UNIVERSIDADE FEDERAL DE SANTA CATARINA CURSO DE GRADUAO EM ENGENHARIA DE MATERIAIS

GUSTAVO RHUAN PEREIRA

EVALUATION OF THE INFLUENCE OF FUEL OIL AND COLLECTOR ON COPPER AND MOLYBDENUM RECOVERY IN THE BIGHAM CANYON ORE

FLORIANPOLIS 2011

UNIVERSIDADE FEDERAL DE SANTA CATARINA CURSO DE GRADUAO EM ENGENHARIA DE MATERIAIS

GUSTAVO RHUAN PEREIRA

EVALUATION OF THE INFLUENCE OF FUEL OIL AND COLLECTOR ON COPPER AND MOLYBDENUM RECOVERY IN THE BINGHAM CANYON ORE

Diploma thesis presented to the Undergraduate Course of Materials Engineering of the Universidade Federal de Santa Catarina as part of the requisite to obtain the degree of Materials Engineer.

Mentor: Professor Dylton do Vale Pereira Filho

FLORIANPOLIS 2011

GUSTAVO RHUAN PEREIRA

EVALUATION OF THE INFLUENCE OF FUEL OIL AND COLLECTOR ON COPPER AND MOLYBDENUM RECOVERY IN THE BIGHAM CANYON ORE.

This Diploma Thesis was assessed adequate to attainment of the title Engenheiro de Materiais and approved by the Undergraduate Course of Materials Engineering of the Universidade Federal de Santa Catarina.

Prof. Fernando Cabral, Ph.D. Coordinator Assessment Committee:

Prof. Dylton do Vale Pereira Filho (Mentor)

Renan Muller Schroeder

Luiz Fernando Vieira

PEREIRA, Gustavo Rhuan, 1986 -

EVALUATION OF THE INFLUENCE OF FUEL OIL AND COLLECTOR ON COPPER AND MOLYBDENUM RECOVERY IN THE BIGHAM CANYON ORE. / Gustavo Rhuan Pereira. 2011 40 f.: il. color. 30cm.

Supervisor: Prof. Dylton do Vale Pereira Filho Trabalho de Concluso de Curso Universidade Federal de Santa Catarina, Curso de Engenharia de Materiais, 2011.

1. Froth Flotation 2. Copper 3. Lab Kinetic Test. I. Pereira Filho, Dylton do Vale. II Universidade Federal de Santa Catarina. Curso de Graduao de Engenharia de Materiais. III. EVALUATION OF THE INFLUENCE OF FUEL OIL AND COLLECTOR ON COPPER AND MOLYBDENUM RECOVERY IN THE BIGHAM CANYON ORE.

What I cannot create, I do not understand. (Richard Feynman)

ACKNOWLEDGES Firstly, I would like to thank Rio Tinto Kennecott Utah Copper for this great opportunity and support. I am very grateful to my supervisors Geraldine Lyons and Michael Dunn, for the internship opportunity, and to my co supervisor Dylan Cirulis, who guided me along the internship. Their continuous supervision and suggestions were very important. I would like to say thank you to Rio Tinto HR People, Ann Rash, Mike Rodgers and Jesse Roberts who helped me with all documentation. Thanks to my family, Elise Hinz, Toni Haag and my brothers of Harmonia Itajaiense, the most important people in my life, for the support and to always believe in me. Thanks Phanindra Kodali, Kambi Pezeshki and Kamran Pezeshki, Ana Paula Boatto my best friends in my American life!

() tenho aprendido que a noite do dia apenas a precursora do dia eterno. (Frank Marshall)

AGRADECIMENTOS Como muitas das pessoas que participaram da minha formao no compreendem ingls resolvi agradecer estas em portugus. Primeiramente agradecer ao Pai Celestial que com sua infinita bomdade, tem iluminando meus caminhos, minha famlia e meus amigos. Aos meus pais, Jos Urbino Pereira e Sandra Maria Severino Pereira pelo amor e carinho demonstrados ao longo da minha vida. A Universidade Federal de Santa Catarina e aos Professores do Curso de Engeharia de Materiais por proporcionar um curso dinmico e de qualidade, formando Engenheiros com alta adaptao e experincia. Aos meus irmos e tios do Captulo Harmonia Itajaiense da Ordem DeMolay por me apresentarem as 7 virtudes e ao longo destes anos nunca esquecerem que nossas amizades so eternas e no tem idade. Aos meus amigos cimjectianos do Laboratrio Cimject por sempre me receberem de portas abertas. Especial agradecimento para o Professor Gean Salmoria e os amigos: Peixoto, Lelo, Pri, Caubi, Calouro, Germanovix, Fernandinho, Ruben, Michel, Fala Mansa, Ju, Pagi, Testoni, Pedro e Jaca. Aos grandes metalurgistas que a cada estgio influenciaram grandemente minha formao cada qual contribuindo com sua experincia e amizade. So eles: Jos Francisco da Silva, Fabiano Miranda, Ren Lelis, Srgio Scherer, Jos Armando Campos, Caetano Nunes da Silva, Denlson Aquino, ngelo Campos Moreira, Sandro Marino, Michael Dunn, Geraldine Lyons, Dylan Cirulis, Phanindra Kodali, Kambi Pezeshki e Kamran Pezeshki. Aos amigos que me incentivaram e tornaram a distncia da famlia menos dolorosa, em especial: Felipe Augusto de Souza, Ricardo Matsukura, Camila Sato, Andr Lozovey, Igor Branco, Ricardo Selke, Guilherme Dalmedico, Eduardo Hulse, Alexandre Werner Reis, Ricardo Reis, Charles Max, Alisson Rizzi e Ana Paula Boatto. A Elise Hinz por sua companhia especial e pacincia nas minhas ausncias.

ABSTRACT The consumption of copper has increased greatly in recent years due to its use principally in the energy and electronics. Approximately 80% of world production of copper is done by flotation followed by pyrometallurgy. In this study the ore QMPSW of Bingham Canyon Mine who will be used in the plant in 2014-2016 was studied by flotation tests in the laboratory to maximize recovery values when applied industrially. After 18 tests, were analyzed the levels of recovery of copper, molybdenum and calculated the value of the constant of reaction kinetics. Mean values of collector S8989 and fuel oil presented best results in 5 minutes of flotation in the laboratory, which parameter is used as the standard for industrial scale.

Key-words: Copper, Molybdenum, Copper extractive metallurgy, Flotation, Collector.

RESUMO O consumo de cobre vem aumentando muito nos ltimos anos devido a sua utilizao principalmente na rea de energia e eletrnica. Aproximadamente 80% da produo mundial de cobre feita atravs de flotao seguida de pirometalurgia. Neste estudo o minrio QMPSW de Bingham Canyon Mine que ser utilizado na planta em 2014-2016 foi estudado atravs de ensaios de flotao em laboratrio para maximizar seus valores de recuperao quando for aplicado industrialmente. Aps 18 testes, foram analizados os teores de recuperao de cobre, molibdnio e calculado o valor da constante de cintica da reao. Mdios valores de coletor S8989 e leo combustvel apresentaram melhores resultados em 5 minutos de flotao em laboratrio, parmetro que ser utilizado como padro para escala industrial.

Palavras-chaves: Cobre, Molibdnio, Metalurgia extrativa cobre, Flotao, Coletor.

LIST OF FIGURES

Figure 1: USA geological map. (www.virtualamericas.net/usa/maps) .................................... 13 Figure 2: Bingham Canyon Mine. (www.kennecott.com) ........................................................ 14 Figure 3: Cross section depicting a hypothetical volcanic edifice over the Bingham Canyon porphyry copper deposit. The reconstructed volcanic cover implies that some Bingham intrusions vented to form domes that collapsed to form the existing debris avalanche deposits (Deino & Keith, 1997) ............................................................................................................. 15 Figure 4: QMPSW Deposit Position. ....................................................................................... 16 Figure 5: Typical hydrometallurgical process for recovery from heap leaching. ................... 17 Figure 6: Typical pyrometallurgical process for copper recovery from sulfide ore. ............... 17 Figure 7: Principle of froth flotation. (http://en.wikipedia.org/wiki/Froth_flotation) ............. 19 Figure 8: Contact angle between bubble and particle in an aqueous medium. ....................... 20 Figure 9: Action of the frother. ............................................................................................... 22 Figure 10: Critical pH value for chalcopyrite. [7] .................................................................. 22 Figure 11: Classification of collectors. (after Glembotskii, 1972) .......................................... 23 Figure 12: Collector adsorption on mineral surface. .............................................................. 24 Figure 13: (1) Laboratory Flotation Cell; (2) Float Test. ....................................................... 26 Figure 14: Rod Mill. ................................................................................................................. 27 Figure 15: Grinding time curve................................................................................................ 27 Figure 16: Representative DOE table showing the dosages used for each test. ...................... 28 Figure 17: Filing the float cell (left) and Reagent addition (right). ......................................... 28 Figure 18: Collecting the concentrate...................................................................................... 28 Figure 19: Flotation Test. ........................................................................................................ 29 Figure 20: ANOVA plots illustrating the main effects on copper recovery (left) and the interaction of effects on copper recovery (right) after 2 minutes. ............................................ 30 Figure 21: ANOVA plots illustrating the main effects on molybdenum recovery (left) and its interaction of effects (right) after 2 minutes. ............................................................................ 30 Figure 22: ANOVA plots illustrating the main effects on copper recovery (left) and the interaction of effects on copper recovery (right) after 5 minutes. ............................................ 31 Figure 23: ANOVA plots illustrating the main effects on molybdenum recovery (left) and the interaction of effects on molybdenum recovery (right) after 5 minutes ................................... 31

Figure 24: ANOVA plots illustrating the main effects on copper recovery (left) and the interaction of effects on copper recovery (right) after 10 minutes. .......................................... 32 Figure 25: ANOVA plots illustrating the main effects on molybdenum recovery (left) and the interaction of effects on molybdenum recovery (right) after 10 minutes ................................. 32 Figure 26: K values and maximum recovery calculated for each test. .................................... 33 Figure 27: Flotation recovery for copper graphic of the tests. ................................................ 33 Figure 28: Results of all tests. .................................................................................................. 36

CONTENTS

1. 2. 3. 3.1.

INTRODUCTION OBJECTIVES OVERALL REVIEW GEOLOGY OF BINGHAM CANYON MINE Tectonic Setting QMPSW Deposit COPPER PRODUCTION METHODS Hydrometallurgy Pyrometallurgy FROTH FLOTATION Principles of flotation Frothers The importance of pH Collectors Choice of collector LABORATORY FLOTATION TESTING EXPERIMENTAL PROCEDURES GRINDING TIME CURVE FLOTATION TESTS RESULTS AND DISCUSSIONS TWO MINUTES FLOTATION ANALYSIS FIVE MINUTES FLOTATION ANALYSIS TEN MINUTES FLOTATION ANALYSIS KINETICS ANALYSIS CONCLUSIONS REFERENCES APPENDIX A

11 12 13 13 14 15 16 16 17 18 18 21 22 23 24 25 27 27 28 29 29 30 32 33 34 35 36

3.1.1. 3.1.2. 3.2. 3.2.1. 3.2.2. 3.3. 3.3.1. 3.3.2. 3.3.3. 3.3.4. 3.3.5. 3.4. 4. 4.1. 4.2. 5. 5.1. 5.2. 5.3. 5.4. 6. 7. 8.

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1.

INTRODUCTION Copper is the third most used metal by man (iron and aluminum are produced and consumed in greater quantities than copper). The critical need for copper began in 1850, with the use of electricity. Given its malleability, conductivity of both heat and electricity, ability to withstand corrosion, and its esthetic characteristics, copper has established crucial importance in virtually all areas of development and newly developing economies most notably in areas of construction, transport, and all kinds of electrical and electronic applications. Since 1850 copper production has increased more than 300 times [1]. After two centuries of great use of natural resources, the economy of the twenty-first century looks at sustainability as something essential for the future of the earth. Every day, society increasingly demands that industries adopt a sustainable approach with a minimal use of nonrenewable resources. To meet the demand of society, the mining sector increasingly invests in innovative technologies that aim to make the most of the original ore products with the least possible pollution. The modern froth flotation process was independently invented in the early 1900s in Australia by C. V. Potter and around the same time by G. D. Delprat. Initially, naturally occurring chemicals such as fatty acids and oils were used as flotation reagents in a large quantity to increase the hydrophobicity of the valuable minerals. Since then, this process has been adapted and applied to a wide variety of materials to be separated, and additional collector agents, including surfactants and synthetic compounds have been adopted for various applications [2]. Today approximately 80% of world copper production uses forth flotation [3]. In this background, the Ore Body Knowledge Team Kennecott Utah Mine in the state of Utah, USA, is developing a project to improve the copper recovery in froth flotation. The present academic work is part of this project and consists of testing one kind of ore that will be used in 2014-2016.

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2.

OBJECTIVES This work has as main objective to maximize the copper and molybdenum recovery for QMPSW ore in froth flotation. The specific objectives are: Verify the influence of collector on recovery rates of copper and molybdenum. Verify the influence of fuel oil on recovery rates of copper and molybdenum. Calculate the Kinetic constant value for copper and molybdenum.

13

3.

OVERALL REVIEW This chapter contains an overview about the subjects which assists the understanding of this work. Here it finds an introduction about the geology of Bingham Canyon Mine, copper extraction process, reagents used in flotation, and froth flotation tests in laboratory.

3.1. GEOLOGY OF BINGHAM CANYON MINE Bingham Canyon hosts one of the worlds largest porphyry copper deposits and is in fact the worlds largest open pit mining excavation. The Figure 1 shows the position of Bingham Canyon in USA geological map, and the Figure 2 shows the Bingham open pit. It is primarily mined for copper but also produces substantial amounts of molybdenum, gold, and silver which also contribute to the profitability of the mine. The Bingham pit is currently more than 3 kilometers in diameter and more than 900 meters deep.

Figure 1: USA geological map. (www.virtualamericas.net/usa/maps)

Bingham Canyon has been explored since 1904 and your current owner is the Rio Tinto Group. The Bingham stock porphyry is a classic giant porphyry copper ore body, with low grade copper disseminated throughout the igneous host rock. Open pit reserves are estimated to last until 2020. There are currently plans being made to mine underground reserves by the block caving mining method estimated to keep the mine running for approximately 15 years after that.

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Figure 2: Bingham Canyon Mine. (www.kennecott.com)

3.1.1. Tectonic Setting The Bingham Canyon mine is located in the central Oquirrh Mountains, and approximately 50 kilometers long north-south oriented, fault-bounded mountain rage in the eastern Great Basin. The range begins in northwest Utah County and stops at the shore of the Great Salt Lake, separating Utahs Salt Lake Valley from the Tooele Valley. The Oquirrh Mountains (Oquirrh is a Ute Indian word meaning The Shining Mountains) represent the eastern most fault block of the Basin and Range Province separated from the Colorado Plateau by the Wasatch Fault [4]. The Oquirrh Mountains region has been tectonically active through much of geologic time. Since early Paleozoic times it was until the late Carboniferous a passive continental margin, where thin carbonates interbedded with clastic sediments were deposited. During late Pennsylvanian time a slight deepening was accompanied by the rapid deposition of several kilometers of shallow water carbonates and siliclastic sediments into the northwest-trending Oquirrh Basin. In the Early Permian time followed the return to the passive margin sedimentation [4]. Two orogenies with Mesozoic age affected the region: the mid Jurassic Elko Orogeny and the late Cretaceous Sevier Orogeny. They formed in south of Bingham Canyon a series of northwest-trending folds, and northeast-trending folds north of Bingham Canyon. Eastward oriented compressional forces during the time of the Sevier Orogeny resulted in several major thrusts and complex faulting and folding in the vicinity of the Cu-Mo-Au ore deposit [5]. Cenozoic activity at Bingham Canyon was dominated by an extensional regime. It started with a minor Eocene extension associated with the emplacement of intrusions, dikes and fissures and evolved into an intense period of Eocene intrusive and volcanic activity along

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the Uinta Axis forming the west-trending Wasatch igneous belt with the Bingham Canyon porphyry copper deposit [5]. The intrusion of igneous rocks in the Bingham Canyon mining district was controlled by northwest-trending and northeast-striking faults. Some of the Eocene magmatic stocks and dikes apparently vented to the surface and formed a composite volcano (Figure 3). Some parts of this volcano are still preserved on the eastern side of the Oquirrh Mountains.

Figure 3: Cross section depicting a hypothetical volcanic edifice over the Bingham Canyon porphyry copper deposit. The reconstructed volcanic cover implies that some Bingham intrusions vented to form domes that collapsed to form the existing debris avalanche deposits [5].

In the Middle Eocene the Bingham and Last Chance Stock were emplaced, but only the Bingham Stock is strongly mineralized. This appears to be due to the vicinity to the later Quartz Monzonite Porphyry. This intrusive body acted as the source and center for the hydrothermal activity. Extension continued with major Miocene to Recent Basin and range extension which opened the Salt Lake Valley and other north-south oriented basis along major listric faults. Thereby the Bingham Canyon deposit was tilted eastwards by 15 to 20 degrees [5]. 3.1.2. QMPSW Deposit The QMPSW Deposit is one area who will be used in 2014-2016, this deposit has high concentration of copper and molybdenum. The Figure 4 shows the position of this deposit on Bingham Canyon Mine.

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Figure 4: QMPSW Deposit Position.

3.2. COPPER PRODUCTION METHODS Copper reserves are mostly present in the form of oxide and sulfide minerals. Copper mining is performed either underground or in open pits. Laterite ores copper oxide minerals such as cuprite and hydrous carbonates (malachite, azurite). Chalcopyrite, chalcocite, bornite, cubanite, and enargite are common examples of copper sulfide minerals. Most of the copper ores contain only a very small percentage of copper minerals, an even less molybdenum and precious metals [6]. The remaining minerals, of little value, are discarded. Average head grade in most of the mines is less than 1% copper. Depending on the ore type (oxide or sulfide) the copper extraction process is designed. Hydrometallurgical processes, such as heap leaching is used to extract copper from copper oxide ore and some copper sulfide ores. Subsequently copper is extracted from the leach solution by solvent extraction and electrowinning. In the case of the Pyrometallurgical process, a copper sulfide concentrate, produced by froth flotation is smelted at high temperature and refined electrolytically [6]. 3.2.1. Hydrometallurgy Hydrometallurgical processes are used to extract copper from low grade ores, especially copper oxide by heap leaching (Figure 5). Copper ore from the mine is crushed typically with jaw crushers to pass about 1,27 cm top size. This crushed ore along with acid solution is introduced into rotating agglomeration drums. In the agglomeration drums fine ore particles are bonded to coarser ore particles via liquid bridges. The agglomeration product is stacked on the heap leach pad to about 7 meters in height. Sulfuric acid solution is introduced on the top of the heap leach pad and dissolves copper as the solution as the solution passes through the heap. Copper recovery from the heap

17

leach pad depends on the particle size distribution, of the ore particle damage, and quality of agglomerates. About 20% of worlds annual copper production is from leaching. Bioleaching and autoclave leaching are also performed depending on ore type and grade in order to improve the leaching efficiency.

Figure 5: Typical hydrometallurgical process for recovery from heap leaching.

Pregnant leach solution (copper rich solution) from the leach pads is concentrated and purified by solvent extraction. During this solvent extraction stage, copper is separated from the acid solution using extractant to stabilize copper in organic phase. After stripping copper from the organic phase, copper metal is produced as cathodes during electrowinning. 3.2.2. Pyrometallurgy About 80% of worlds annual copper production is from the pyrometallurgy of copper sulfide ore (Figure 6). Copper ore from the mine is crushed with a gyratory or jaw crusher. Discharge from crusher feeds a grinding circuit where, sag mills and ball mills further reduce the ore particles to about 75 microns in size. This slurry of fine ore particles is conditioned with chemicals to separate the copper sulfide mineral particles by flotation. In about 80 to 90% of the copper is recovered during flotation.

Figure 6: Typical pyrometallurgical process for copper recovery from sulfide ore.

The copper concentrate from flotation is sent to filtration to remove the water and to dry the concentrate. Dry concentrate is introduced into the smelting furnaces. Smelting furnace produces matte (high grade Cu/Fe sulfides). The matte is sent to the convertor where blister copper is produced. The blister copper is cast into anodes and refined electrolycally as final product (copper 99,99%). In the present study, the influence of burner-oil and collector on copper and molybdenum recovery has been studied.

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3.3. FROTH FLOTATION Flotation is undoubtedly the most important and versatile mineral processing technique, and both its use and application are continually being expanded to treat greater tonnages and to cover new areas [7]. Originally patented in 1906, flotation has permitted the mining of low grade and complex ore bodies which would have otherwise been regarded as uneconomic. In earlier practice the tailings of many gravity plants were of a higher grade than the ore treated in many modern flotation plants [7]. Flotation is a selective process and can be used to achieve specific separations from complex ores such as lead-zinc, copper-zinc, lead, copper-molybdenum, and zinc. The field of flotation has now expanded to include platinum, nickel, gold-hosting sulphides, and oxides, such as hematite and cassiterite, oxidized minerals, such as malachite and cerussite, and nonmetallic ores, such as fluorite, phosphates, and fine coal [6]. 3.3.1. Principles of flotation Flotation is a physico-chemical separation process that utilizes the difference in surface properties of the valuable minerals and the unwanted gangue minerals. The theory of froth flotation is complex, involving three phases (solids, water, and froth) with many subprocesses and interactions, and is not completely understood [6]. The process of material being recovered by flotation from the pulp comprises three mechanisms: (1) Selective attachment to air bubbles (or true flotation); (2) Entrainment in the water which passes through the froth. (3) Physical entrapment between particles in the froth attached to air bubbles (often referred to as aggregation.

The attachment of valuable minerals to air bubbles is the most important mechanism and represents the majority of particles that are recovered to the concentrate. Although true flotation is the dominant mechanism for the recovery of valuable mineral, the separation efficiency between the valuable mineral and gangue is also dependent on the degree of entrainment and physical entrapment. Unlike true flotation, which is chemically selective to the mineral surface properties, both gangue and valuable minerals alike can be recovered by entrainment and entrapment. Drainage of these minerals occurs in the froth phase and

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controlling the stability of this phase is important to achieve an adequate separation. In industrial flotation plant practice, entrainment of unwanted gangue can be common and hence a single flotation stage is uncommon. Often several stages of flotation (called circuits) are required to reach an economically acceptable quality of valuable mineral in the final product. True flotation utilizes the differences in physico-chemical surface properties of particles of various minerals. After treatment with reagents, such differences in surface properties between the minerals within the flotation pulp become apparent and, for flotation to take place, an air bubble must be able to attach itself to a particle, and lift it to the water surface. The Figure 7 illustrates the principles of flotation in a mechanical flotation cell. The agitator provides enough turbulence in the pulp phase to promote collision of particles and bubbles which results in the attachment of valuable particles to bubbles and their transport into the froth phase for recovery [6].

Figure 7: Principle of froth flotation. (http://en.wikipedia.org/wiki/Froth_flotation)

The process can only be applied to relatively fine particles, because if they are too large the adhesion between the particle and the bubble will be less than the particle weight and the bubble will therefore drop its load [6]. In flotation concentration, the mineral is usually transferred to the froth, or float fraction, leaving the gangue in the pulp or tailing. This is direct flotation and the opposite is reverse flotation, which the gangue is separated into the float fraction [6]. The function of the froth phase is to enhance the overall selectivity of the flotation process. The froth achieves this by reducing the recovery of entrained material to the concentrate stream, while preferentially retaining the attached material. This increases the concentrate grade whilst limiting as far as possible the reduction in recovery of valuables. The relationship between recovery and grade is a trade-off that needs to be managed according to operational constraints and is incorporated in the management of an optimum froth stability.

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As the final separation phase in a flotation cell, the froth phase is a crucial determinant of the grade and recovery of the flotation process [6]. The mineral particles can only attach to the air bubbles if they are to some extent water-repellent, or hydrophobic. Having reached the surface, the air bubbles can only continue to support the mineral particles if they can form a stable froth, otherwise they will burst and drop the mineral particles. To achieve these conditions it is necessary to use the numerous chemical compounds known as flotation reagents [6]. The activity of a mineral surface in relation to flotation reagents in water depends on the forces which operate on that surface. The forces tending to separate a particle and a bubble are shown in Figure 8. The tensile forces lead to the development of an angle between the mineral surface and the bubble surface. At equilibrium, / = / + / cos (3.1)

where / , / and / are the surface energies between solid air, solid and water, and water and air, respectively, and is the contact angle between the mineral surface and the bubble.

Figure 8: Contact angle between bubble and particle in an aqueous medium.

The force required to break the particle-bubble interface is called the work of adhesion, / , and is equal to the work required to separate the solid-air interface and produce separate air-water and solid-water interfaces. / = / + / /

(3.2)

Combining with Equation 3.1 gives / = / (1 cos )

(3.3)

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It can be seen that the greater the contact angle the greater is the work of adhesion between particle and bubble and the more resilient the system is to disruptive forces. The hydrophobicity of a mineral therefore increases with the contact angle; minerals with a high contact angle are said to be aerophilic, they have a higher affinity for air than for water. The terms hydrophobicity and floatability are often used interchangeably. Hydrophobicity, however, refers to a thermodynamic characteristic, whereas floatability is a kinetic characteristic and incorporates other particle properties affecting amenability to flotation [6]. Most minerals are not water-repellent in their natural state and flotation reagents must be added to the pulp. The most important reagents are the collectors, which adsorb on mineral surfaces, rendering them hydrophobic (or aerophilic) and facilitating bubble attachment. The frothers help maintain a reasonably stable froth [6]. 3.3.2. Frothers When mineral surfaces have been rendered hydrophobic by the use of a collector, stability of bubble attachment, especially at the pulp surface, depends to a considerable extent on the efficiency of the frother [8]. Ideally the frother acts entirely in the liquid phase and does not influence the state of the mineral surface. In practice, however, interaction does occur between the frother, mineral and other reagents, and the selection of a suitable frother for a given ore can only be made after extensive test work. In sulphides mineral flotation it is common practice to employ at least two frothers and more than one collector. Specific frothers are chosen to provide adequate physical properties to the froth, while the second frother interacts with the collectors to control the dynamics of the flotation process. Froth build-up on the surfaces of thickeners, and excessive frothing of flotation cells, are problems occurring in many mineral processing plants. A good frother should have negligible collecting power, and also produce a froth which is just stable enough to facilitate transfer of floated mineral from the cell surface to the collecting launder [8]. Frothers are generally heteropolar surface-active organic reagents, capable of being adsorbed on the air-water interface. When surface-active molecules react with water, the water dipoles combine readily with the polar groups and hydrate them, but there is practically no reaction with the non-polar hydrocarbon group, the tendency being to force the latter into the air phase [8].

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Figure 9: Action of the frother.

3.3.3. The importance of pH One of most important parameters for best results in flotation is the balance between reagent concentration and pH. Flotation where possible is carried out in an alkaline medium, because the most collectors, are stable under these conditions, and corrosion of cells, is minimized. Alkalinity is controlled by the addition of lime or sodium carbonate. These chemicals are often used in very significant amounts in almost all flotation operations. Although they are cheaper than collectors and frothers, the overall cost is generally higher with pH regulators per ton of ore treated than with any other processing chemical [6]. Lime, being cheap, is very widely used to regulate pulp alkalinity, and is used in the form of milk of lime (suspension of calcium hydroxide particles in a saturated aqueous solution). Lime, is often added to the slurry prior to flotation to precipitate heavy metal ions from solution in this sense, the alkali is acting as a deactivator [6]. The critical pH value depends on the nature of the mineral, the particular collector and its concentration, and the temperature. The Figure 10 shows how the critical pH value for pyrite depends on the concentration of sodium dithiophosphate.

Figure 10: Critical pH value for chalcopyrite. [7]

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3.3.4. Collectors Hydrophobicity has to be imparted to most minerals in order to float them. In order to achieve this, surfactants known as collectors are added to the pulp and time is allowed for adsorption during agitation in what is known as the conditioning period. Collectors are organic compounds which render selected minerals water-repellent by adsorption of molecules or ions on to the mineral surface, reducing the stability of the hydrated layer separating the mineral surface from the air bubble to such a level that attachment of the particle to the bubble can be made on contact [9]. Collector molecules may be ionizing compounds, which dissociate into ions in water, or non-ionizing compounds, which are practically insoluble, and render the mineral waterrepellent by covering its surface with a thin film [6]. Ionizing collectors have found very wide application in flotation. They have complex molecules which are asymmetric in structure and are heteropolar, the molecule contains a non-polar hydrocarbon group and a polar group which may be one of a number of types. The non-polar hydrocarbon radical has pronounced water-repellent properties, whereas the polar group reacts with water [6].

Figure 11: Classification of collectors. (after Glembotskii, 1972)

Ionizing collectors are classed in accordance with the type of ion, anion or cation that produces the water-repellent effect in water. This classification is given in Figure 11. Because of chemical, electrical, or physical attraction between the polar portions and surface sites, collectors adsorb on the particles with their non-polar ends orientated towards the bulk solution, thereby imparting hydrophobicity to the particles (Figure 12). They are usually used in small amounts, substantially those necessary to form a monomolecular layer on particle surfaces (starvation level), as increased concentration, apart from the cost, tends to

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float other minerals, reducing selectivity. It is always harder to eliminate a collector already adsorbed than to prevent its adsorption.

Figure 12: Collector adsorption on mineral surface.

An excessive concentration of collector can also have adverse effect on the recovery of valuable minerals, possibly due to the development of collector multi-layers on the particles, reducing the proportion of hydrocarbon radicals orientated into the bulk solution. The hydrophobicity of the particles is thus reduced, and hence their floatability. The flotation limit may be extended without loss of selectivity by using a collector with a longer hydrocarbon chain, thus producing greater water-repulsion, rather than by increasing the concentration of a shorter chain collector. However, chain length is usually limited to two to five carbon atoms, since the solubility of the collector in water rapidly diminishes with increasing chain length and, although there is a corresponding decrease in solubility of the collector products, which therefore adsorb very readily on the mineral surfaces, it is, of course, necessary for the collector to ionize in water for chemisorption to take place on the mineral surfaces. Not only the chain length but also the chain structure, affects solubility and adsorption, branched chains have higher solubility than straight chains [8]. It is common to add more than one collector to a flotation system. A selective collector may be used at the head of the circuit, to float the highly hydrophobic minerals, after which a more powerful, but less selective one, is added to promote recovery of the slower floating minerals [8]. 3.3.5. Choice of collector In most porphyry copper molybdenum operations, xanathe or dithiophosphates are used as the primary collector, while a variety of secondary collectors are used including xanthogen formats, thionocarbamates, xanthic esters and mercaptobenzothiazole. In some cases, only dithiophosphate collectors are used. There is no general rule by which secondary collectors

25

are selected. There are, however, several factors that influence the selection of this collector such as presence of clay minerals in the ore, presence of middlings and type of frother used. Approximately 50% of worlds molybdenum production comes from coppermolybdenum ore as a by-product. The floatability of molybdenum during copper flotation also depends on many factors, including type of collector, type of frother, flotation pH and type of hydrocarbon oil used. During the flotation of copper molybdenum ores, fuel oil or kerosene is added to the grinding to enhance molybdenum recovery [8]. In this study, Cytec S8989 and fuel oil were used as collector.

3.4. LABORATORY FLOTATION TESTING One of most widely used techniques to determine the amount and what reagents (collectors and frothers) will be used on industrial scale is the laboratory flotation test. Flotation testing is also carried out on ores in existing plants to improve procedures and for development of new reagents [9]. It is essential that test is carried out on ore which is representative of that treated in the commercial plant. Samples for test work must be representative, not only in chemical composition, but also degree of dissemination. A mineralogical examination of drill cores or other individual samples should therefore be made before a representative sample is selected. Composite drill core samples are ideal for testing if drilling in the deposit has been extensive; the cores generally contain ore from points widely distributed over the area and in depth. It must be realized ore bodies are variable and that a representative sample will not apply equally well to all parts of the ore body. It is used therefore for development of general flotation procedure. Additional tests must be made on samples from various areas and depths to establish optimum conditions in each case and to give design data over the whole range of ore variation [9]. Having selected representative samples of the ore, it is necessary to prepare them for flotation testing, which involves comminution of the ore to its optimum particle size. Crushing must be carried out with care in order to avoid accidental contamination of the sample by grease or oil, or with other materials which have been previously crushed. Even in commercial plant, a small amount of grease or oil can temporarily upset the flotation circuit [9]. Storage of the crushed sample is important, since oxidation of the surfaces is to be avoided especially with sulphides ores. Not only does oxidation inhibit collector absorption,

26

but it also facilitates the dissolution of heavy metal ions, which may interfere with the flotation process. Sulphides should be tested as soon as possible after obtaining the sample and ore samples must be shipped in sealed drums in as coarse a state as possible. Wet grinding of the samples should always be undertaken immediately prior flotation testing to avoid oxidation of the liberated mineral surfaces. Batch laboratory grinding, using ball mills, produces a flotation feed with a wider size distribution than that obtained in continuous closed-circuit grinding; to minimize this, batch rod mills are used which give products having a size distribution which approximates closely to that obtained in closedcircuit ball mills. True simulations is never really achieved, however, as overgrinding of high density minerals , which is a feature of closed-circuit grinding, is avoided in a batch rod mill. The optimum grinding size of the particles depends not only on their grain size, but also on their floatability. Initial examination of the ore should be made to determine the degree of liberation in terms of particle size in order to estimate the grinding time. Tests should then be carried out over a range of grinding sizes in conjunction with flotation tests in order to determine the optimum mesh of grind. In certain cases, it may be necessary to over grind the ore in order that particles are small enough to be lifted by air-bubbles [9]. The bulk of laboratory test is carried out in batch flotation cells, usually with the same density of the production (26-38% of solids). The cells are mechanically agitated, the speed of rotation of the impellers being variable, and simulate the large-scale models commercially available. Introduction of air to the cell is normally via a hollow standpipe surrounding the impeller shaft.

Figure 13: (1) Laboratory Flotation Cell; (2) Float Test.

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4.

EXPERIMENTAL PROCEDURES These experiments could be divided in two parts: grinding and flotation. In the first moment, the blast ore was received and characterized by size and grinded up to 32% of particles were greater than 100 mesh. After grinded, the ore was floated in laboratory to analyze the best combination of fuel oil and collector who gives the best recovery. 4.1. GRINDING TIME CURVE Approximately 1500g of ore was used in each test. This ore was received in the laboratory with a particle size higher than considered optimal to do a flotation test. Two tests were done in the laboratory rod mill to take the optimal particle size. In one test the grinding time was 5 minutes and in the other test grinding time was 12 minutes. After grinded, each sample was dried and screened to take the percent of particles higher than 100 mesh.

Figure 14: Rod Mill.

With these two points, it was possible to take the grinding time, 7 minutes and 12 seconds, corresponding to 32% of +100 mesh particles.

Figure 15: Grinding time curve.

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4.2. FLOTATION TESTS After determining the grinding time, 18 tests were done. The configuration of each test is showed in the Figure 16. In each test the ore sample was prepared in the rod mill with 1.5g of lime (for pH control), and 22 l of frother Dow Chemicals X-237.

Figure 16: Representative DOE table showing the dosages used for each test.

Flotation tests were performed after each grinding cycle. In these tests, samples were collected at 0.5, 2, 5, and 10 minutes and sent for assay analysis. The results will be discussed below.

Figure 17: Filing the float cell (left) and Reagent addition (right).

The parameters of Denver Flotation Machine were: 4 liters of solution, 1500 rpm and 4 m/h of air flow.

Figure 18: Collecting the concentrate.

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5.

RESULTS AND DISCUSSIONS The recovery of copper and molybdenum was calculated for every test after 30 seconds, 2, 5 and 10 minutes respectively. Appendix A shows the calculated recovery tables.

Figure 19: Flotation Test.

To determine the effect of the reagents on the overall recovery of the minerals, ANOVA was used to identify what reagent dosages would give the best results, as well as what combinations could give the best recovery. Although the analysis was done for every test after 2, 5 and 10 minutes, the main focus was on the 5 minutes recovery since it is representative of the plant process and can be scaled up to fit the plant requirements. The analysis at different times was done to determine how the flotation kinetics in the system worked and to determine if there was a relationship between them. Also the data could be used to decide whether a longer residence time could be applied to the process or not. 5.1. TWO MINUTES FLOTATION ANALYSIS The ANOVA showed that after 2 minutes there was a better recovery with a combination of 20 l of S8989 collector and 33 l of fuel oil dosages respectively (Figure 20). This shows that after 2 minutes increasing the amount of fuel oil provides a better copper recovery but it is not the same when the S8989 dosage increases. However, if analyzed separately it is shown that only a medium level of S8989 and burner oil improves copper recovery. Thus, ANOVA shows that the two variables are not linearly related and only a combination of high burner oil dosage and an intermediate level of S8989 would provide good results. For the molybdenum recovery (Figure 21), the trend was not the same as in the copper recovery interaction plot. Molybdenum had a better recovery with a low burner oil dosage and a low S8989 (13l and 14l respectively). However, the difference between the recovery using these dosages and using the dosage that gave the best copper recovery is only 1%. After

30

the 2 minutes it can be assumed that if at a combination of 20l S8989 and 33l fuel oil dosages respectively, the recovery of copper and molybdenum is significantly higher. The two variables, S8989 and fuel oil, are not linearly related and only a combination of high fuel oil dosage and an intermediate level of S8989 would provide good results. At this point neither the S8989 nor the burner oil plays a significant effect on the recovery of valuable mineral.

Figure 20: ANOVA plots illustrating the main effects on copper recovery (left) and the interaction of effects on copper recovery (right) after 2 minutes.

Figure 21: ANOVA plots illustrating the main effects on molybdenum recovery (left) and its interaction of effects (right) after 2 minutes.

5.2. FIVE MINUTES FLOTATION ANALYSIS After 5 minutes the recovery patterns stayed almost the same as the patterns observed after the 2 minutes time frame. If analyzed individually, only a medium level of S8989 and fuel oil helped improve copper recovery. If the interaction plot is analyzed, there was a better recovery with a combination of 14l of S8989 and 23l fuel oil dosages respectively (Figure 22). Thus, the dosage of reagents decreased but the recovery was increased by approximately 7 % (also attributed to the residence time). Moreover, when performing a t-test, to identify the variable that contributes more significantly to the result, the test indicated that S8989 is the

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most significant variable and has a higher effect on the copper recovery. The test only accounts for marginal or partial contribution but it is a good indicator of which variable would have the most significant effect on overall recovery. The test reveals important information since the 5-minute refloat data is representative of the plant process and is usually used for scale-up. Nonetheless, more experiments should be carried out to support these statements.

Figure 22: ANOVA plots illustrating the main effects on copper recovery (left) and the interaction of effects on copper recovery (right) after 5 minutes.

In the case of MoS2, when the reagents were analyzed individually, it was observed that increasing the level of fuel oil also increased the recovery of Molybdenum. The opposite occurred with S8989, since the lowest the level of S8989 conferred the highest overall recovery. The t-test showed that the most significant effect on recovery was attributed to the level of S8989. Thus, changing the dosage of S8989 will have a detrimental effect on the recovery of Molybdenum. However, if the interaction plots are analyzed, the combination of 14l of S8989 and 13l of fuel oil provides the best recovery. The second best combination (20l of S8989 and 33 of fuel oil) is with a medium level of S8989 and a high dosage of fuel oil. The trade-off is only 1% recovery decrease, thus showing that increasing fuel oil dosage and decreasing S8989 is detrimental for a good Molybdenum recovery. If this trend is followed for the copper recovery, the trade-off will be only 0.5% decrease in Cu recovery.

Figure 23: ANOVA plots illustrating the main effects on molybdenum recovery (left) and the interaction of effects on molybdenum recovery (right) after 5 minutes

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5.3. TEN MINUTES FLOTATION ANALYSIS The analysis of the interaction plots after 10 minutes showed that increasing the levels of S8989 and fuel oil was beneficial for the recovery of all minerals. However, when analyzed individually, it was observed that the reagent dosage followed the same trend as the 5 minutes analysis. The recoveries observed with the increasing levels of S8989 show that S8989 plays a significant role in the recovery of the valuable minerals. Although it is not linearly related to fuel oil, S8989 is statistically significant for the recovery of the minerals and changes on the dosage may significantly affect the process.

Figure 24: ANOVA plots illustrating the main effects on copper recovery (left) and the interaction of effects on copper recovery (right) after 10 minutes.

If the combination of 20l of S8989 and 33l of burner oil is analyzed, the recovery of copper is not the best but the difference between the highest recovery and the recovery under these conditions is only 1.5%. The recovery is very good recovery and the losses are minimal. The same occurs with the recovery of molybdenum. Overall, a good combination would be the use of 20l of S8989 and 33l of fuel oil in the process.

Figure 25: ANOVA plots illustrating the main effects on molybdenum recovery (left) and the interaction of effects on molybdenum recovery (right) after 10 minutes

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5.4. KINETICS ANALYSIS Flotation kinetics analysis was performed using the command solve of Microsoft Excel for the mathematical expression: Rx = Rmax * (1-e-kt), where Rx is the cumulative recovery in the selected time, Rmax is the maximum recovery of the reaction, k is the kinetic constant, and t is the selected time. To calculate the k value of each test, 2 rules for the mathematical expression were created: (1) Rmax < 1; (2) Rmax >R10min. The Figure 26 shows the k value and the maximum calculated recovery for each test of this experiment.

Figure 26: K values and maximum recovery calculated for each test.

Faster kinetics was usually a good indicator of good recovery performance and vice versa. The best recovery was found with high S8989 and high fuel oil, but for this good recovery a long residence time is necessary what cannot be industrially viable. The Figure 27 shows the kinetic curve for copper of the experiment.

Figure 27: Flotation recovery for copper graphic of the tests.

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6.

CONCLUSIONS Evaluating the results obtained in this work, the following conclusions can be affirmed: Collector is the most important component for recovery, but big amounts of collector not mean one greater recovery rate within 5 minutes flotation, 20 l is the ideal amount. Fuel oil as previously investigated in literature, has an important role to molybdenum recovery, large quantities of fuel oil with small amounts of collector results in better recovery rates for molybdenum.

Kinetics constant values showed that small amounts of reagents resulting in a faster kinetics and higher recovery values, however to achieve these high recovery levels a long residence time is necessary, which makes it uneconomical.

So the main objective of this work, which was maximize the copper and molybdenum recovery of QMPSW ore is possible with 20 l of collector and 23 l of fuel oil, however more tests with different percent of solids, different pH, and different frother is necessary before use of this ore in the plant.

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7. [1] [2] [3] [4]

REFERENCES Kodali, P. .: Pretreatament of copper prior to heap leaching , Master thesis(2010); http:// en.wikipedia.org/wiki/Froth_flotation, accessed in Feb/06/2011; http://en.wikipedia.org/wiki/Copper_extraction_techniques, accessed in Feb/06/2011; Martinek, K. .: High precision U-Pb (zircon) dating of the mineralization history of Bingham Canyon porphyry Cu-Mo-Au deposit, Utah, Master thesis (2009); [5] Inan, E.: Metasomatic processes in contact aureoles of porphyry Cu deposits A case study of Bingham District, Utah, Master thesis (2003); [6] [7] [8] [9] Wills, B.A.: Mineral Processing Technology, Seventh Edition, BH (2006); Davenport, W.G.: Extractive Metallurgy of Copper, Fourth Edition, Pergamon (2000); Handbook of Flotation Reagents: Elsevier (2010); Cytec: Mining Chemicals Handbook (2010);

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8.

APPENDIX A

Copper Recovery (%)

2 min Test #1 Test #2 Test #3 Test #4 Test #5 Test #6 Test #7 Test #8 Test #9 Test #10 Test #11 Test #12 Test #13 Test #14 Test #15 Test #16 Test #17 Test #18
88.65 85.14 81.78 87.89 88.95 87.82 89.44 90.68 86.96 88.65 86.22 83.64 81.45 87.59 89.51 85.68 83.04 77.19

Molybdenum Recovery (%)

2 min
79.15 74.97 69.67 76.60 77.40 77.92 75.88 79.82 78.32 79.15 72.90 70.50 64.98 76.44 77.90 64.60 73.78 72.34

5 min
93.91 93.62 92.65 93.56 94.28 92.94 94.71 94.01 94.31 93.91 94.65 92.74 92.55 92.97 94.20 92.17 91.17 86.58

10 min
95.81 95.53 94.75 95.40 95.44 95.21 96.05 95.20 96.05 95.81 94.91 94.85 95.06 94.95 95.80 93.46 93.87 95.93

5 min
87.53 86.80 84.54 86.72 86.34 86.04 87.53 86.43 89.06 87.53 84.65 84.91 83.22 86.07 87.67 77.00 84.65 83.33

10 min
90.78 90.68 88.81 90.71 89.04 90.36 90.63 88.63 92.31 90.78 89.56 89.49 89.11 89.82 90.96 80.13 89.01 92.05

Figure 28: Results of all tests.