resistive coating applied to the base
titanium mesh or cloth structure. The applied non-catalytic coating will not drive the anodic
oxygen reaction, rather its function is to dissipate and distribute the localized current from the
incoming copper dendrite bridge. The MCU electronic unit for alert transmission is installed on
each anode, is self-powered and always active. The system measures, records and transmits the
current flowing into the anode and the steerhorn bar temperature every five minutes. The SDS
system alerts the operator of a dendrite contact when the measured current exceeds a preset
threshold. It provides both an audible signal from the control box located within the tankhouse
and at the control room system laptop, allowing ample time for operator dendrite corrective action
intervention. Software provides a cellroom schematic indicating the exact cell and anode/cathode
position where operator intervention to eliminate the dendrite short is to be performed. Informed
operators can address the dendrite short in real-time, restoring plating current efficiency, knowing
precise cell position/location, and minimize the time in the tankhouse to resolve the short. The time
function associated with dendrite short detection alarm and operator dendrite action to remove
said short is 8 -12 hours to prevent subsequent damage to the primary MMO anode mesh. The SDS
will incur some copper plate-out in the proximity of the dendrite contact, but arrests any further
directional growth of the dendrite toward the MMO anode active mesh, thus, preventing electrical
short damage to the MMO active anode. The copper over plated onto the SDS mesh during a
prolonged dendrite bridging will re-dissolve following operator intervention to dislodge the
dendrite contact or when the cathodes are lifted for copper harvest. The benefits of the SDS
provide for long-life MMO anode operations and improved on-stream copper plating production.
See attached photo of the control alarm box, Figure 7. Photo of operating Short Detection System
(SDS) configured MMO anode in Figure 8. A Ti-Clad copper steerhorn with acid resistance heat
shrink protective covering is shown in Figure 9 below.
5
Junction
Box
Figure 7 MCU WIFI signal to cell control alarm box
Figure 8 Commercial field operated MMO-SDS anode
6
Figure 9 Titanium Clad Primary Copper Steerhorn with acid resistant heat shrink applied to angled regions.
Provides chemical resistance to acid mist and elevated cell electrolyte levels during operation.
Self-Protected Anode “SPA-T” Design with Thermal Electronic embedded switching

Technology
De Nora places a high commitment on the development and commercial implementation of
advanced anode design technologies. Team efforts allowed for a parallel path, continuous
improvement development project based on customer response and operational knowledge gained
from the SDS cell. While the SDS system provided real-time monitoring and operator feedback on
developing anode to cathode shorting, it still required operator intervention to disengage the
dendrite short to prevent continued dendrite growth and resultant damage to the primary MMO
mesh anode. It was further observed that when anode to cathode pairs were misaligned or bent
cathodes were inserted that resulted in a localized close spacing, then significant dendrite bridging
resulted and separation of the SDS anode to opposing cathode pair added to the operator effort.
This feedback prompted De Nora to investigate a novel advancement in our technology which lead
to the Self-Protected Anode “SPA-T” technology development and rapid commercial introduction
trialed. An introduction to our next generation SPA-T technology is described as follows. This
product was introduced into our partner’s tankhouse operation in the fourth quarter of 2015. The
SPA-T anode mesh is arranged in individual small discrete rectangular segments. The discrete
anode mesh segments allow for ease of manufacture and separation from the whole of the anode
when a copper cathode dendrite occurs and bridges making anodic contact. This novel (patent
pending) anode system moves beyond the SDS monitoring system where a tensioned titanium
mesh placed in front of the MMO anode allowed for the dendrite contact and signaled a location
specific alarm, followed by required operator intervention. The SPA-T through the application of
advance embedded electronic switching device allows the anode to self-correct in the advent of an
opposing copper dendrite contact strike. The thermal-switching device will detect when a dendrite
contact has occurred and switch off the current flow to the individual MMO anode mesh panel
instantaneously, thereby restricting further current conduction in this anode/cathode pair and thus
protecting the MMO anode mesh from sustaining structural damage. Upon disengagement of the
dendrite contact, either by direct operator intervention or at cathode harvesting, the SPA-T anode
will return all MMO anode mesh panels to full operation. The ability to prevent physical MMO
anode shorting damage due to shorting and minimize operator tankhouse intervention is seen as
having tremendous operational rewards. A photo of a commercial SPA-T anode is provided in
Figure 10. An operational comparison between unprotected MMO and SPA-T anode schematic is
shown for technology reference in Figure 11. Development and manufacturing advancements have
7
moved this novel technology package forward at a rapid pace rewarding the team with pre-
commercial tankhouse evaluations in operation.
Figure 10 “Self-Protected” Anode Technology utilizing electronic thermistor-type short intervention system.
SPA-T type anode technology
8
Figure 11 MMO unprotected anode vs. SPA-T Thermal switch protected anode under dendrite short occurrence.
Description of SPA-R Resistor type anodes

An additional technology for “Self-Protected” titanium anodes is under pre-commercial trails and is
included in the De Nora technology electrowinning portfolio. The technology, shown in Figure 12,
is named SPA-R for the incorporated titanium resistor bridge providing for the “self-protection”of
the coated mesh panels during copper cathode dendrite bridging encounters. It is best
characterized by the following features:
1) “Self-Protected”: the anode does not result in large scale shorting damage under
intense and extended dendritic short circuiting. Under dendritic short occurrence the
titanium incorporated resistor imposes an ohmic drop sufficient to decrease the electric
potential on the shorted segment, thus minimizing copper deposition from the dendrite
contacting tip.
2) “Full Metal”: all structural wetted parts are titanium made. Only add-on
ancillaries’ like
spacers are of plastic composition. All materials are compatible with tankhouse operations.
3) “No parasitic copper plating”: the anode, being segmented in design, prohibits full
mesh surface plate-out of copper in situations of dendrite short circuit occurrences.
4) “Efficient”: limited current dissipation under cathode to anode bridged short
circuit. The copper cathode plating efficiency remains very high even in the case of frequent
short circuits.
9
5) Each anode mesh segment is welded to the Ti-clad conductor bars through a
calibrated titanium resistor.
Figure 12 “Self-Protected” Anode Technology utilizing titanium resistor type short intervention system.
SPA-R technology
10
Copper Harvest Quality
Through the application of MMO “Self-Protected” anodes applied in the production of CuEW,
numerous benefits are realized relative to copper quality. Removal of the lead alloy anodes
immediately eliminates lead oxide being generated as part of the anode reaction; therefore, no lead
oxide is available to transfer to the copper cathode as an undesirable product contaminate when the
cellroom is operating with De Nora’s MMO anodes. The elimination of lead particulates into the
electrolyte also has a direct correlation into the reduction in seed sites for cathode dendrite
nucleation and thus a direct reduction in cathode dendrite formations. This will result in an
improvement in cellroom current efficiencies as plating current is not directed to shorting current.
The implementation of SPA anodes can also provide another level of copper cathode production
value. When a cathode dendrite contacts the anode mesh panel, the panel is de-energized
preventing short damage to the MMO anodes. However, the current is redirected to the remaining
active mesh panels producing the highest tankhouse current efficiency possible. Upon full
tankhouse MMO anode conversion, it can be expected that Quality Assurance copper sampling for
ppm lead contamination in the harvested product can be redirected. MMO anode operations
produce no lead sludge contribution and thus results in zero-lead in the copper cathode product.
Additionally, with the elimination of anodic lead oxide generation, the requirement of quarterly
maintenance cell cleaning and operator exposure to lead is a thing of the past. Eliminating
quarterly cell cleaning allows for an improved copper production on-stream factor as well.
Uniform side to side, top to bottom MMO anode throwing potential produces smooth uniform
copper plate distributions as evident by Figure 13 harvest photo.
Figure 13 Representative uniform smooth copper cathode at harvest generated by MMO anode
Conclusions
cell operation (450 A/m2).
11
The De Nora Self-Protected anode product offering for CuEW is represented in our “Value
Technology Package”. The Development Team has listened to our customers’ needs and desires
and applied our company’s 90+ years of technology innovation to meet the challenge. Key
economic milestones achieved with the VTP include:
1. 10-15% Power savings through reduced anodic operating potential
2. Improved copper product quality with the elimination of lead in the system
3. Elimination of cobalt sulfate electrolyte additions
4. SDS option providing real-time electronic monitoring of copper dendritic shorting
occurrences
5. Self-Protected long-life anode structure and MMO coating optimized for operation
conditions in CuEW
6. Improved on-stream production factor for CuEW with elimination of lead oxide cell
cleaning maintenance.
The total package of advance anode coating, robust all titanium anode design, integrated “Self-
Protected Short Detection System” provides all the performance benefits an MMO anode can offer
with economic value to the CuEW market. Through continuous improvement technology
advancements, the SPA anodes are being developed on parallel paths and introduced to the EW
market establishing customer benefit and appreciation.
12
CHAPTER 8
Recycling of Metals
and Alloys
Acid Leaching and Precipitation of Metals from
Spent Li-ion Batteries
Sebastian Armas and Diana Endara
ABSTRACT
A hydrometallurgical process was performed to recover lithium, cobalt, manganese and nickel from
spent batteries of cell phones and laptops. Spent batteries were disassembled manually to remove
the residue of interest; after size reduction a d80 of 560 microns was obtained in the cell phone
residue and 800 microns in laptops, with a density of 2.19 and 2.25 g/cm3, respectively. Aluminum
and copper causing interference to leaching were removed by sieving. The best recovery
percentages: 98.9 % for lithium, 99.8 % for cobalt, 99.5 % for manganese and 98.9 % for nickel for the
waste from spent cellular batteries were reached with the following conditions: 4.0 M sulphuric
acid, with a liquid / solid ratio of 10:1, 70° C, 250 rpm and 120 minutes. The best recovery
percentages for waste from spent laptop batteries were achieved with the following conditions: 3.0
M sulphuric acid, with a liquid/solid ratio of 10:1, 70° C, 250 rpm and 120 minutes; and were 99.6 %
for lithium, 96.0 % for cobalt, 99.9 % for manganese and 98.7 % for nickel.The liquor leachate was
neutralized with sodium hydroxide, at different pH values (7, 12 and 13) to precipitate manganese
carbonate, cobalt hydroxide and lithium bicarbonate respectively. Then the evaporative
crystallization of precipitated products was made and recoveries of 99%, 97% and 96%, were
achieved, respectively. Purity of products were tested by XRD analysis. Finally a process of
recovery of the metals of interest was designed with the best process conditions.
1
INTRODUCTION
Lithium batteries have become one of the most chosen by consumers worldwide, with a production
of about 2 044 million units per year (Nakajima, 2015). In the last decade, global demand for lithium
has increased from 45 000 to 125 000 tons (Fox-Davies Resources Specialist, 2013). Disposal of these
articles becomes an unsustainable environmental problem (Shin et al., 2005), since only in Ecuador
15 350 tons of hazardous wastes were generated during 2012 (INEC, 2013) and lithium batteries
represents approximately 30 % of all them. (EPA, 2012).
The lithium battery cells are basically composed of aluminium sheets (cathode), covered generally
by a layer of metal oxides, mostly LiCoO2, in form of fine powder, whereas the copper (anode) sheets
are covered by a thin layer of carbon. It is in these where the reactions that generate the potential
required for the operation of the equipment take place, due to the energy produced by the migration
of lithium ions into the electrolyte solution, lithium salts (usually LiPF6) dissolved in organic solvents.
The powdered materials adhere to their respective sheets with a polymeric binder, usually PVDF
(polyvinylidene fluoride). The sheets are rolled cylindrically with a layer of plastic material that acts
as an insulator and also protects the integrity of the cell (Ferreira et al., 2009). The whole cell is covered
by a completely sealed metal housing that protects it from the environment and is used as a
connection port between the electronic device and the cell.
In order to recover the valuable metals (lithium, cobalt, manganese and nickel) present in these waste,
a number of investigations have been made using different types of inorganic acids such as sulphuric
acid (Nan et al., 2006; Shin et al., 2005), hydrochloric acid (Wang et al., 2009), nitric acid (Ferreira et
al., 2009) and ammoniacal leaching (Senanayake et al., 2010). Nayl, Elkhashab, Badaway and El-
Khateeb (2014) developed a process in which lithium, cobalt, manganese and nickel were recovered
from lithium commercial cell battery models through two basic and one acidic leach stages, in which
they achieved recoveries of the order of 90% for each metal. One of the main limitations for the
recycling of this type of batteries is the difficulty of extracting the residue that contains valuable
metals given the insulation provided by the casing and the physical risks involved in their separation.
Another factor that can affect the recycling and processing of this type of waste is the heterogeneity
of the material, since according to the manufacturer there are many formulations and therefore
different compositions of the metals to be recovered. This is why a highly selective method is required
to recover very specific components without removing other substances from the residue; chemical
precipitation is a proven and relatively simple and efficient technique, which under specific
conditions can reach high recoveries.
The objective of this work is to recover lithium, cobalt, manganese and nickel from discarded cell and
laptop batteries, by leaching and subsequent chemical precipitation.
METHODOLOGY
2.1 Physical and chemical characterization

Each type of battery was manually disassembled and the three components of the cells were
separated: cathode, anode and insulation plastic sheet. The sheets of the three components were
washed with distilled water to remove the remaining electrolyte and dried in a Venticell stove at
120 °C for 24 h (Dorella and Mansur, 2007). The three components of the cell were then crushed in a
Dayton Braun Chipmunk VD67 shredder and once the size reduction was complete, the crushed
2
metal sheets were separated, the plastic cover was discarded and the size residue less than 5.0 mm
corresponding to the previously impregnated material in the sheets was collected (Mantuano et al.,
2006). The residue was ground in a Leeson C6T17FC25 ball mill with a solids content of 62.5 % for
4 h, and the sludge obtained was then dried in a Venticell oven at 120 °C for 24 h. The d80 of the dry
residue was determined by the ASTM C136/C136M-05 method, the density of the product was
determined with the INEN standard NTE 0856: 2010.
To determine the amount of lithium, cobalt, manganese, nickel, copper and aluminium, present in
the different residue samples, 100 mg of each type of residue was disaggregate to be analysed by
atomic absorption (AA) on a Perkin Elmer AAnalist 300 equipment.
2.2 Evaluation of the best leaching conditions for the recovery of metals
First one basic leaching with ammonium hydroxide was made for the lixiviation of copper and
aluminium and second an acid leaching of the precipitate obtained in the first lixiviation with
sulphuric acid to lixiviate lithium, cobalt, manganese and nickel.
2.2.1 Basic leaching with ammonium hydroxide

A mass of 33.3 g of the dry residue were treated by adding ammonium hydroxide solutions in
concentrations of 3.0 to 4.0 M with a liquid / solid ratio of 15: 1 (Chen et al., 2011). After the
temperature of 60 °C had been reached, stirring was started at 250 rpm for 2 h to ensure a good mass
transfer, each flask was sealed with paraffin wax to avoid losses by evaporation of the leaching agent
and to prevent contamination of the solution. After the leaching time, the agitation was suspended,
the pulp was filtered and the paste was dried at 80 °C for 120 min.
2.2.2 Acid leaching with sulphuric acid

In the present work the variation of concentration of the leaching agent against the percentage of
recovery of the metals of interest was examined. After drying, the dry paste obtained in the prior
leaching, was leached with sulphuric acid solutions of 3.0 and 4.0 M concentrations with a liquid /
solid ratio of 10: 1 (Ferreira et al., 2009) at a temperature range from 25 °C (room temperature) to
70 °C for 120 min. Then, the solution was filtered.
The solutions from the basic and acidic leaching of each type of residue were analysed by atomic
absorption (AA) spectrometry in Perkin Elmer AAnalist 300 equipment.
2.3 Evaluation of the best precipitation and crystallization conditions of the metals
The acid leach liquor was taken and sodium hydroxide was added in 3 and 4 M concentrations,
respectively, to adjust the pH and precipitate the compounds of interest. For manganese
precipitation, the solution was brought to a pH between 7 and 7.5 (Sayilgan et al., 2010) by adding
Na2CO3 (Araneo, 1989) at 200 rpm and 60 °C for 120 min. For nickel precipitaion, the pH value of the
leach liquor was adjusted to 9 (Araneo, 1989) by addition of NaOH, then sodium bicarbonate was
added to obtain nickel carbonate (200 rpm, 120 min, 60 °C). Cobalt hydroxide was obtained by
bringing the liquor leached to pH 12 (Araneo, 1989) at 200 rpm, 120 min, 60 °C by addition of an
excess of 10% NaOH in the presence of oxygen (Danguillecourt, et al., 2001). Subsequently, lithium
carbonate was precipitated by addition of excess sodium bicarbonate at 90 °C and 250 rpm at pH of
13 (Li et al., 2009; Zhu et al., 2012). At each recovery, the solution was filtered to obtain the precipitate
3
and this was washed with hot water to remove undesired salts. Then, in a Venticell stove,
evaporative crystallization of the precipitated products was carried out by progressive heating of the
samples for 24 h, in which the temperature was varied between 70 and 120 °C, in increments of 20 °C
every 2 hours, to ensure the formation of crystals. Finally the mineralogical characterization of the
products precipitated by X-ray diffraction (XRD) was carried out in Bruker D8 Advance equipment.
3.1. Results of physical and chemical characterization

In the particle size distribution of the waste cell and laptop batteries, it was observed that the d80 is
800 and 560 μm, respectively. The density of cell phone residue was 2.2 g/cm3 and that of laptops was
2.3 g/cm3. This small variation may be due to the contributing amounts of each component metal in
the cells. Table 1 shows that the residue from laptop batteries presented more metals of interest than
cell phones. This is due to the characteristics of the cell since it has greater weight, durability and
requires a high specific energy (Patil et al., 2007). The cobalt content was higher in the residue samples
of both residues because the cathode has a high amount of lithium oxide and cobalt (LiCoO 2).
Table 1 Chemical composition of the waste from cell phones and laptops
Concentration according to battery type

Element
Cellphones (%) Laptops (%)
Li 4.5 6.2
Co 19.2 37.3
Mn 7.9 6.3
Ni 0.7 0.7
Al 1.1 0.8
Cu 1.5 1.2
For the manganese, copper and aluminium content, it was observed that the residue from laptops is
slightly inferior and depends on the cathodic and anodic material that the manufacturer used to make
the cell. It is also noted that the percentages of copper and aluminium, are much lower than the metals
of interest which may be due to the separation of material realized in the size reduction process.
Another fact that may influence the variation of the aluminium and copper content, compared to
other investigations that have composition values of 2 and 4 %, respectively (Nayl et al., 2014), is that
the battery model varies from one to another electronic device.
4
3.2 Results for the evaluation of the best leaching conditions
3.2.1 Results of the basic leaching with ammonium hydroxide

Table 2 shows the effect of the variation of the concentration of ammonium hydroxide in the basic
leaching of the residue of cell and laptop batteries; a moderate increase in copper recovery can be
observed by increasing the concentration of hydroxide in the residue from the cell phones, against
the low values in the recovery of the metals of interest. The percentage of copper recovered increased
as the ammonium hydroxide concentration varied from 3 to 4 M in the cell residue.
Table 2 Effect of the variation of ammonium hydroxide concentration on the basic leaching of cell
and laptop batteries residues (ratio l/s: 15/1, 60° C, 250 rpm and 120 min)
Cell battery residue Laptop battery residue
Element
[NH4OH] [NH4OH] [NH4OH] [NH4OH]
3,0 M 4,0 M 3,0 M 4,0 M
% Li 12.09 10.69 33.88 18.68
% Co <0.01 <0.01 0.01 <0.01
% Mn <0.01 <0.01 0.02 <0.01
% Ni <0.01 <0.01 0.02 0.01
% Al <0.01 0.03 0.49 0.04
% Cu 17.49 29.95 34.66 22.44
The residue from laptops presents a tendency contrary to the one of cellular, in which it is observed
that when increasing the concentration of the ammonium hydroxide, the recovery of copper and
lithium decreased. In the case of aluminium, values lower than 1 % were obtained in the tests using
NH4OH, with concentrations of 3 and 4 M in each type of residue, the highest value reached in the
tests was 0.49 % in the waste of laptops, with a concentration of ammonium hydroxide of 3 M. The
incipient recovery of copper and aluminium may be due to the low content of these according to the
characterization of the two types of residues and the heterogeneity of the cells used for this study.
This indicates that the grinding and sieving process may be sufficient to remove most of these metals.
The low copper and aluminium content in the filtered solutions benefits the process by avoiding
interference in the acid leaching of the metals of interest, since they react with the concentrated
sulphuric acid at moderately high temperatures (60 to 90 °C). (Vogel, 1996). For cobalt, manganese
and nickel, recovery values even less than 1 % are observed in all tests; lithium on the other hand
reached values of 12.1 and 10.7 % in the leaching tests of the cellular waste, compared to 33.8 and
18.7 % in the tests with laptops, which can be related to the composition of the two types of samples
since the one of laptops presents greater amount of lithium than the residue of cellular. Given the
affinity of lithium for ammoniacal salts (Vogel, 1996), it is not uncommon to observe moderate
5
recoveries of lithium in basic leaching. The total reactivity of this metal may be influenced by the
nature of the active material in which it is housed. Because of the intercalation and migration of
lithium between the different oxides, it does not leach completely during this stage (Nitta et al., 2015).
The basic leaching with ammonium hydroxide shows a similar selectivity for copper and lithium but
does not present recovery rates higher than 40 % in the studied concentrations; on the other hand, it
was observed that this leaching agent is not selective for cobalt, manganese and nickel and that it was
not enough selective with lithium in the residue from cell phones. In addition, the precipitate from
basic leaching can be separated by filtration thereby reducing the chances of reactions interfering
with acid leaching and subsequent precipitation.
3.2.2 Results of the acid leaching with sulphuric acid 98%

Figure 1 shows the effect of the variation of the sulphuric acid concentration on the waste from
cellular batteries for the recovery of lithium, cobalt, manganese and nickel. It can be noticed that
increasing the concentration of sulphuric acid improved the cobalt and manganese recovery
percentage, which reached values of 99.8 and 99.5 %, respectively. While at 3.0 M, their maximum
recovery values are at 97.9 and 76.3 %, respectively. Although lithium and cobalt exhibited similar
behaviour at both concentrations, a rapid growth between the first 40 minutes, and a marked
tendency to stabilize after 40 min, the recovery rates at 3.0 M were slightly higher than those obtained
in 4.0 M and corresponding to 99.4 and 99.2 %, respectively.
100 100
90 90
80 80
70 70
Li 60
Recovery (%)
60 Li
Recovery (%)
50
50 Co Co
40
40
Mn 30 Mn
30 20
20 Ni Ni
10
10 0
0 0 40 80 120 160
0 40 80 120 160
Time (min) Time (min)
Figure 1 Effect of the variation of sulphuric acid concentration on leaching of cell battery waste a) [3.0 M] and
b) [4.0 M] (ratio l/s: 10/1, 70 °C, 250 rpm and 160 min)
The manganese presents a particularity with respect to the rest of the metals of interest, in which the
percentage of recovery decreased 13.7 % when reaching the total reaction time, this could be because
the equilibrium of the reaction was displaced towards the formation of reagents after a loss by
evaporation of the leaching agent. Similarly, in Figure 2, it is observed that higher recovery values
were obtained during the leaching with 3.0 M sulphuric acid than those reached with a concentration
of 4.0 M, in the residue from laptops. For the lithium the values were 99.6 and 98.7 %, for the cobalt
values of 96.0 and 95.3 % were obtained for manganese 99.9 and 99.9 % and for nickel, 98.7 and
94.9 % in 3.0 and 4.0 M, respectively. The same trend observed in the cellular residue was observed,
a rapid increase at 40 min and stabilization between 40 and 160 min, although recovery values at 40
min were slightly lower than in the experiments with the cell phone residue.
6
100 100
90 90
80 80
70 70
60 Li 60 Li
Recovery (%)
Recovery (%)
50 50
Co Co
40 40
Mn Mn
30 30
20 Ni Ni
20
10
10
0
0
0 40 80 120 160
0 40 80 120 160
Time (min) Time (min)
Figure 2 Effect of the variation of sulphuric acid concentration on the leaching of residual batteries of laptops
a) [3.0 M] and b) [4.0 M] (ratio l/s: 10/1, 70 °C, 250 rpm and 160 min)
The percentage recovery of lithium in 40 min and concentration 3.0 M in the cell waste is 90.4% and
under the same conditions, the value of lithium in the laptop waste was 83.9 %. At a concentration of
4.0 M, the difference between the recovery percentages is even higher, for lithium, for example,
92.4 % was reached in the cellular waste while in the laptop waste at same conditions, reached
26.5 %. This may be due to the amount of metals present in each type of waste. As shown in Table 1,
the composition of these metals is greater in the waste of laptops and thus may require more time to
dissolve a greater number of them. The two types of residue present similar recovery rates, which
indicates that the leaching agent is suitable for the dissolution and concentration of the metals of
interest and that it works effectively in the two types of waste. Since the maximum recovery values
of the metals were obtained between 100 and 160 min, it was taken as the time interval to obtain the
best condition for the following experiments.
3.3 Results of the precipitation and crystallization conditions of the metals

The precipitation of lithium carbonate was achieved with pH of 13 and an excess of 20% Na2CO3, at
90° C, 200 rpm for 120 min. As shown in Figure 3, the XRD analysis showed that 96.0 % of the
precipitate crystallized as Zabuyelite (Li 2CO3) and the remaining 4.0% as Nahcolite (NaHCO3). The
percentage of NaHCO3 impurity may be related to excess sodium bicarbonate used for precipitation;
given the nature of the leach liquor.
7
Figure 3 XRD pattern of the precipitation of lithium carbonate
Precipitation of cobalt hydroxide occurred at a pH of 12 with 10 % excess of NaOH at 60° C, 200 rpm
for 120 min. The XRD analysis showed that 97.0 % of the purified precipitate crystallized as Co(OH)2,
the remaining 3.0 % formed Thenardite (Na2SO4). In the case of manganese, 99.0% of manganese
carbonate MnCO3 was obtained with the following conditions: pH 7.5 and excess of 10 % of Na2CO3,
60 °C, 200 rpm for 120 min. (See Figure 4).
In carrying out the tests with nickel, it was noted that despite being at pH values adequate for its
precipitation, it did not show a similar and spontaneous behaviour as the other metals of interest,
which could be due mainly to the low value in the composition of the residue of each type of battery.
8
Figure 4 XRD patterns of the precipitation of cobalt hydroxide a) and manganese carbonate b)
CONCLUSIONS
The best recovery percentages for the waste from spent cellular batteries were reached with the
following conditions: 4.0 M sulphuric acid, with a liquid / solid ratio of 10:1, 70 °C, 250 rpm and 120
minutes; and were 98.9 % for lithium, 99.8 % for cobalt, 99.5 % for manganese and 98.9 % for nickel.
This indicates a high selectivity for the 4 metals of interest by the sulphuric acid and notes that the
leaching stage is key to the concentration of the same.
The best recovery percentages for waste from spent laptop batteries were achieved with the following
conditions: 3.0 M sulphuric acid, with a liquid/solid ratio of 10:1, 70 °C, 250 rpm and 120 minutes;
and were 99.6 % for lithium, 96.0 % for cobalt, 99.9 % for manganese and 98.7 % for nickel. As in the
cellular waste, a high leaching efficiency and recoveries above 96.0 % are observed, indicating that
the process is feasible for both types of waste.
For the precipitation processes, 96.0 % of Zabuyelite (Li2CO3), 97.0 % of cobalt hydroxide Co(OH)2,
and 99.0 % in the form of Rhodocrosite (MnCO3) were obtained.
ACKNOWLEDGEMENTS
The authors are grateful for the financing granted by the Department of Extractive Metallurgy of the
Escuela Politécnica Nacional for the realization of the project.
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11
Neodymium Recovery from Post-Consumer
Computer Hard Drive Magnets using 𝐇𝟑 𝐏𝐎𝟒 and 𝐇𝐂𝐥
Solutions
Raquel Ibarra and Ernesto de la Torre
ABSTRACT
The permanent NdFeB magnets are known as fundamental components in hard disks structure
because they have replaced the traditional ferrite magnets that are too much heavier and their
magnetic field intensity is lower. The post consume computer hard disks magnets were
demagnetized by heating (350 °C, while 4 h), they were characterized by X ray diffraction (Fe2 O3 ,
Fe3 O4 y NdFeO3 ) and atomic absorption spectrophotometry (57,9 % Fe; 32,5 % Nd). The leaching
agent concentration (H2 SO4 , HCl, HNO3 and H3 PO4 ) (100-350 g/L), the effect of leaching time (1-24 h),
the solids percentage (1 -20 %), the purification of the leached solutions by solvents extraction
(HDEHP, TBP, Hostarex PO-224 y Lix 984) and the precipitation with NaOH (pH 1-6) were studied
to determinate the best conditions for the neodymium recovery. The excessive presence of iron in
the magnets motivated to modify the traditional methods. A phosphoric acid pretreatment was
included, it was followed by a hydrochloric acid leaching. The process showed a removal (76,7 %
Fe) corresponding to phosphoric acid (250 g/L, 24 h y 10 % solids) and a secondary leaching
recovery (100 % Nd) with hydrochloric acid (100 g/L, 24 h and 10 % solids). The purification of
leached solutions with extracting agents reaches a 60,2 % Nd recovery with HDEHP (2 M in n-
hexane). Regarding to sodium hydroxide (pH=2) precipitation, an x-ray diffraction analysis (DRX)
(Fe2 O3 , Fe3 O4 and NdFeO3 ), revealed the neodymium phosphate obtainment with 99 % purity.
1
INTRODUCTION
Approximately 63 000 t magnets of NdFeB used in electronic devices will finish their useful life in
sanitary spillway in 2007, and about 120 000 t magnets will finish in sanitary spillway in 2020.
Recently, this waste has grabbed people’s attention because of the presence of rare soil content such
as neodymium which has great economic value (Xun, 2002). Therefore, it is important to start to
recover neodymium from wasted magnet. It could be using a low cost process designing with
efficient resources use and contaminants reduction. (Takeshi et al, 2005).
Most recently researches outline the magnetic mud grinding with a previous demagnetization. It is
possible to dissolve the high Nd content (35% weigh) with acids solutions. If you work with H2 SO4
a selective precipitation is performed, later with HCl a solvents extraction is performed (Lee et al,
2013). The use of HNO3 is avoided because it produces nitrated residual water. The Fe elimination by
treated solution precipitation is given at 99 % with pH=2, at the same time the Nd, Dy and B was
reduced to 22, 5 and 30 % respectively. Finally, oxalic acid is added to the solution and Nd
precipitates as neodymium oxalate as it is shown in Rx1:
2 𝑁𝑑 3+ (𝑎𝑞) + 3 𝐶2 𝑂42− (𝑎𝑞) → 𝑁𝑑2 (𝐶2 𝑂4 )3 (𝑠) (1)
Therefore HCl leached solution a solvents extraction is performed. (Muñoz, 2011; Ritcey, 2004):
D2EHPA (di 2 Ethyl hexyl phosphate), PC88A (mono-2- ethylhexyl ester) y LIX 272 (5, 8- diethyl-7-
hydroxy-6-dodecanone oxime). Chemical speciation curves of watery phase are made establishing
the ion ph Nd range. This recovery method has an overall rare earth yield of 58 %.
Another Nd recovery method is the monazite processing or rare earth phosphate 𝑅𝐸(𝑃𝑂4 )
(Kanazawa y Kamitani, 2006). This mineral contains up to 70 % rare earth content after a physic
concentration (Tanaka et al, 2013). The alkaline method is one of main technologies of monazite
leaching now. After of mineral treatment with a NaOH solution (70 %, Tamb.) for 4h.
𝑅𝐸𝑃𝑂4 (𝑠) + 3𝑁𝑎𝑂𝐻(𝑎𝑞) → 𝑅𝐸(𝑂𝐻)3(𝑠) + 𝑁𝑎3 𝑃𝑂4 (𝑎𝑞) (2)
The products can be leached selectively with HCl at 3 % and recover the Nd. The conversion time is
shorter (45 min), however, the recovery rate is near to 89 % (Merritt, 2009; Kuzmin et al, 2012).
Figure 1 shows the Nd − Cl − Fe − P − H2 O Pourbaix diagram, which is obtained from the HSC 6.0
simulation program. It indicates the neodymium phosphate stability on the pH 1-12 region.
Mentioned compound is the one that is habitually on nature.
2
Figure 1 Pourbaix diagram of the system: Nd − Cl − Fe − P − H2 O
(HSC Chemistry 6.0 Simulation)
METHODOLOGY
A demagnetization process was performed through heating (350 °C y 4 h). The particle size was
determinate by a mechanic separation with standard sieves Tyler brand, ensemble to a vibro-sieve
ATM Arrow. The mineralogical analysis was performed with D8 Advance (DRX) difractometer.
The software Diffrac Plus was used to the quality analysis. The sample was characterized through a
semi quantitative chemical analysis in a sweep electronic microscopy (MEB) and the metals content
(Fe, Co, Mn y Nd) was determinate using the atomic absorption spectrophotometry technique.
In the leaching tests, working at room temperature and magnetic agitation. The firsts essays were
done with HCl, HNO3 , H3 PO4 y H2 SO4 . First, a primary leaching was made with the purpose of
separate the iron present in the raw material. The tailing resulting that contains the rare earth was
submitted next to a secondary leaching for the Nd recovery. The influence of the leaching agent,
concentration and the contact time were evaluated in each essay.
All the tailings were dried in a Venticell stove at 110°C for 4h. For the metals (Fe, Co, Mn y Nd)
content determination in each trailing, an acid disaggregation was performed in hermetic reactors
and microwave oven; finally the samples were analyzed by atomic absorption spectrophotometry
(AA). Whit these results a metallurgical balance was made and the metal recovery was calculated.
In the leached solutions purification by solvents extraction stage, the influence of the organic
extracting agent in n-hexane was taken into account. The watery phase will be the strong solution
obtained from the secondary leaching. Four extracting agents were evaluated: HDEHP, TBP,
Hostarex PO-224 y Lix-984 with a volume relation 1:1 for 15 min under magnetic agitation. The Nd
concentration in watery phases was analyzed through atomic absorption spectrophotometry and
the organic phase concentration was obtained by strong leaching solution difference.
The precipitation process was made with NaOH; pH was controlled into 1-6. The charged solution
precipitated was filtered and analyzed by atomic absorption spectrophotometry (AA). The
metallurgical balance was obtained to compare the inicial and final Nd concentration. Finally, the
3
salt precipitated was calcinated at 600 °C for 3 h and was analyzed by X-ray difraction (DRX) with
Bruker AXS D8 Advance equip where the compound formatted was known.

Hard drive magnets (demagnetized and pulverized) show a particle size equal to 350 𝜇𝑚 and 8,5
uniformity coefficient; that show a high grade heterogeneity. The chemical characterization through
atomic absorption spectrophotometry as indicated in Table 1.
Table 1 Hard drive magnets metals composition (AA)
Element Content
Fe (%) 57,9
Nd (%) 25,2
Co (%) 1,4
Mn (%) 0,4
The permanent magnets have a high content of iron oxides; hematite mainly, magnetite and
neodymium ferric oxide. In this kind of analysis any compound with Boron were found as this cite
propose (Miura et al, 2008). Consider that the equip detection limit is 1 % for compound defined
crystallization. The mineralogical permanent hard drive magnets composition is exposed on Table2.
Table 2 Mineralogical composition of computer hard drive magnets
Compound Formula Content (%)

Hematite 𝐹𝑒2 𝑂3 30
Magnetite 𝐹𝑒3 𝑂4 20
Neodymium iron oxide 𝑁𝑑𝐹𝑒𝑂3 20
Neodymium chromium 10
𝑁𝑑(𝐶𝑟0,6 𝑀𝑛0,4 )𝑂3
manganese oxide
Kamacite (𝐹𝑒, 𝑁𝑖) 10
Plagioclase group (𝑁𝑎, 𝐶𝑎)𝐴𝑙(𝑆𝑖, 𝐴𝑙)𝑆𝑖2 𝑂8 10
Primary leaching tests

Iron makes up 57 % elemental composition, as seen in the treatment sample characterization. By
this reason, primary leaching tests were performed to eliminate Fe.
Leaching agent influence

The tests performed with HCl reached recovery higher to 99 % for Fe, Nd, Co, and Mn; this fact
makes the process the best leaching agent alternative. However, the affinity with Fe is high.
Otherwise, essays made with HNO3 show Nd (62,6 %) and Co (68,3 %) lower recoveries in
comparison to Fe (32,7 %). In later process, the high Fe content makes the filtration separation
difficult.
Best results were achieved from leaching essays with H3 PO4 , has higher Nd affinity because it is
more electropositive and ionic. The Fe present in raw material is found as oxide, which give way to
4
the formation of a mineral passivating layer, by this reason stay as Fe2 O3 ; obtaining a 66,5 %
recovery in the solution.
The H3 PO4 becomes the best alternative to Fe elimination without Nd dissolution. Furthermore, as a
practical result of every performed essay, is possible to verify that all reactions are highly
exothermic and show hydrogen liberation.
Concentration Influence
Varying H3 PO4 concentration (50-250) g/L in the primary leaching essays, it gets successfully Nd
recovery without lost it in solution. (Nd recovery 0 – 0,02 %). In addition, the Fe separation for 50 –
150 g/L of H3 PO4 is 2,5 – 4,9 %. However, the agent concentration increases to 250 g/L possible to
reach 76,6 % of removal. This is because to the phosphate ions consume for neodymium and the
others metals found in the hard drive magnets covering.
Kinetics of primary leaching
Figure 2 shows the primary leaching kinetic for iron, cobalt and manganese with 𝐻3 𝑃𝑂4 .
100
Metals recovery in solution (%)
80
60
40
20
0
0 6 12 18 24 30 36 42 48
Time (h)
Hierro Neodimio Cobalto Mn
Fe Nd Co
Figure 2 Leaching kinetics of Fe, Nd, Co and Mn with 𝐻3 𝑃𝑂4 (250 g/L and 10 % solids)
The recovery found in the solution at 48 h is 77 % for iron. However, the Nd tendency over the
leaching time interval is totally different to the others present metals, since its recovery percentage
at a time of 1 h is 0,04 % decreases to 0 % at 24 and 48 h of H3 PO4 treatment.
The neodymium present in the magnets reacts with the phosphoric acid to form a solid product
which remains stable as shown in Figure 1 (Pourbaix Diagram Nd − P − H2 O). The main reaction of
the leaching process is:
𝑁𝑑𝐹𝑒𝑂3 (𝑠) + 2𝐻𝑃𝑂4 (𝑎𝑞) → 𝑁𝑑(𝑃𝑂4 )(𝑠) + 𝐹𝑒(𝑃𝑂4 )(𝑎𝑞) + 3𝐻2 𝑂 (𝑎𝑞) (3)
5
Secondary leaching tests
The primary leaching tailing was subjected to a second leaching with HCl, it presented the
maximum recovery of Nd and other metals (Co and Mn) (99 %) in solution.
Kinetics of secondary leaching

The best results obtained in the secondary leaching tests were with HCl (100 g/L and 10 % solids).
From these parameters, tests were carried out to study the influence of time on metal leaching as
shown in Figure 3.
100
Metals recovery in solution (%)
80
60
40
20
0
0 6 12 18 24 30 36 42 48
Time(h)
Nd Fe Co Mn
Neodimio Hierro Cobalto Manganeso
Figure 3 Influence of leaching time with HCl (100 g/L and 10% solids) (Pretreated samples H3 PO4 , 250 g/L, 24h
and 10 % solids)
The recovery of Nd in 1 h of leaching is 91 % and reaches 100 % in 24 h. All curves described by the
tests have a maximum point corresponding to 24 h. When the two leaching carried out in the Nd
recovery process was analyzed, it was evidenced that when the neodymium phosphate, leaching
product with H3 PO4 , was subjected to a second leaching with HCl (100 g / L, 10 % solids and during
24 h); the compound obtained in solution is diacid phosphate of neodymium with release of
chlorine:
𝑁𝑑(𝑃𝑂4 )(𝑠) + 2𝐻𝐶𝑙(𝑎𝑞) → 𝑁𝑑𝐻2 𝑃𝑂4 (𝑎𝑞) + 2𝐶𝑙 − (𝑎𝑞) (4)
According to Figure 4, it corresponds to the simulation obtained in the HSC Chemistry 6.0 program
of the Pourbaix diagram of the system: Nd − Cl − Fe − P − H2 O . It can be seen that the recovered
Nd is totally dissolved in the strong solution.
6
Eh (Volts) Cl - Fe - Nd - P - H2O - System at 18.00 C
2.0
ClO4(-a)
1.5
1.0
FeCl2(+a)
0.5
0.0
Cl(-a)
-0.5 NdCl(+2a)
-1.0
-1.5
-2.0
0 2 4 6 8 10 12 14
C:\HSC6\EpH\NdClFeP1.iep pH
ELEMENTS Molality Pressure

Figure 4 Pourbaix
Nd diagram of the system: 𝐶𝑙 − 𝐹𝑒
1.000E+00 − 𝑁𝑑 − 𝑃 − 𝐻2 𝑂
1.000E+00
Cl 1.000E+00 1.000E+00
Fe
(HSC Chemistry 6.0
1.000E+00
Simulation)
1.000E+00
P 1.000E+00 1.000E+00
Purification of the solutions leached by solvent extraction

Figure 5 shows the influence of the extractant in the organic phase on the recovery of Fe, Nd, Co
and Mn at a concentration of 2 M in n-hexane.
100
Metals extraction in the organic
80
60
phase (%)
40
20
0
HDEHP TBP Hostarex PO Lix 984
224
Iron Neodymium Manganese
Hierro Neodimio Manganeso
Figure 5 Influence of extractant in the organic phase for the extraction of Fe, Nd, Co and Mn at a concentration
2 M in n-hexane (A/O = 1, 15 min)
Analyzing Figure 5, a conflict arises in the use or not of the solvent extraction process. Because it
has a high affinity for Nd but the extraction does not exceed 60 %, it represents rare earth losses to
recover with the presence of Fe. If one of the proposed extractants is selected (the one that
represents the largest extraction); an unnecessary expenditure of resources would be realized, this
involves: extractant, solvent, acid for re-extraction and a possible waste treatment.
7
The solvent extraction process for the purification of Nd from the magnets is not the most adequate
if a previous process is carried out for the removal of Fe from the sample. Furthermore, it is known
that the use of solvents in rare earth recovery is one of the most recent technologies, when there are
two or more lanthanides and actinides in the same mineral due to their similar chemical properties
(Zhang et al., 2015). Due to all of the above, it is considered only as a purification process to the
precipitation with NaOH.
Precipitation tests
The selective precipitation of Nd was carried out by pH control with NaOH. The behavior of
𝑁𝑑𝐻2 𝑃𝑂4 described in the Pourbaix diagram as shown in Figure 4 was considered. The effect of pH
on the precipitation of Nd, Fe, Co and Mn with NaOH is shown in Figure 6.
100
Metals recovery in the precipitate
80
60
(%)
40
20
0
0 1 2 3 4 5 6 7
pH
Hierro
Fe Neodimio
Nd Cobalto
Co Manganeso
Mn
Figure 6 Influence of pH on the precipitation of Fe, Nd, Co and Mn in the leach solution (HCl 100 g/L and 10%
solids)
The highest recovery of Nd (99.9 %) is evidenced from a pH=2, with the presence of Fe, Co and Mn
in concentrations lower than those present in the raw material.
The precipitated solid (pH=2) was calcined and analyzed by XRD. The crystallographic analysis
indicated that the product obtained is neodymium phosphate with a purity of 99 %. The
precipitation process from the secondary leach solution was successful with NaOH. The
commercial price of the compound obtained is approximately 2600 USD/kg (American Elements,
2017).
CONCLUSION
The permanent magnets consists of a mixture of Fe2 O3 , Fe3 O4 , NdFeO3 and Nd(Cr0,6 Mn0,4 )O3 ; and
quantitative chemical composition is: 25,2 % Nd; 57,9 % Fe; 1,4 % Co and 0,4 % Mn. Finding a
significant amount of Nd for your recovery.
Removal of Fe with H3 PO4 as primary leaching agent, at a concentration of 250 g/L, 10 % solids and
24 h, reach 76,8 %; with a Nd loss of 0,02% throughout the process.
8
The HCl as a secondary leaching agent allowed the highest Nd recovery in the concentration range
between 100 g/L and 250 g/L; with a 10 % solids percent a 99,4 % Nd recovery is obtained.
The use of HDEHP as extractant reaches a separation of 60,2 % of Nd and 6,8 % of Fe. The TBP
separated about 44,5 % of Nd, results that are not optimal for its selection as part of the process.
Finally, the analysis of the crystalline phases of the precipitate with NaOH to pH=2 indicates that
the product obtained is neodymium phosphate with a purity of 99 %.
REFERENCES
American Elements. (2017). The World`s Manufacturer of Engineered & Advanced Materials. Merelex
Corporation. 10 884.
Kanazawa, Y. y Kamitani, M. (2006). Rare earth minerals and resources in the world. Journal of alloys
and compounds, 408-412, 1339-1343 (http://dx.doi.org/10.1016/j.jallcom.2005.04.033).
Lee, C., Chen, Y., Liao, C., Popuri, S., Tsai, S. y Hung, C. (2013). Selective Leaching Process for
Neodymium Recovery from Scrap Nd-Fe-B Magnet, 44A, 5825–5833 (http://dx.doi.org/10.1007/s11661-
013-1924-3).
Miura, K., Itoh, M. y Machida, K. (2008). Extraction and recovery characteristics of Fe element from Nd-
Fe-B sintered magnet poder scrap by carbonylation. J Alloys Comp, 408-421:1391-1395.
Merritt, R. (2009). High temperature methods for processing monazite: I. Reaction with calcium chloride and
calcium carbonate. Journal of the Less Common Metals, 166 (2), 197–210
(http://dx.doi.org/10.1016/0022-5088(90)90001-Z).
Muñoz, J. (2011). Separación de La (III), Ce (III), Pr (III) y Nd (III) mediante extracción por solventes
utilizando extractantes organofosforados. Tesis para optar al título de Químico. Chile. 2011-2013.
Ritcey, G. (2004). Solvent Extraction. New York: Elsevier Science Publishers B.V.
Takeshi, I., Ryo, S. y Hideaki, I. (2005). Resource recovery from Nd-Fe-B sintered magnet by hydrothermal
treatment. Journal of Alloys and Compounds, 408, 1382-1385 (doi: 10.1016/jallcom.2005.04.088).
Tanaka, M.., Oki, T., Koyama, K., Narita, H. y Oishi, T. (2013). Recycling of rare earths from scrap.
Pecharsky, V.K. Handbook on the Physics and Chemistry of Rare Earths, 43. 159–211.
Xun, Z. (2002). Mineral Facts of China. Science Press. Beijing.
Zhang, Q. y Saito, F. (2015). Non-thermal process for extracting rare earths from bastnaesite by means of
mechanochemical treatment. Hydrometallurgy, 47 (2–3), 231–241. (http://dx.doi.org/10.1016/S0304-
386X(97)00048-0).
9
A Sustainable Process for the Recovery of Valuable
Metals from Spent LiNi1/3Co1/3Mn1/3O2 Batteries
Liping Xu1, Conghao Sun1, Xiangping Chen2 and Tao Zhou1
1. Central South University, China
2. Shaanxi University of Science & Technology, China
ABSTRACT
Spent LIBs consist of heavy metals, organic chemicals and plastics in the proportion of 5-20%
cobalt, 5-10% nickel, 5-7% lithium, 15% organic chemicals and 7% plastics. Many metals in the spent
LIBs are rare and should be recycled from the point view of economics. Many methods has been
developed for recycling spent LIBs, mainly including pyrometallurgy, biological and
hydrometallurgy processes. Compared with other processes, hydrometallurgy process is
considered as an ideal route due to lower energy consumption, higher recovery efficiency and
purity of metals.
An environment-friendly hydrometallurgical process has been investigated for the dissolution of
Li, Co, Ni and Mn from the cathode active materials of spent LiNi1/3Co1/3Mn1/3O2 batteries. After
pretreatment, the spent LiNi1/3Co1/3Mn1/3O2 was then dissolved using DL-malic acid as the leaching
agent and hydrogen peroxide as the reductant. The optimal leaching efficiency, 98.9%, 94.3%, 95.1%
and 96.4% for Li, Co, Ni and Mn respectively, were obtained at a DL-malic acid concentration of 1.2
M, hydrogen peroxide of 1.5 vol.%, solid–to-liquid (S/L) ratio of 40 g/L, with a leaching temperature
of 80ºC and a leaching time of 30 min. Besides, the leaching kinetic was investigated. Results reveal
that the leaching process (0-10 min) is controlled by chemical reactions and the activation energy
(Ea) for Li, Co, Ni and Mn are 21.3 kJ/mol, 30.4 kJ/mol, 27.9 kJ/mol and 26.2 kJ/mol, respectively. As
the leaching goes on (15~30 min), diffusion becomes the limiting step and the activation energy (Ea)
are 20.2 kJ/mol, 28.9 kJ/mol, 26.3 kJ/mol and 25.0 kJ/mol for Li, Co, Ni and Mn, respectively.
1
INTRODUCTION
Since marketed by Sony in 1991, lithium-ion batteries (LIBs) have been widely used for portable
electronics (Bertuol et al., 2015). LIBs allow higher operating voltage, higher energy density and
longer cycle life (Chen et al., 2015b), which can greatly promote the production and consumption of
LIBs. The LIBs consumption worldwide was about 500 units in 2000 and 4.6 billion in 2010 (Fan et
al., 2016). The continuous increasing use of Li-ion batteries leads to an increased generation of
waste LIBs (Li et al., 2016). Valuable metals in the spent LIBs are rare and should be recycled from
the point of economics view. Besides, spent LIBs can cause potential risk for public health from
both poisonous electrolytes and possible explosion (Chen et al., 2015a). Therefore, recycling of spent
LIBs is not only benefit for environment but may also result in economic benefits (Chen et al., 2016).
Strong inorganic acids (HCl (Li et al., 2009), H2SO4 (Leea and Rhee, 2003) and HNO3 (Swain et al.,
2007) ) were used widely because of their high leaching efficiency. However, due to the emitting of
toxic gases as Cl2, SO3 and NOx during leaching, the focus of research in recent years has turned to
organic acids (Chen et al., 2015c. Sun and Qiu, 2012), which are more environmentally friendly.
Herein, present work will focus on the leaching of waste LiNi1/3Co1/3Mn1/3O2 with DL-malic acid and
H2O2 as leaching reagents. The optimal leaching conditions were obtained through a series of single
factor experiments. Finally, the kinetics aspect of the leaching reaction was also investigated to
determine the reaction rate controlled step.
EXPERIMENT
Spent LiNi1/3Co1/3Mn1/3O2 batteries were firstly discharged by soaking in NaCl solution for 24 h. The
battery components were separated from the LIBs by manual dismantlement and separation. The
cathode was bathed in NMP solvent at 90ºC for 1.5 h, after which step the mixed active materials
could be peeled from the current collector. The powders from the cathode were calcined at 700ºC
for 2 h under atmosphere to remove the impurities (C and PVDF).
RESULT AND DISCUSSION
Characterization of waste LiNi1/3Co1/3Mn1/3O2

The SEM images of the active materials obtained from the cathodes before and after calcination, as
well as the leaching residues recovered from the acid leaching process, are shown in Fig. 1a-c.
Apart from the active materials, large amount of small particles were observed before calcination.
The majority of these particles vanished after calcination at 700ºC for 2 h (Fig. 1b), which can be
explained by the combustion of the conductor carbon and binder and release in the form of gas. The
image of the residue obtained after leaching with DL-malic acid shown in Fig. 1c exhibits a
narrower particle size distribution than that before leaching.
2
a b c
Figure 1 SEM images of the cathodic active materials: (a) waste cathodic materials before calcination; (b)
cathodic materials after calcination; (c) leaching residue
Leaching study
The effect of DL-malic acid concentration was studied under the conditions of 1.5 vol.% H 2O2 , S:L
ratio- 40 g·L-1, leaching time- 30 min and reaction temperature- 80ºC. As revealed by Fig. 2a, the
leaching efficiencies of different metals increase with the increase of DL-malic acid concentration
from 0.5 M to 1.5 M, and a satisfied efficiency over 95% can be achieved for all metals. A sharp
increase in the leaching efficiency can be observed as the DL-malic acid concentration increases
from 0.5 M to 0.8 M, and then followed by a gradual improvement in a range of 0.8-1.2 M. Further
increase of the DL-malic acid concentration cannot show any significant improvement in leaching
efficiency. Hence, the optimal DL-malic acid concentration for the leaching process is 1.2 M.
The effect of the reaction time (5-40 min) was investigated. As shown in Fig. 2b, the time can
remarkably affect the leaching efficiency. Most obvious improvement in leaching efficiency can be
found in the first 10 min. With the reaction goes on, the slope becomes less steep. The leaching
efficiency reaches the maximum after 30 min and do not vary much afterwards. Therefore, 30 min is
selected as the most suitable value for the leaching time.
Fig. 2c illustrates the effect of the leaching temperature on the leaching efficiency. The leaching
efficiency increases from the initial value of around 60% to higher than 90% as the temperature
increases from 50 °C to 80°C. This may be due to the dissociation of DL-malic acid during the
endothermic process. Elevated temperature promotes the process and allows more H+ present in
the solution. When the dissolution is complete, a further increase in the temperature does not
enhance the leaching efficiency in greater extents. Therefore the optimal leaching temperature was
determined to be 80°C.
3
100
100 Li Li
Ni Ni
90 Co Co
Mn 80 Mn
Leaching efficiency (%)

80
70 60
60
40
50
40
20
30 a b
0.4 0.6 0.8 1.0 1.2 1.4
a 1.6 0 10 20 30 40
Acid concentration (mol/L) Leaching time(min)
100 Li
100 Li
Ni Ni
Co Co
90 Mn Mn
80

80 60
40
70
20
60
c d
0
50 60 70 80 90 0.0 0.5 1.0 1.5 2.0 2.5
Leaching temperature(C) Amount of H2O2 (vol. %)
100
90
Li
80 Ni
Co
70 Mn
60
50
40
30
e
20 30 40 50 60
Solid/Liquid (g/L)
Figure 2 Effect of leaching conditions on leaching efficiency: (a) DL-malic acid concentration, (b) time, (c)
temperature, (d) H2O2 volume percent, (e) solid-to-liquid ratio
In this step, the effect of H2O2 concentration on the leaching efficiency of the waste cathode active
materials was investigated. The results (see Fig. 2d) indicate that the amount of H2O2 plays an
important role in the leaching. In the absence of H2O2, the leaching efficiency of the waste
LiNi1/3Co1/3Mn1/3O2 was low. This low leaching efficiency can be attribute to the fact that Li+, Ni2+,
and Co2+ ions can be readily leached under the presence of the acid only while Ni 3+, Ni4+, Co3+, and
Mn4+ would not without a reducing agent. With the addition of H 2O2, the leaching efficiency rose
remarkably and reached above 95% for all the four contents while the H 2O2 content is 1.5 vol.%.
High solid/liquid ratio is usually more desirable in terms of the process throughput. Fig. 2e
indicates that the leaching efficiencies of Li, Co, Ni and Mn increase with the decrease of S:L, and
more than 98% lithium, 94% cobalt, 95% nickel and 96% manganese can be leached at 40 g·L-1.
When the S:L exceeded 40 g·L-1, the leaching efficiency decreases sharply. Taking both the chemical
consumption and leaching efficiency into account, the optimal solid/liquid ratio is therefore
determined to be 40 g·L-1.
4
Kinetic studies
Kinetic studies was conducted to determine the reaction kinetics of leaching lithium,
nickel, manganese and cobalt with the acid under different leaching times (0-30 min) and
temperatures (40-80ºC). At the beginning of the reaction (0 to 10 min), the kinetic data for all the
metals fit satisfactorily to the chemical reaction model regardless of operating temperatures. Fig. 3
indicates that the initial leaching process was controlled by the chemical reaction. As shown in Fig.
4, further increased leaching time to 30 min, the kinetics conforms to diffusion control.
Figure 3 Plots of 1-(1-X)1/3 vs. leaching time at temperatures (50-80ºC) by 1.2 M DL-malic acid solution: (A) Li;
(B) Co; (C) Ni; (D) Mn.
5
Figure 4 Plots of 1-2X/3-(1-X)2/3 vs. Leaching time at temperatures (50-80ºC) by 1.2 M DL-malic acid solution:
(A) Li; (B) Co; (C) Ni; (D) Mn.
CONCLUSION
In this paper, valuable metals in waste LiNi 1/3Co1/3Mn1/3O2 of spent batteries were leached by using
the environmentally friendly malic acid. The optimum leaching conditions are found to be 1.2 M
DL-malic acid, 40 g·L-1 initial S:L ratio, 90ºC, 1.5 vol.% H 2O2 and 30 min and the resulting leaching
efficiencies are Li (98.9%), Co (94.3%), Ni(95.1%) and Mn(96.4%). Kinetics studies revealed that the
leaching process of 0-10 min is controlled by the chemical reaction, while the leaching process (15-
30 min) is controlled by diffusion process. The process may promise an effective and
environmentally friendly route for the leaching of metal values from spent LIBs.
ACKNOWLEDGEMENTS
The authors acknowledge with gratitude for financial support of the Hunan Provincial Science and
Technology Plan Project, China (No.2016TP1007) and National Natural Science Foundation of
China (No. 21176266).
REFERENCES
Bertuol DA, Toniasso C, Jimenez BM, Meili L, Dotto GL, Tanabe EH and Aguiar M.L (2015)
‘Application of spouted bed elutriation in the recycling of lithium ion batteries’, Journal of Power
Sources 275: 627-632.
6
Chen XP, Fan BL, Xu LP, Zhou T, Kong JR (2016) ‘An atom-economic process for the recovery of
high value-added metals from spent lithium-ion batteries’, Journal of Cleaner Production 112: 3562-
3570.
Chen XP, Chen YB, Zhou T, Liu DP, Hang Hu and Fan SY (2015a) ‘Hydrometallurgical recovery of
metal values from sulfuric acid leaching liquor of spent lithium-ion batteries’, Waste Management 38:
349-356.
Chen XP, Xu B, Zhou T, Liu DP, Hu H and Fan SY (2015b) ‘Separation and recovery of metal values
from leaching liquor of mixed-type of spent lithium-ion batteries’, Separation and Purification
Technology 144: 197-205.
Chen XP, Zhou T, Kong JR, Fang HX, Chen YB (2015c) ‘Separation and recovery of metal values
from leach liquor of waste lithium nickel cobalt manganese oxide based cathodes’, Separation and
Purification Technology 141: 76-83.
Fan BL, Chen XP, Zhou T, Zang JX, Xu B (2016) ‘A sustainable process for the recovery of valuable
metals from spent lithium-ion batteries’, Waste Management & Research 34: 474-481.
Leea CK and Rhee KI (2003) ‘Reductive leaching of cathodic active materials from lithium ion
battery wastes’, Hydrometallurgy 68: 5-10.
Li J, Wang G and Xu Z (2016) ‘Environmentally-friendly oxygen-free roasting wet magnetic
separation technology for in situ recycling cobalt, lithium carbonate and graphite from spent
LiCoO2 graphite lithium batteries’, Journal of Hazardous Materials 302: 97-104.
Li JH, Shi PX, Wang ZF, Chen Y and Chang C (2009) ‘A combined recovery process of metals in
spent lithium-ion batteries’, Chemosphere 77: 1132-1136.
Sun L and Qiu KQ (2012) ‘Organic oxalate as leachant and precipitant for the recovery of valuable
metals from spent lithium-ion batteries’, Waste Management 32: 1575-1582.
Swain B, Jeong J, Lee J, Lee G and Sohn J (2007) ‘Hydrometallurgical process for recovery of cobalt
from waste cathodic active material generated during manufacturing of lithium ion batteries’,
Journal of Power Sources 167: 536-544.
7
Selective Extraction of Lithium from Waste Cathode
Materials of Spent Lithium-Ion Batteries using
Phosphoric Acid
Xiangping Chen1,2, Conghao Sun1, Liping Xu1 and Tao Zhou1
1. Central South University, China
2. Shaanxi University of Science & Technology, China
ABSTRACT
A huge amount of spent lithium ion batteries (LIBs) will be inevitably generated with their
extensive application in terms of portable electronics and electric vehicles. On the other hand,
sustainable recycling of valuable metals from these spent lithium-ion batteries may be necessary to
alleviate the depletion of strategic metal resources and potential risk towards the eco-system.
Herein a hydrometallurgical process was proposed to explore the possibility for the selective
extraction of lithium from waste cathode materials (LiCoO 2) of spent LIBs using phosphoric acid as
leaching agent under mild leaching conditions. According to the leaching results, over 99 % Li can
be extracted to the leaching solution by a short-cut process involved merely with leaching and
filtrating under the optimized leaching conditions of 40 oC (T, leaching temperature), 60 min (t,
retention time), 4 vol.% H2O2 (reductant dosage), 20 mL·g-1 (L/S, liquid and solid ratio) and 0.7
mol/L H3PO4 (acid concentration). Then leaching kinetics was investigated based on the logarithmic
rate kinetics model, and the obtained results indicate that the leaching of Li fits well with this
model with high R2 values over 0.95 and the activation energies (Ea) for Li is 10.2 kJ/mol. All the
experimental and theoretical results contribute to an effective extraction of Li from waste LiCoO 2 of
spent LIBs.
1
INTRODUCTION
As an emerging device for energy storage, lithium-ion batteries (LIBs) have been recently
considered as one of the best alternatives for sustainable transport in electric vehicle industry due
to their attractive electro-chemical properties (e.g. high energy density, long service life, modest
size and weight) [1]. However, these batteries will eventually flow into waste stream after several
years of service lifetime (about 1000 charging-discharging cycles) and a huge quantity of spent LIBs
will be generated annually as their extensive applications in portable electronics and electric
vehicles [2-4]. Besides, these end-of-life batteries usually contain a certain amount of heavy metal
and poisonous organic which may present potential threats to the ecosystem and human health [3,
5]. On the other hand, the sustainable recycling of valuable materials (especially high value-added
metals) from these batteries may be an preferable way to alleviate or eliminate the adverse impact
on the environment caused by landfill or incineration method, and it may also promise economic
benefits [6].
Current efforts and concerns are mainly focused on the following technologies concerning the
recycling of metals from these spent LIBs: pyro-metallurgical, hydrometallurgical and bioleaching
methods [7-9]. Among them, hydrometallurgical and bioleaching methods demonstrate significant
superiorities over pyro-metallurgical method in terms of environmental protection and energy
conservation [10-12]. However, hydrometallurgical and bioleaching methods may also present
some drawbacks during the recovery processes. For example, hydrometallurgical method may be
discouraged by tedious recovery procedures (e.g. reductive leaching, solvent extraction, selective
precipitation or their combination) [11], which may complicate the recycling process and enhance
the cost [13]. In addition, it can also be concluded from previous study that bioleaching process
may be frustrating by some undesirable leaching conditions (e.g. rigorous leaching conditions, poor
adaptability) [14]. Therefore, it is necessary to develop a simple process with mild recycling
conditions for the sustainable recovery of valuable metals from spent LIBs.
Recently, there is an increasing interest concentrated on using organic acids (e.g. citric acid[15, 16],
succinic acid[17], malic acid[18]) as eco-friendly leaching reagents instead of strong mineral acids
(e.g. H2SO4[19], HCl[20], HNO3[21]). Table 1 briefly summarizes different leaching systems for the
recovery of metals from spent LIBs. It can be observed that organic acids present similar leaching
performances as mineral acids, and these mild acids may effectively alleviate adverse impacts on
environment during leaching. For example, oxalic acid[22], ascorbic acid[23], citric acid[15] and
succinic acid[17] all show similar leaching performances as the typical mineral acids (i.e. H2SO4[19],
HNO3[21], HCl[20]). Although organic acids can be efficient and eco-friendly alternatives instead of
mineral acids, their industrialized applications may be discouraged by their relatively high prices
and difficulties in terms of the separation and recycling of metals from the leaching solution [8].
2
Table 1 A brief summary of different leaching systems
Type of acid Leaching Leaching Sample Leaching References

conditions
system rate
H2SO4 2 M H2SO4, LiCoO2 94% Li, [2, 8, 21]
& H2O2 5 vol.% H2O2, 93% Co.
40 min, 75oC,
S/L = 100 g L-1.
Mineral acid HNO3 1 M HNO3, LiCoO2 >95% Li, [7, 8]
& H2O2 1.7 vol.% H2O2, >95% Co.
30 min, 75oC,
S/L = 20 g L-1.
HCl 4 M HCl, LiNi1/3Co1/3 [20]
60 min, 80oC, Mn1/3O2
S/L = 20 g L-1.
H2C2O4 1.5 M H2C2O4, 120 LiCoO2 >98% [22, 26]

min, 80 C,
o
& H2O2
S/L = 50 g L-1.
1.25 M C6H8O7, 1.0

Citric acid vol.% H2O2, LiCoO2 100% Li, [8, 15]
& H2O2 30 min, 90oC, >90% Co.
S/L= 20 g L-1.
1.25 M C6H8O6, 20
3
Organic acid Ascorbic acid min, 70oC, LiCoO2 98.5% Li [23]
S/L = 25 g L-1. 94.8% Co
1.5 M C4H5O6, 4.0

vol.% H2O2,
DL-malic acid & LiCoO2 60% Li [18]
H2O2 40 min, 90 C,
o
60% Co
S/L = 20 g L . -1
1.5 molL-1,
Succinic acid 4 vol.% H2O2,

LiCoO2 100% Co, [17]
& H2O2 S/L = 15 gL , -1
70oC, 40 min. 96% Li.
Therefore, this study will be concentrated on exploiting a hydrometallurgical process to solve the
above issues in terms of the secondary pollution, difficulty in separation process and relatively high
investment. Phosphoric acid (H3PO4) was innovatively adopted as leaching agent to separate and
recover Li from the waste LiCoO2 after pretreatment of spent LIBs. Expectedly, Co and Li can be
separated and recovered as Co3(PO4)2 precipitate and Li+ in leaching solution by a single leaching
step. Leaching conditions optimization and leaching kinetics investigation were conducted to
investigate the possibility of using phosphoric acid to recover Li from waste LiCoO2 of spent LIBs.
EXPERIMENTAL
Pretreatment of spent LIBs

Spent LIBs were kindly provided by a local battery recycling center (Changsha, China) and these
batteries are commonly pre-treated before metal recycling process. As shown in Fig.1, the
main pre-treatment steps include (A) the manual dismantling process and (B) the peeling off
Al/Cu foils and thermal & mechanical treatment. Firstly, spent batteries were immersed in
an electrolyte solution (10 % Na 2SO4, w/v) for 24 h to discharge the remained electricity, and
then washed with deionized water and dried at 90 oC for 12 h. Then, these batteries were
manually dismantled into plastics, metallic shells, separators, anodes and cathodes.
Afterwards, anodes and cathodes foils (cut into 1×1cm pieces) were immersed in NMP (N -
methyl-2-pyrrolidone) at 90 oC for 2 h to dissolve PVDF binder and detach Al/Cu foils from
4
active materials (a mixture of C and LiCoO 2). Finally, the active materials were filtrated,
dried and ground into smaller particles (i.e. LiCoO 2), which will facilitate the leaching
reaction. After pre-treatment, plastics, metallic shells, separators and Al/Cu foils can be
directly recycled as their original forms, and waste LiCoO2 obtained will be used as raw
materials for leaching.
Materials and reagents

In this study, only spent LiCoO2 based spent LIBs (cell phone batteries) were selected as the
source materials and the active materials are a mixture of C and LiCoO 2. Waste LiCoO2
powders (particle size < -0.075 mm) used in this study can be obtained after the pretreatment of
spent LIBs. A fixed amount (~1.0 g) of waste LiCoO 2 was completely dissolved in concentrated
hydrochloric acid (10 mol/L HCl) and the contents of different metals in solution were then
determined by ICP-OES. Table 2 lists the detailed contents of different elements in the waste
LiCoO2. Phosphoric acid (H3PO4), hydrogen peroxide (H2O2) and other chemicals used in this study
are analytical purity and they were purchased from Sinopharm Chemical Reagent Co., Ltd. All
leaching agents and precipitates were prepared or washed using de-ionized water.
Al foils
A B
Cathode Separator
Cu foils
Spent lithium ion batteries Anode Metallic shell
Waste LiCoO2
Figure 1 The main pre-treatment procedures for spent LIBs (A - manual dismantling process; B-
peeling off, thermal and mechanical treatment).
5
Table 2 Detailed contents of different elements in waste cathode materials
Element Mass content (wt.%)
Li 6.69
Co 58.11
Ni 0.39
Mn 0.14
O 34.55
Others 0.12
Leaching experiments
All the leaching experiments were carried out in a 250-mL, three-necked and round- bottomed
flask equipped with impeller stirrer, vapour condenser, heating device and other supporting
appliances. During the leaching experiments, we mainly investigated the effects of retention
time (t, min), reaction temperature (T, oC), reductant dosage (V H2O2, vol.%), pulp density (L/S,
mL·g-1) and concentration of phosphoric acid (C H3PO4, mol/L) on the leaching of Li. Cobalt and
lithium ions were separated and recovered as Co3(PO4)2 precipitate and soluble Li+ in leaching
solution, respectively. In this study, a designed orthogonal table L16(45) was selected to explore
the optimal leaching conditions, in which 5 factors with 4 levels were studied during leaching.
The recovery efficiencies for Li can be calculated according to Eq. (1):
R = m’/m × 100% (1)
where R is the recovery rate of Li; m’ and mo are the weights of metal recovered in waste
LiCoO2.
Leaching kinetics
Initially, shrinking core model was employed to investigate the leaching kinetics of Li from the
waste LiCoO2. However, the fitting degrees for Li (R2 values) are relatively low (below 90 %)
according to the fitting results, which may be attributed to the oxidation- reduction
phenomenon during the leaching reactions (LiCoO 2 and H2O2 as oxidant and reductant,
respectively) [24, 25]. Therefore, the logarithmic rate law model was adopted to investigate the
leaching kinetics of Li instead [24]. The logarithmic rate law can be described as Eq. (2).
(-ln(1-x))2 = k·t (2)
where x is the fraction reacted in leaching time t (min) and k is the specific rate constant for the
empirical model.
6
In addition, a good applicability can be obtained for Arrhenius equation during leaching
within an inconspicuous temperature variation during leaching [25]. Therefore, the curve of
lnk vs. 1/T was plotted to explore the relationship between leaching temper ature and reaction
rate constant and to predict the apparent activation energies (Ea) for Li in the leaching
reactions.
Analytical methods
Metal concentrations in solution were determined by Inductively Coupled Plasma Optical
Emission Spectrometer (ICP-OES Optima 2100 DV, Perkin Elmer instruments, U.S.A.). Three
parallel experiments were conducted in the whole recovery process and the mean values of the
experimental results would be taken as the final results to avoid random errors.
Thermodynamics analysis
As a commonly-used acid, one molar phosphoric acid (H3PO4) can potentially release three molars
H+ in aqueous solution, which is equivalent with citric acid (H3Cit) as reported by Li et al. [15]. In
addition, both Co2+ and Li+ can be precipitated as Co3(PO4)2 and Li3PO4 in the presence of PO 43-,
while excessive H3PO4 may further dissolve the above two precipitates to water-soluble compounds
of Co(H2PO4)2 and LiH2PO4, which is considerably similar with the oxalic acid (H 2C2O4) leaching
system investigated by Sun and Qiu [22]. Besides, it can be also concluded from the ionization
constants of phosphoric acid that H3PO4 presents a mild acidity (pKa1 = 2.12). Based on the above
analysis, it may be assumed that the colorless H3PO4 can be applied as an efficient leaching and
precipitating agent to separate and recover Co as Co3(PO4)2 precipitate from waste LiCoO2 due to
its similar chemical properties with H2C2O4. Possible reactions can be divided into the following
two steps, including (A). The generation of Co3(PO4)2 and Li3PO4 precipitates (Reaction. i-ii) and
(B). The dissolving of the above two precipitates to dissolvable Co(H2PO4)2 and LiH2PO4 (Reaction.
iii-iv).
LiCoO2(s) + 3H+(aq) + H2O2(l) = Co2+(aq) + Li+(aq) + 3/2H2O(l) + 1/4O2(g) i
Co2+(aq) + Li+(aq) + PO43-(aq) = 1/3Co3(PO4)2(s) + 1/3Li3PO4(s) ii
Li3PO4(s) + 6H+(aq) + 2PO43-(aq) = 3Li+(aq) + 3H2PO4-(aq) iii
Co3(PO4)2(s) + 12H+(aq) + 4PO43-(aq) = 3Co2+(aq) + 6H2PO4-(aq) iv
Herein, thermodynamics analysis was firstly conducted to explore the reaction trend for the
leaching of Co and Li by phosphoric acid in the presence of H2O2. Based on the thermodynamic
data calculated and the Gibbs-Helmholtz equation, theoretical calculation was then carried out to
obtain the values of ∆rHmθ, ∆rSmθ and ∆rGmθ to predict the trends for different leaching reactions [26].
It can be discovered from the calculated results that all values of ∆rGmθ are below zero (-1892, -380, -
499 and -687 kJ·(K·mol)-1), indicating that Reaction. i-iv are spontaneous chemical reactions and
7
both Co3(PO4)2 and Li3PO4 can be generated firstly and then dissolved under the excessive
phosphoric acid conditions.
Then our purpose would be to obtain as much as possible of Co3(PO4)2 precipitate and Li+ in
solution, which may be attained by controlling the leaching conditions to promote the desired
reactions (Reaction. i-iii) and prevent the undesired one (Reaction. iv). Therefore, following work
will be focused on uncovering and investigation of leaching conditions for the effective separation
of Co and Li from waste LiCoO2 in phosphoric acid medium.
Orthogonal experiments
To obtain the optimal experimental conditions, all leaching experiments were conducted based on
the designed orthogonal experiment table and the effects of reaction temperature (T), retention time
(t), reductant dosage (RD), liquid-solid ratio (L/S) and acid concentration (C) on the leaching of Co
and Li from waste LiCoO2 were investigated. Table 3 shows the detailed leaching results and
corresponding analysis of the obtained results. It can be observed that both Co 2+ and Li+ ions are
found in the leaching liquor, indicating that LiCoO2 can react with phosphoric acid in the presence
of H2O2. Besides, it can also be discovered that different concentrations of Co 2+ can be obtained
under different leaching conditions while most of Li + ions can be dissolved in the leaching solution
under all leaching conditions. This phenomenon may be attributed to the formation of Co3(PO4)2
precipitate at controlled experimental conditions [26]. Based on above analysis, it may suggest
that Reaction i-ii occur with the addition of H 3PO4 and H2O2, and Co3(PO4)2 and Li3PO4
precipitates can be further dissolved in excessive H 3PO4 solution (Reaction. iii-iv).
Furthermore, it can also be concluded from the leaching results that most of Li can be easily
leached in phosphoric acid medium at different leaching conditions, and high precipitation
efficiency of Co 2+ can be achieved at specified conditions (For example, over 99 % at No. 7, 13,
14, 15), confirming that Li 3PO4 is much more easily to be dissolved than Co 3(PO4)2 and Co and
Li can be separated according to their solubility differences in the phosphoric acid solution by
controlling leaching conditions.
Then the analysis of priority order and optimal level were carried out to explore effects of
different parameters on leaching and obtain the optimal experimental conditions[27].
8
Table 3 Results of the designed orthogonal experiments and corresponding analysis
No. t (min) T (oC) VH2O2 L/S CH3PO4 wLi wCo Recovery rate (%)
(vol.%) (mL·g-1) (mg·L-1) (mg·L-1)

(M) Li
1 30 40 1 15 0.5 759 4744 36.5
2 30 50 2 20 0.6 1335 2563 84.5
3 30 60 3 25 0.7 1929 383 99.9
4 30 70 4 30 0.8 1908 3613 99.9
5 40 40 2 25 0.8 1494 10170 99.5
6 40 50 1 30 0.7 1317 9001 99.8
7 40 60 4 15 0.6 1523 0.7 78.2
8 40 70 3 20 0.5 1348 20 74.8
9 50 40 3 30 0.6 1607 55 99.9
10 50 50 4 25 0.5 1345 6 92.3
11 50 60 1 20 0.8 1680 9115 85.3
71.5
12 50 70 2 15 0.7 1260 1.8
99.9
13 60 40 4 20 0.7 1829 47
76.7
14 60 50 3 15 0.8 1352 18.9
93.2
15 60 60 2 30 0.5 944 4.5
75.4
16 60 70 1 25 0.6 1192 3707
Analysis Effects of different parameters Priority order & optimal level analysis
K1 317.0 292.8 211.0 372.8 372.8 Priority order:
K2 239.9 300.4 301.1 326.0 352.7 VH2O2 > CH3PO4 > t ≈ L/S > T.
9
K3 344.9 342.2 395.9 289.5 316.2 Optimal level:
K4 371.8 338.2 365.6 285.3 231.9 Reaction temperature: 40 oC;
k1 79.3 73.2 52.8 93.2 93.2 Retention time: 60 min;
k2 60.0 75.1 75.3 81.5 88.2 Reductant dosage: 4 vol.% H2O2;
k3 86.2 85.6 99.0 72.4 79.1 Liquid-solid ratio: 20 mL·g-1;
k4 93.0 84.5 91.4 71.3 58.0 Acid concentration: 0.7 M H3PO4.
*ED 23.0 12.4 46.2 21.9 35.2 * ED: Extreme deviation.
It can be discovered that the priority order presents in following order: VH2O2 > CH3PO4 > t ≈ L/S > T,
and the optimized leaching conditions are reaction temperature of 40 oC, retention time of 60 min,
reductant dosage (H2O2) of 4 vol.%, liquid to solid ratio of 20 mL·g -1 and acid concentration of 0.7
M. Over 99 % of Co and Li could be separated and recovered as Co3(PO4)2 precipitate and
LiH2PO4 solution under the optimized leaching conditions.
Leaching kinetics
Leaching kinetics was investigated to explore the leaching behaviors of Co and Li from waste
LiCoO2 at different leaching times (30-150 min) and temperatures (40-80 oC) at controlled conditions
of reductant dosage- 4 vol.%, liquid to solid ratio- 20 mL·g-1 and acid concentration- 0.7 M.
Logarithmic rate law model (see Eq. (2)) was adopted to investigate the leaching kinetics of Co
and Li. Then apparent activation energy (Ea) can be obtained according to the slope of lnk vs. 1/T
curve (based on Arrhenius equation), which can also be adopted to evaluate the difficulties of
relevant reactions.
According to Fig. 2, the leaching of Co and Li fits well with the logarithmic rate law model. And
the fitting degrees (the values of R2) of Li are over 0.96. This indicates that the logarithmic rate
law model can work well in the oxidation-reduction reactions (reductive leaching of waste
LiCoO2). The unsatisfied fitting degrees in shrinking core model may be caused by the different
oxidation states of Co before and after leaching (i.e. Co(III) in LiCoO2 and Co (II) in Co3(PO4)2) [28].
10
4
40 oC, R2 = 0.96
50 oC, R2 = 0.96
60 oC, R2 = 0.98 -5.0
3
70 oC, R2 = 0.98 2
R =0.920 y=-1.223x-1.540
80 oC, R2 = 0.97
-1
(-ln(1-x))2
ln k, min
2 -5.2
1
-5.4
2.8 2.9 3.0 3.1 3.2

0 30 60 90 120 150
3
Leaching time (min) 1/T (10 ), K
Figure 2. Kinetic studies as a function of leaching Figure 3. Arrhenius plots for the leaching of Li from
time and temperature for Li under logarithmic waste LiCoO2 in the temperature range of
rate kinetics model. 313-353 K.
Fig. 3. shows the plot of lnk vs. 1/T under the leaching conditions of retention time- 60 min,
reductant dosage- 4 vol.%, liquid to solid ratio- 20 mL·g-1 and acid concentration- 0.7 M. It can be
observed that the plot of lnk vs. 1/T for Li presents a relatively good fitting degree (0.920).
Activation energy value (Ea) based on the Arrhenius plots is 10.168 kJ/mol for Li in a temperature
range of 313 -353 K. The relatively low activation energy values can further confirm that the
leaching reactions can be easily promoted using phosphoric acid as leaching and precipitating
agent, and high yield of Li can be achieved even under mild leaching temperature (e.g. 40 oC).
Recovery of Li from leaching solution

After leaching and filtration, the leaching solution is a mixture of Li + and unreacted phosphoric acid
and Co can be directly recovered as Co 3(PO4)2 precipitate from. Waste H3PO4 and Li+ should be also
recycled or reused for the sake of comprehensive recovery of valuable metals and waste
minimization. As previously reported by Li et al. [29], a kind of spinel λ-MnO2 ion-sieves with high
selective adsorption capacity toward Li+ was used for the recovering of Li+ from leaching solution of
spent LIBs. Besides, Li+ can be easily precipitated by some other precipitants such as sodium
carbonate, ammonium oxalate. Hence the repeated recycling experiments for Li will not be carried
out in this study, and its recycling or reuse may be explored in our future work.
CONCLUSIONS
In this study, a novel leaching process was explored and established for the effective extraction of
Li from waste LiCoO2 by phosphoric acid under mild leaching conditions. Based on the results,
over 99% of Li can be leached in leaching solution according to results obtained from orthogonal
experiments (including corresponding analysis). And the optimized leaching conditions are
reaction temperature- 40 oC, retention time- 60 min, reductant dosage- 4 vol. % H2O2, liquid to solid
ratio- 20 mL·g-1 and acid concentration- 0.7 M. The leaching kinetics model of Li fits well with the
11
logarithmic rate law model, with high fitting degrees (R 2) over 0.96. In addition, activation
energy value (Ea) for Li is 10.168 kJ/mol in the temperature range of 313 -353 K.
ACKNOWLEDGEMENTS
The authors acknowledge with gratitude for financial support of the Fundamental Research Funds
for the Central Universities of Central South University (No. 72150050350) and National Natural
Science Foundation of China (No. 21176266).
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13
CHAPTER 9
Treatments of Acid
Drainage and Mine
Waters
Underground Acid Drainage Treatment in Mina San
José Oruro
Gerardo Zamora, Elvis Trujillo and Milton Salas
Universidad Técnica de Oruro, Bolivia
ABSTRACT
Different treatments for the Acid Mine Drainage were tested and compared for San Jose Mine in
Oruro. In fact the AMD is being discharged to environment directly to the Uru – Uru Lake. It´s
AMD is very acid (pH from 1.2 to 2.5) and has large contents of heavy metals. The flowrate is 8 L/s
(690 m3/day)
The objective of the present experimental work was to find the best technical, environmental, and
economical treatment of AMD. The options tested at laboratory and plant scale were: evaporation,
crystallization, neutralization, precipitation with calcite at the surface, anoxic calcite drainage and
underground neutralization-precipitation in mine. The technological, economical, environmental
and social aspects were assessed and compared each other.
The best solution was the in mine underground treatment. It was performed in a abandoned mine
gallery. 6.9 tons of lime were used. The treated water overflow at pH level of 6.7. It was pumped to
the surface level and in most cases the heavy metals had contents at a lower level than the
environmental regulations limits. The formed sediments was discharged continually with a mud
pump and will be disposed in abandoned underground tunnels 150 m away.
The costs were around 300,000 US$ (three hundred thousand), and the operational costs are around
386,000 US$ yearly.
1
IN MINE UNDERGROUND ACID MINE DRAINAGE TREATMENT
INTRODUCTION
Acid Mine Drainage, called Copagira-water in Bolivia, is caused by a natural oxydation of sulfide
minerals in contact with water and oxygen, catalyzed by Thiobacillus Ferroxidans. This acidic
reaction leaches heavy metals from the minerals (PPO 1996).
Water flows transports these heavy metals directly to the environment. AMD is the main heavy
metal and acid pollution source in mining regions (Dames & Moore Norge, 2000)
San Jose Mine, located at Oruro City at 4032 meters above sea level, is a Pb-Ag-Sb sulfide deposit
and produces a strong acid AMD (pH of 1.2 to 2.5 (Perry 1999, Zamora 1999).
The deeper levels of the mine have to be drained, to allow for mineral exploitation. Therefore
around 8 L/s (690 m3/d) of AMD has to be pumped out. Also there are uncontrolled infiltrations of
AMD to underground (Zamora 1999).
The pumped AMD reaches the City and damages the wastewater sewage, and discharges in the
Uru Uru lake, without being treated.
The AMD from San Jose Mine carries yearly 1,1600 tons of solids yearly and 1 t of Cd, 11 t of Cu, 14
t of Pb, 13 t As, 0.3 t of Sb, 22 t of Zn and 760 t of Fe. (Ignacio 2000).
The quality of the water in the Uru Uru Lake is poor and varies between the rain and dry periods
and is directly affected by the AMD, for instance in the pH, heavy metal content, and sulfate
content
Table 1 Quality of water in Uru Uru Lake
Rain fall period Dry period
Conductivity mS/cm 4.66 57
Total dissolved solids g/L 2.34 28.60
SO4 mg/L 500 4000
As mg/L - 0.09
Sn mg/L 0,2 0.6
Pb mg/L 0.08 0.1
Cd mg/L 0.02 0.05
Co mg/L 0.08 0.15
Ni mg/L 0.12 0.15
2
The aim of this study was to compare different treatments and select the most favourable one for
San Jose´s AMD.
TREATMENTS
The type of treatments compared were:
 Solar water evaporation and dissolved salts crystallization
 Lime neutralization and dissolved salts precipitation at surface
 Anoxyd Calcium Carbonate neutralization and dissolved salts precipitation at surface
 Underground neutralization and precipitation
Evaporation and crystallization (quezada 2000)

Water is the major component in AMD by volume. Separating water from AMD withdraws the
heavy metal´s transport medium. Dry environments favor the natural evaporation. Also San Jose´s
high solar radiation can help water evaporate faster.
Large pools of AMD were left to natural evaporation. The salts dissolved precipitate and
crystalized as less soluble sulfates (acicular gypsum CaSO4:2H2O and fine powder anglesite PbSO4),
ocher iron incrustations (jarosite KFe3(SO4)2(OH)6 , hydroniumjarosite H2Fe3(SO4)2(OH)7,
natrojarosite NaFe3(SO4)2(OH)6 goethite -FeOOH, and minor amounts of Fe(OH)2.7Cl0.3 and
Fe(OH)3 ) and sodium chloride (cubic NaCl).
Conventional at surface level neutralization and precipitation

The treatment uses lime to rises pH. Under these conditions precipitates iron hydroxides and
calciumsulfates. Before the treatment a separation of the sediments have to be performed. But the
strong acidity hampers the separation. The best way is to settle down the AMD and separate them
as a high density sediment.
The addition of lime elevates the pH to 6.7, and achieves an effluent satisfying the bolivian
environmental regulations on heavy metal allowable contents (Zamora 1996).
The lime consumption is displayed in the following table:
Table 2 Lime consumption for conventional at surface level neutralization and precipitation
Lime consume pH of treated

kg/m 3 effluent
8.5 6.0
11.0 9.0
3
Reduction and alcalinity generation
The AMD of San Jose Mine has very high acidity and sulfate contents that hampers the treatment
with anoxic limestone drains (ALD) (Ahmed 2000, Hedin 1994, Faulkner 1994, Nairn 1992).
Preliminary test had to be performed.
Underground neutralization and precipitation

The treatment with lime elevates the pH levels and precipitates sulfates and heavy metals as
known, but the innovation to conduct the treatment in the underground mine allows handle the
strong acid, AMD, and permits the final sediments to be deposited in a unique new way.
The system was tested at a small scale and also at pilot scale in Santa Fe mine.
A stirring tank mixes lime and water to prepare a lime suspension. The lime is added to the AMD
stream that discharges to a underground pool of 83 m3 to treat 221.4 m3/h (61.5 L/s). The residence
time was 0.38 h (23 minutes)
The effluent at the end of the pool is pumped out of the mine. It has a pH of 6 and can be used as
irrigation in agriculture.
The sediments are purged discontinuously from the bottom of the pool and flows down to final
deposition in abandoned mine galleries.
San Jose mine produces 28.8 m3/h (691 m3/day) of AMD. To elevate the pH to 6.0 the consumption
will be 10 kg of lime / m3 of AMD. The effluent can be used for sanitary purposes (bath) as well. The
different treatments were assessed despite of:
 Technical operability (technical difficulties, installation time, requirements of maintenance,
difficulties of operation and system failures)
 Costs (investment, operation, Underground neutralization and precipitation , administration
and closure)
 Environmental impacts (solid residues, reusability of water, decontamination efficiency,
environmental impacts, chemical and physical rehabilitation)
 Social (benefits, risks, future health impacts, employment and social acceptance)
RESULTS
Evaporation and crystallization treatment

San Jose mine is located on a mountain, with high slopes and near a human settlement,
consequently there is no availability of the surface needed in the vicinity. The next possibility
would be 10 km away.
The surface needed to evaporate 28.8 m3/h (8 L/s) was calculated to 44 Ha.
The construction of the transport facilities, and evaporation pools were estimated to 3.5 million US$
and the operational cost 57,700 US$.
4
Conventional on ground neutralization and precipitation
The treatment of 28.8 m3/h (8 L/s) San Jose AMD would need:
Stirring tank to prepare the lime slurry
Volume = 4.9 m3, high = 3 m, diameter = 1.4 m
Rector stirring tank
Volume 18 m3, high = 3.5 m, diameter = 2.6 m
Clarifier to settle down sediments
Volume= 13.3 m3, high 3 m, diameter 4.09 m
The produced sludge sediments contains high heavy metal contents and toxicity. According to 40
CFR 261.30 (EPA 1312) they are not chemical stable and the final deposition demands additional
efforts.
The investment costs could rise to 520,000 US$ and a yearly operational cost of 820,000 US$.
Reduction and alcalinity generation

Experimental test indicates that the treatment of 28.8 m3/h AMD (8 L/s) for a time of treatment of 20
years will need 2347.7 ton of limestone.
The anoxic limestone drain would be 61.1 m long and 12 m width (large: width relation 5.09 : 1) ,
the thickness will be 2 m.
The investment cost would be 300,000 US$.
The alcalinity of the effluent rises to 132 mg/L after the first 48 h of contact with AMD, but after 192
hours the alkalinity lowered to 6 mg/L.
200
180
160
Alcalinity in mg/lt
140
120
100
80
60
40
20
0
0 50 100 150 200 250 300 350
Time in h
Figure 1 Variation of alcalinity over time
5
The lowering of alcalinity is due to obstruction of the limestone by the sulfates precipitated. This
makes this treatment for San Jose AMD not viable.
Underground neutralization and precipitation

The treatment of 28.8 m3/h (8 L/s) San Jose AMD would need 691.2 kg/day (10 kg/ m3) of lime.
The treatment was realized in a 340 m deep underground mining gallery, 105 long, 2.2 m width and
1.8 m high. The volume of the drift was around 415 m3. This drift was sealed to be used as a reactor
to treat the AMD of the mine with lime. The precipitated sludge will be pumped sequentially to
open abandoned shafts. The sludges hardens sealing the abandoned shafts.
The treated water had a pH of 6 and is pumped to the surface and can be used for irrigation and
sanitary purpose.
The investment costs are 280.000 US$ and the operational costs are 380,000 US$ yearly.
The comparison shows that the most suitable treatment of AMD in the case of San Jose mine is the
treatment in underground facilities.
THE FINAL PROJECT

After a geotechnical evaluation a suitable mining gallery was selected for the construction of a pool
inside. Its reactions with lime, precipitation and sediment were studied and tested. Hydrological
studies for AMD and treated effluents and sediments were performed. Also the hardening of the
sediments were important to the geochemical stability of the final deposition in the shafts.
The constructions needed were:
1) A pond for the mixture of AMD with the lime suspension. The pond was formed by two dykes
separating a section of an underground gallery.
The two trapezoidal dykes were made of reinforced concrete of 1.4 m width at the basis and 0.7
m at the top side. The high was 1.9 m. The dyke thickness was 0.3 m.
Steel bars were anchored in the floor of the gallery.
A deflection baffle was installed 6 m away from AMD entrance to disrupt the turbulence and
favor sedimentation.
2) Reinforcement of the drift walls with wooden balk frames of 6 x 8 inches with a separation of 5
m.
The treated water effluent are discharged by a pump of 30 HP, with a capacity of 90 m3/h (25 L/s)
The precipitated sediments are discharged discontinuously by a 30 HP pump with a capacity of 36
m3/h (10 L/s). The sediments are pumped to abandoned shafts 340 m deep 200 m away. The solid
content is 24.3 %
The treatment capacity was 691.2 m3/day (8 L/s)
The lime consume was 691.2 kg/day (10 kg/ m3) of lime.
The lime suspension had 100 g/L.
The treated water effluent has a pH of 6.7 and have heavy metal contents lower than the acceptable
limits.
The estimated sedimentation time is 25 minutes.
6
IMPACT
The region around San Jose Mine is a dry and arid one. There are two lakes nearby, which are
threated by heavy metal contamination and acidity from the AMD discharges. The principal
pollutants are Cd, As, Sb, Pb, Ni, Co, Cu, Fe y Zn.
The treatment of AMD from San Jose mine is important in order to preserve the scarce bodies of
water and the biodiversity surrounding it.
Also, social and economical activities depends on the availability of high quantity and quality of
water.
This new treatment innovation was implemented at San Jose Mine in June of 2016, financed by the
environment protection Project of the Poopo Basin of the European Community.
REFERENCES
Ahmed M., Shayya, W., Hoey, D., Mahendran, A., Morris, R., Al-Handaly, J., 2000, Use of
evaporation ponds for brine disposal in desalination plants, Desalination Volume 130, Issue 2.
Dames & Moore Norge, 1999, Feasibility and design study for the remediation of sources of
contamination, San Jose Mine, Subproject Nº 6, Progress Report. Oruro.
Dames & Moore Norge, 2000, ’Definición del Plan de Remediación Global’, “PMAIM Suproyecto 6
– Informe Final No.3. La Paz 2000.
Dames & Moore Norge, 2002, ’Estudio de ingeniería, factibilidad y diseño para la remediación de
las fuentes de contaminación de la Mina San José de Oruro’, Sub Proyecto Nº 6, Estudio de
Evaluación de Impacto Ambiental, Informe final.
Faulkner, B.B. and J.G. Skousen. 1994. Treatment of acid mine drainage by passive treatment
systems. International Land Reclamation and Mine Drainage, Third International Conference on the
Abatement of Acidic Drainage, Pittsburgh, PA. pp. 250-256.
Hedin, R.S. and G.R. Watzlaf. 1994. The effects of anoxic limestone drains on mine water chemistry.
international land reclamation and mine drainage, Third International Conference on the
Abatement of Acidic Drainage, Pittsburgh, PA. pp. 185-194.
Ignacio, G., 2000, Tratamiento de aguas acidas de mina, proyecto de grado. UTO-FNI, Oruro.
Nairn, R.W., Hedin, R.S. and G.R. Watzlaf. 1992. Generation of Alkalinity in an Anoxic Limestone
Drain. Achieving Land Use Potential through Reclamation, Annual Meeting of the American
Society for Surface Mining and Reclamation, Duluth Minnesota. pp. 206-219.
Perry, R. H., Green, D. W. y Maloney, J. O., 1999, Perry’s Chemical Engineers’ Handbook, McGraw-
Hill. USA.
PPO (Proyecto piloto Oruro), 1996, Evaluación de la contaminación de ríos y lagos, Oruro.
Zamora, G. y Quezada, R., 2003, Aplicación de la evaporación - cristalación como alternativa de
tratamiento de aguas ácidas de mina, UTO, 2003.
7
Zamora, 1999, G. ’Aplicación de Aguas Ácidas de Mina en Procesos de Lixiviación’. Revista
Metalúrgica Nº19, Oruro.
Zamora, G. 1996, ’Posibilidades fisico - químicas para la eliminación de elementos tóxicos de
efluentes’. II Congreso Nacional de Metalurgia y Ciencia de Materiales. Oruro.
8
Adsorption: an Interesting Hydrometallurgical
Option to Remove Ions from Mine Waters
Fernando Valenzuela1, Carlos Basualto1, Gonzalo Montes2, Viviana Ide 1 and Geraldine
Quintana1
1. Laboratorio de Operaciones Unitarias, Universidad de Chile
2. Minerals and Metals Characterisation and Separation (M2SC) Research Group, Universidad de
Chile
ABSTRACT
Undoubtedly, one of the most promissing hydrometallurgical alternatives for removal of ionic
pollutants from acidic aqueous solutions are adsorption methods due to their simplicity of use and
availability of many different types of natural and synthetic adsorbents. Many adsorbents have very
different properties and adsorption capabilities but their applicability is limited by cost, being
unpractical and/or uneconomical, which precludes in their implementation into industrial
applications. In general, inorganic adsorbents (oxides and salts) are more convenient to use than
biological agents because of their stability in highly acidic oxidising environments. This stability is
due to their chemical composition and structure. However, their use is limited as they are sensitive
to many variables, including the pH and the ionic strength of the solution to treat, the concentration
of the adsorbate in the aqueous phase and on the size and condition of their surface area. Normally
they are incapable of adsorbing cations and anions simultaneously. Furthermore, it is often very
complicated to separate the spent adsorbent loaded with contaminants from the raffinate solution
due to their small particle size and colloidal character. There is a strong need for adsorbent materials
that have the capacity for removing both anions and cations simultaneously from industrial and
mining solutions.
In this communication, we are describing the synthesis, characterization and application of magnetic
nano-structured calcium silicate hydrates, to be used as adsorbent to remove simultaneously several
ions (heavy metals and oxyanions) from acidic aqueous mine solutions. Magnetic saturation
measurements demonstrated that the nano-structured particles have superparamagnetic
characteristics which allow separating the contaminant-loaded adsorbent particles from the treated
aqueous solution using conventional magnets. Effectively, these adsorbents showed a high efficiency
to decontaminate the treated acidic mine waters.
Acknowledgements: The authors wish to thank to The National Fund for Development of Science
and Technology of Chile, FONDECYT, for financial support given to this research through Grant N°
1140331.
1
CHIEF EDITOR
Fernando Valenzuela
Professor of Unit Operations and mining and metallurgical chemistry at Universidad de Chile. He is a
chemist and has a Master,s degree in Chemical Engineering from Kyushu University, Japan. He is author
of 85 ISI scientific publications, chapters of books and international patents on mining wastewaters
processing. Today is a member of the PhD in Chemistry staff meeting of his university and holds the position
of Academic Director of his Faculty.
EDITORS
Jesús Casas
Senior Consultant working in extractive metallurgy for the mining industry. He is a Chemical Engineer
and has a PhD in Chemical Engineering Sciences from Universidad de Chile. He is a qualified person in
mining resources and reserves, area mineral processing. He is editor of international proceedings, reviewer
of papers and projects, author of scientific publications and engineering project reports on chemical and
metallurgy. He is also an Academic of GeoMineMetallurgy Diploma at Universidad de Chile.
Pía Hernández
She holds a M. Sc. and doctoral degree in Engineering of Mineral Processes from Universidad de Antofagasta.
Currently, she is an assistant professor in the Chemical Engineering and Mineral Processes Department at
Universidad de Antofagasta. Her research interests include leaching in chloride medium and crystallization
related subjects in the field of mineral processes.
Patricio Martínez
Director of Hydrometallurgical and Biotechnological Processes at CodelcoTech, Chile. Biologist, (Pontificia
Universidad Católica de Valparaíso), Doctor in Biological Sciences (Pontificia Universidad Católica de Chile),
with more than 12 years of experience in Applied Research projects in biotechnology and hydrometallurgy,
including four Patents and five publications in journals indexed in this area.
Sergio Rivera
Professor of hydrometallurgy and concentrate and separation processes at the Mining Engineering
Department, Engineering Faculty at Universidad Andrés Bello. He is a Chemical Engineer and has a Master,s
degree in Industrial Process and a Ph.D. in Physical-Chemistry from Danish Technical University, Denmark.
He has been Process Engineer and Researcher over 20 year for several companies in metallic and no-metallic
industry as well as international engineering service companies (SQM, CODELCO, SKM).

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9 th I nte r n ation a l S e m i n a r on

Pro ce ss H y d ro m e ta llu rgy

Cover and book design by Estudio Vicencio

Challenges in 20 Years of Operation of the Leaching Plant, Solvent Extraction and

Path to a Cultural Transformation with “C+” Gabriela Mistral Division, Codelco

Scale Up of Hydrodynamic and Metallurgical Parameters in Heap Leaching Operations

PLCC Project: Autoclave Technology Applied to Complex Copper Concentrates

Copper Ore Leaching with Pre-Treatment

Speciation and Conditioning of Copper Leach Solutions

Application of an Operative Model of Excellence for the Optimization of Hydrometallurgical Plants

Multizone Process Water Metering using Distributed Acoustic Sensing (DAS)

An Effective New Leaching Aid Successfully Tested with Copper Ores

Development of an Active Carbon: Polydopamine Composite to Increase the Adsorption Capability of

Advanced Control System to Maximize Copper Recovery in Heap Leaching Operations

Oxidation Plant Optimization at Empresa Nacional de Minería

Development of a Geometallurigcal Model for the Oxides of Mantoverde, Chile

Bioleaching of Enargite: Copper Recovery with Microorganisms from Arsenic-Containing Ores

Outotec Process Solutions and Equipment for Hydrometallurgical Treatment of Cu Sulfides

New Electrolytic Process to Remove Copper Impurities from Molybdenite Concentrate by

BioCobre® Technology: an Improved Methodology for Leaching Mineral Concentrates

The FLSmidth® ROL Process: BASF-FLS Pilot Plant Testing

Effect of Degradation Products on the Performance of Hydroxyoxime Extractant

Effect of PLS Characteristics and Extractant Concentration on the Iron Transfer in

Study on the Effect of Diluent on the Performance of Extractant

Study on the Effect of Modifiers on the Extraction Performance of

Separation of Didymium from Lanthanum by Liquid-Liquid Extraction using

The Mith of Aromatic Compounds in Metallurgical Grade Kerosenes

SX Operation under High Chloride Content Conditions

Development and Implementation of SELE® Technology in EW Tank House, Radomiro Tomic

Start-Up Solvent Extraction – Electrowinning

Adsorption: An Interesting Hydrometallurgical Option to Remove Ions from Mine Waters

The Hydroprocess-ICMSE 2017 Seminar was organized by KopperChem, Universidad de

Kopper Chemical Industry, KopperChem

Universidad de Antofagasta, Department of Chemical Engineering and Min-

Colorado School of Mines, Kroll Institute for Extractive Metallurgy

Organizing Committee Celmer, Fluor, Chile • Virginia Ciminelli, National

Technical Chair Yamana Gold, Chile • Mario Núñez, Radomiro Tomic

Directing Members Committee

Executive Organizing Committee

There is no full article associated with this abstract.

There is no full article associated with this abstract.

Gabriela Mistral Division, Codelco Chile

There is no full article associated with this abstract.

There is no full article associated with this abstract.

There is no full article associated with this abstract.

Figure 1 Copper Production from Concentrates (Source: Cochilco 2016)

Figure 2 Copper Production in Chile (Source: Cochilco 2016)

Figure 3 Complex Copper Concentrates Production (Source: Wood & Mackenzie)

LABORATORY AND PILOTING TEST WORK

Table 1 Pilot Autoclave Characteristics

Item Sherritt SGS

Type Horizontal Horizontal

Agitation [rpm] 750 – 1.050 500 – 600

Solids to Solids and

Figure 6 PLCC Block Diagram

CAPEX, OPEX AND ADVANTAGES OF PLCC PROJECT

INSERTION OF THE PROJECT IN CODELCO OR OTHER COMPANIES

Figure 1 Mined head grades for base metals and gold

TREATMENT OF COMPLEX ORES THROUGH THE CONCENTRATOR

Figure 3 Conceptual flotation plant

Figure 4 Modification of the conventional flowsheet for fine grinding

GT PROCESS FOR THE TREATMENT OF COMPLEX ORES

Figure 6 GT concept for complex ore treatment

Case 1 – Copper NW Queensland