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MCT Redbook

Solvent Extraction Reagents


and Applications
Going to extremes is our business.
Today, the mining industry is faced with a multitude of demands as well as
challenges. These include maintaining occupational safety, ensuring
increased environmental compatibility, and securing higher product
quality and lower costs. Cognis addresses these market demands by
continuing to emphasize product/process research and development, and
by customizing our service packages to meet the special needs of each
customer. Metal purification processes can reach higher levels of efficiency
and produce purer final metal products through the added value of
Cognis reagents and services.

With 50+ years of experience in solvent extraction and related


technologies, Cognis delivers comprehensive, high-performance solutions
that meet the new challenges of the mining industry and set new
standards for the future. We provide a full line of chelating and liquid ion
exchange reagents and systems designed to recover metals from aqueous
solutions. We specialize in base metals and energy metals recovery, and
we offer superior support services under the MSP® banner for all of our
products.

The Cognis Mining Chemicals Technology division is a reliable and


strategic partner of the leading international companies in the global
mining industry.
MCT Redbook
Contents

01
INTRODUCTION

03
DESCRIPTION OF THE SOLVENT EXTRACTION PROCESS
I. Extractable Metal Species
II. Reagent Requirements

07
TYPES OF EXTRACTANTS
I. Chelating Agents
A. General Comments
B. Commercial Applications for Copper Recovery
1. Sulfuric Acid Leaching Solutions
a. Commercial Copper Solvent Extraction LIX® Reagents
b. Cognis Copper Solvent Extraction LIX® Reagents
2. Ammonia Leach Solutions
C. Cognis Chelating Reagents and Some of Their Other
Possible Uses
D. Capital Costs for Copper SX-EW
E. Laboratory Evaluation Program for a Copper Leach
Solution
1. Extraction and Strip Isotherms
2. McCabe-Theile Diagrams
3. Continuous Copper SX Circuit
F. Isocalc® Computer Generated McCabe-Thiele Diagrams for
Copper

37
II. Ion-Pair Extractants
A. Alamine® Series
B. Aliquat® Series
C. Laboratory Evaluation Program for Ion-Pair Extractants
D. Present and Possible Future Uses of Amine Extractants

41
III. Neutral or Solvating Type Extractants

IV. Organic Acid Extractants

V. Ligand Substitution
MCT Redbook

47
REAGENTS IN DEVELOPMENT, GOLD

49
SOLVENT EXTRACTION DILUENTS

49
CONCLUSION

51
COGNIS QUALITY CONTROL AND OTHER USEFUL PROCEDURES
I. Standard Cognis Quality Control Test for LIX® Oxime Reagents
II. Analysis of Copper in Organic Solvent Extraction Solutions
III. Analysis of Copper in Aqueous Leach Solutions
IV. Cognis Quality Control Test for LIX® Nickel Oxime Reagents
V. Clay Treatment Test Procedure
VI. Direct Colorimetric Determination of Uranium on Amine

69
REFERENCES

Photos of mineral specimens courtesy of the Arizona Sonora Desert Museum


MCT Redbook
INTRODUCTION The cost of developing a new reagent, increased
regulations concerning toxicity of chemicals and the
An increasing demand for metals in general, and small markets of many metals all weigh against the
higher purity metals in particular, decreasing ore development of new metal extractants.
grades and more stringent environmental regulations
are continually driving research into finding more It is important for the reader to understand that
effective and efficient methods for processing the ores solvent extraction is only one unit process in a series of
available to us as well as the recycling of previously unit processes needed to win metal from ore. For this
used metals. Hydrometallurgy has provided, and will
continue to provide, many of the new processes.
Solvent extraction technology will certainly play an
important role in many of these new processes.

Solvent extraction as a simplified technique to purify


and recover a metal goes back to at least 1842 when
Peligot extracted uranyl nitrate into ethyl ether.1 The
chemical literature has hundreds of references to the
use of solvent extraction as a technique in analytical
chemistry and a large amount of fundamental
knowledge in solvent extraction, particularly in the
areas of solution chemistry and organic based
extractants, comes from analytical chemistry.2

Solvent extraction technology has been applied on a


commercial scale to the recovery of uranium, reason, solvent extraction must be compatible with,
vanadium and molybdenum since the 1950s3 and to and complimentary to, the leaching process which
copper and nickel since late 1960 – early 1970.4,5 For precedes it and the final metal recovery process which
this same length of time, Cognis Corporation (formerly follows (Figure 1). The success of the whole operation
General Mills Chemicals, Inc.) has been committed to then is dependent on the success of each individual
the development of solvent extraction technology in unit process.
general, and solvent extraction reagents in particular.
This commitment has resulted in the development and This booklet is designed to familiarize the reader with
manufacture of the LIX®, Alamine® and Aliquat® some of the basic concepts of solvent extraction
Reagents used by many commercially successful metal technology as well as with the LIX®, Alamine® and
recovery operations around the world. These Cognis Aliquat® brands of solvent extraction reagents.
reagents are noted for the wide range of conditions in Furthermore, this booklet will introduce other
which they operate and for their pollution-free flow reagents, systems and services provided by the Mining
sheets. While it is within the realm of technical Chemicals Technology business of Cognis. More
feasibility that the hydrometallurgist could one day detailed information about specific reagents, metals, or
have an unlimited selection of commercially available process systems is available on request and on the
chemical reagents at his disposal in order to make Cognis website: www.cognis.com.
efficient separations of virtually all metals in solution,
LIX®, Alamine® and Aliquat®, Isocalc®, MSPTM, Cognis and Cognis logo
this will be difficult to achieve because of economics. (Cognis & Design) are registered trademarks of the Cognis Group.

1
Copyright© 2007 by Cognis Group
MCT Redbook
Figure 1.
Generalized Metal Recovery Flowsheet Incorporating
Solvent Extraction and Cognis Reagents

ch Solution Reagent Strip Solution


d Lea d LIX® eous
le pe u
yc rip Aq
c

St
Re

Metal Leaching Metal Extraction Metal Stripping


Pure Metal Product
Im

ed
pu

e nt ifi
e ur
r

M
eta ag Conc & P
l Le a Me
t a l Lo a d e d L I X ® R
e entrated lution
ch S olution Metal So

Leaching Solvent Final Metal


Process Extraction Recovery

2
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MCT Redbook
DESCRIPTION OF THE metal recovery usually takes place from the aqueous
SOLVENT EXTRACTION PROCESS solution. The recovery of metal directly from the
loaded organic phase is also possible but it is practiced
Solvent extraction (SX) is applicable in any instance commercially in only special cases probably because of
where it is desirable to selectively remove or extract a organic contamination of the final product.6,7,8 Because
species from one solution into another. This can apply the solvent extraction process resembles metal
either to the removal of a valuable component from extraction with solid ion exchange resins, it is
contaminants or to the removal of contaminants from sometimes called “liquid ion exchange.”
the valuable component. The solution originally
containing the desired species and the solution into Figure 2 shows a typical counter-current, mixer-settler
which this species or the contaminants are to be solvent extraction circuit having 3 countercurrent
extracted must be immiscible to effect separation. extraction stages and 2 countercurrent strip stages. An
individual mixer-settler is known as a stage. In some
In metal recovery systems, specific problems make it desirable to add
operations, the one or more organic “wash”or “scrub”stages on the
valuable compo- loaded organic phase and / or the stripped organic
nent is normally a phase in order to prevent the transfer of deleterious
metal ion or a species from extraction to strip or vice versa.
metal ion complex
contained in an Solvent extraction and Cognis reagents, as part of an
aqueous solution. overall metal recovery process, have three main
This aqueous objectives:
solution is mixed
intimately with an 1. The purification of a metal(s) from unwanted
immiscible organic impurities either by extracting the desired metal(s)
phase containing from the impurities or by extracting the impurities
the active from the desired metal(s).
extractant at which
time the active extractant transfers the desired metal 2. The concentration of metal in order to reduce
from the aqueous phase into the organic phase. The downstream processing costs.
aqueous / organic dispersion passes from the mixer to
a settler where the phases disengage. The “loaded 3. The conversion of the metal values to a form which
organic”phase, now containing the desired metal, is simplifies eventual recovery.
then transferred from the extraction settler to the
stripping mixer. Here the “loaded organic”phase is In any given solvent extraction process, one, two or all
mixed intimately with an aqueous stripping solution three objectives may be accomplished.
containing a chemical that provides the driving force
required to strip the loaded metal from the organic These objectives can usually be met by choosing the
phase into the aqueous stripping phase. The aqueous / proper reagent and operating under the optimum
organic dispersion passes from the mixer into a settler conditions. A variable number of mixer-settler stages,
from which the “stripped organic”is recycled back to adjustable flow rates and the ability to use wash stages
extraction while the aqueous phase, now containing allows the optimization of operating conditions as well
the desired metal, goes to final metal recovery. Final as design flexibility.

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Copyright© 2007 by Cognis Group
MCT Redbook
Figure 2. Copper Continuous Liquid Ion Exchange Unit

Extraction Stripping
Stripped Organic

E-3 E-2 E-1 S-1 S-2

Loaded
Organic
Aqueous Surge Stripping Solution
Aqueous

Barren Stripping
Solution
Aqueous
Barren Aqueous Feed (PLS)
Raffinate

Pregnant
Stripping Solution

4
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MCT Redbook
I. Extractable Metal Species
If a metal is to be extracted from impurities or vice
versa it is important to know the various metal and
other species present in solution. With respect to
metals, the extractable species can be divided into four
categories:

1. Metal cations such as Cu2+, Ni2+, and Co2+

2. Complex metal anions, for example UO2(SO4)34-,


and Mo8O264--

3. Complex metal cations such as MoO22+

4. Neutral metal specials like UO2(NO3)2

The examples above represent metal species which


have been recovered commercially in solvent
extraction plants. There are many others.

5
Copyright© 2007 by Cognis Group
MCT Redbook
II. Reagent Requirements Cognis reagents possess this balance of properties.

It is obvious that if a metal species is to be transferred There are misconceptions about the selectivity of
from an aqueous leach solution into an organic reagents which merit discussion. It should be realized
solution, there must be some chemical interaction that few if any reagents are selective for only one metal
which causes this to happen. The component in the under all conditions, but that many reagents are
organic phase, which chemically interacts with the selective for only one metal under certain conditions.
metal, is properly called the “extractant”but is also Selectivity is dependent upon the conditions and the
commonly called the “reagent.” challenge is to match the conditions presented by a
given leach solution to the selectivity characteristics of
At the present time, there are organic extractants the reagents available. A perfect match is not always
known for virtually all metals in one form or another.9 possible and is, in fact, rare. Most of the time, the
As stated previously, this body of knowledge is due in researcher either settles for a reagent which, even
large part to analytical chemists, however, the though not perfect, functions well, or the researcher
requirements for a successful extractant in analytical tries to alter the leaching method to give a leach
chemistry are much different than the requirements for solution from which a reagent will be more selective. In
a reagent to be successful in large scale metal recovery order to do this successfully, the chemistry of
operations, especially as they relate to process extraction processes must be understood.
continuity and economics. In order for a metal
extraction reagent to be commercially successful, it
must:

a. Extract the desired metal(s) selectively from the


metal-containing aqueous solution.
b. Be strippable with a solution from which eventual
metal recovery can take place.
c. Be stable to the circuit conditions so it can be
recycled many times.
d. Be nonflammable, nontoxic, noncarcinogenic, etc.
e. Be soluble in an inexpensive organic diluent or have
a low enough viscosity that a diluent is not required.
f. Load and strip metal at a rate fast enough to allow
for the use of economical mixing times.
g. Not promote stable emulsions.
h. Not transfer deleterious species from strip to
extraction.
i. Have an acceptable cost.

Normally, reagent behavior with respect to the above


list is not a black and white, pass or fail situation. No
one reagent is the best with respect to all of the
properties in the list; rather, successful reagents possess
a good balance of all of the properties in the list.

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MCT Redbook
TYPE OF EXTRACTANTS fact is not always important for iron(III) since it is only
slightly soluble at pH 5. It is important to realize that in
There are five classes of metal extractants as order to make a direct comparison of the pH isotherms
char-acterized by structure, extraction mechanism of two different reagents with the same metal, or of
and the metal species extracted: chelation, organic two different metals with the same reagent, the pH
acids, ligand substitution, neutral or solvating and ion isotherms must be determined under exactly the same
pairing. Cognis markets chelation reagents and ion conditions.
pairing reagents and has research interests in ligand
substitution reagents. A tabular method to express these extraction
characteristics is shown in Table I.
I. Chelating Extractants
A. General Comments Table I. Relative Extraction Power of
LIX® 84-I for Metals at pH 2.0
Chelating refers to “claw”, which is a graphic
description of the way in which the organic extractant Metal Relative Extractive Power
binds a metal ion. i.e., the extractant chemically bonds Cu(II) Very strongly extracted
to the metal ion at two sites in a manner similar to Fe(III) Slightly extracted
holding an object between the ends of the thumb and Mo(VI) Somewhat strongly extracted
the index finger. In many cases, upon bonding with the V(V) Slightly extracted
metal ion, the extractant releases a hydrogen ion into Zn(II) Nil
the aqueous solution from which the metal was
Sn(II) Nil
extracted. The simplified equation shown below is for
Ca(II) Nil
the extraction of a metal cation with a +2 charge.
Mg(II) Nil
As(III) Nil
Extraction Al(III) Nil
[2RH]org + [M2+SO4=]aq [R2M]org + [2H+ + SO4=]aq
Stripping Fe(II) Nil
Si(V) Nil
Co(II) Nil
One of the important parameters controlling the Ni(II) Nil
equilibrium position of this reaction is the acid content
of the aqueous phase. A graphic representation of this *The chemistry of Mo(VI) and V(V) is complex on the acid side,
however, these metals do not normally present a problem to a
behavior is referred to as a pH isotherm. Some typical copper solvent extraction circuit.
pH isotherms for the reagent LIX 84-I are shown in
Figure 3. These pH isotherms can be used to predict
the extraction characteristics of the reagent with
respect to the metals shown under a variety of The investigator screens the reagent against the metals
conditions. For example, from Figure 3, it is apparent most likely to be found in the aqueous feed solutions
that at pH 2.0 copper(II) is strongly extracted and ferric of interest under conditions similar to those expected
iron is slightly extracted by LIX 84-I while nickel(II) and in the solvent extraction process. This is normally
cobalt(II) are not extracted. However, at pH 5, all four of referred to as selectivity data and holds only at the
these metals are strongly extracted, except that this conditions under which it is determined. These

7
Copyright© 2007 by Cognis Group
MCT Redbook
Figure 3. Metal Extraction by LIX® 84-I as a function of pH.

Cu2+
Ni2+ Co2+
2
(Metal) in g/l

1
Zn2+
Fe3+

1 2 3 4 5 6
pH

8
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MCT Redbook
conditions include the metal and reagent with Cu(II) and Ni(II) (Figure 3) suggests that a good Cu-
concentrations, the oxidation state of the metal, the pH Ni separation can be made with LIX 84-I by controlling
of the aqueous feed solution and the organic-aqueous the pH in the extraction stages. All of the copper can
contact time. From Table I, it is obvious that Cu(II) and be extracted at low pH (1.5 to 2.0) before the system is
Mo(VI) are the only metals listed which are strongly adjusted with ammonia to higher pH (9.0 to 9.5) where
extracted by LIX 84-I at pH = 2. While the extraction the nickel is extracted. This type of scheme has been
data suggests Mo(VI) could be a problem in a copper used on a commercial scale at the S.E.C. Corporation in
solvent extraction circuit using LIX 84-I, in fact, it El Paso, Texas, for the recovery of copper and nickel
typically is not a problem for two reasons. Copper will from a refinery bleed stream using the extractant LIX
readily displace Mo(VI) from LIX 84-I and molybdenum 64N.5
loaded on LIX 84-I is not readily stripped with a sulfuric
acid solution as is copper. In most cases, only Fe(III) The LIX 84-I ammonia dependent extraction curves in
presents a potential problem to the preparation of a Figure 4 show that copper(II) is more strongly extracted
pure copper solution from a “normal”copper leach from an ammoniacal solution than is nickel. Thus,
solution at pH = 2. This data is in agreement with the copper-nickel separations from ammonia leach
pH isotherms shown in Figure 3 on page 8. solutions should be possible, and indeed have been
studied, for a similar reagent.10 The study concentrated
The extraction of metals from ammoniacal solution is on a flow scheme where copper is preferentially
also an area of interest, thus, the extractive behavior of extracted from an ammonia solution containing
some metals from ammoniacal solutions has been copper and nickel before the nickel is extracted. A high
examined. In general, this data is expressed as copper / nickel ratio on the copper loaded organic is
ammonia dependent extraction isotherms, several of obtained by using an extra extraction stage in which
which are shown for LIX 84-I in Figure 4. The tendency copper crowds nickel from the loaded organic, i.e., the
for extraction to decrease with increasing ammonia copper in an ammoniacal copper and nickel containing
concentration can readily be explained by the solution, when contacted with an organic loaded with
extraction/stripping equation for a typical +2 metal nickel, will replace some of the loaded nickel.
cation shown below:
After the copper and nickel are loaded in separate
extraction operations, each “metal loaded organic”
[M(NH3)42+]aq + [2RH]org [R2M]org + [2NH3]aq + [2NH4+]aq phase is separately washed and stripped to give a
copper-rich and a nickel-rich strip aqueous phase,
respectively. Circuit complexity, overall operational
In essence, ammonia in solution with its lone pair of ease and the number of stages required are dependent
electrons on the nitrogen atom competes with the upon the aqueous feed.
extractant for the metal ion. The reaction is reversible
and stripping with ammonia might be practical in An alternative separation scheme on the same type of
some situations. The number of ammonia molecules solution has been reported11 and also studied by
coordinated to the metal will vary depending on the Cognis.12 This scheme involves the coextraction of
conditions; four being a favored number. nickel and copper with the same organic stream
followed by a pH controlled wash to remove the small
By considering extraction isotherms and selectivity amount of co-extracted ammonia. The nickel and
data, it is possible to develop metal separations copper loaded organic is stripped using pH control to
schemes. For example, the pH isotherms of LIX 84-I give a copper free, nickel-rich solution and a copper-

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Copyright© 2007 by Cognis Group
MCT Redbook
Figure 4. Metal Extraction by LIX® 84-I as a function of total NH3

Ni Cu
100

80
% Metal Extracted

60

40

20
Zn

20 40 60 80 100 120 140 160


+
g/l Total NH3 (NH3/NH =2/1)
4

rich solution with a small amount of nickel. This flow The study of pH isotherms, selectivity data and
scheme is based on the ammonia isotherms, which ammonia isotherms leads to the conceptual
show that copper and nickel are strongly extracted development of metal separation processes. However,
from ammoniacal solutions by LIX 84-I, and the pH this type of data does not tell in a detailed way how to
isotherms, which show that while LIX 84-I loads copper do a given metal separation, or the way the circuit
very well at a pH of 2.5 to 3.0, nickel is readily stripped must be set up in order to do the separation in the
at that pH. most effective, least costly manner. Laboratory work is
required.

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MCT Redbook
B. Commercial Applications for Copper Other common constituents of leach solutions include:
Recovery Fe, Mo, Mn, Al, Mg, Na, K, sulfate ions and, at times,
chloride ions. Most copper EW tankhouses, coupled
1. Sulfuric Acid Leach Solutions with SX in the acid sulfate system, plate copper from an
electrolyte exiting the cell containing 32 to 40 g/l Cu
The use of chelation type extractants in liquid ion and 150 to 185 g/l sulfuric acid. Under these
exchange has enjoyed its greatest commercial success conditions, an EW tankhouse should produce high
for the recovery of copper from dilute sulfuric acid quality copper. Over time, the current density at which
leach solutions. These solutions are generated from the copper is plated has increased from 160 amps / m2 in
leaching of copper oxide and/or sulfide ores using a the late 1960’s to well over 300 amps / m2 today. In
variety of leaching techniques including dump, heap, order to help assure high quality copper is produced at
in-situ, vat, thin layer and agitation. Leaching of copper high current density, the copper in the electrolyte
concentrates is an emerging area. Leach-SX-EW exiting the cell is typically > 35 g/l Cu and at times > 40
technology begins with leaching and Cognis advises g/l Cu. There is also evidence that slightly higher
that companies considering this technology quality copper is obtained when the copper is plated
thoroughly investigate the leaching characteristics of from acid in the lower end of the acid concentration
their ore. Money spent up front in leaching studies range.
usually pays handsome dividends.
As of June 2006, there were 55 operating copper SX
Typical leach solutions may contain less than 1 g/l Cu plants outside of China recovering copper from dilute
up to about 50 g/l Cu over a pH range of < 1.0 to 3.0. sulfuric acid leach solutions with several new plants
The leach solution may also contain high levels of under engineering / construction and others planned.
chloride and a host of other impurities depending on Actual operating costs for a relatively large plant, the
the ore, available water and evaporation rate. Typical tailings leach plant of the Chingola Division, Zambia
sulfuric acid leach solutions successfully treated by Consolidated Copper Mines, Ltd., in Zambia, Africa,13
solvent extraction are summarized in Table II. and one of the smaller, the Cyprus Bagdad Copper
Company plant in Bagdad, Arizona,14 have been
published. In addition, Jenkins et. al. have published
Table II. Typical Sulfuric Acid Leach operating data from a large number of copper
Solutions L/SX/EW operations.15 One advantage of copper
leach/SX/EW technology is that it is economical on a
Type Cu (g/l) pH very large or very small scale. For example, Phelps
Dump, Heap, In-situ < 1 to 6 1.3 to 2.2 Dodge Morenci produces about 32,000 tons per
month of high quality cathode copper, and Dos
Ferric Cure, Thin Layer 3 to 6 1.5 to 2.2 Amigos in Chile produces about 900 tons per month of
superior quality cathode copper. A second advantage
Vat 5 to 50 1.6 to 2.0 is that operating costs for a proposed leach / SX / EW
operation can be predicted with good accuracy.
Agitation 1 to 35 1.4 to 2.0

Concentrate 25 to 80 < 1 to > 2

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Copyright© 2007 by Cognis Group
MCT Redbook
a. Commercial Copper Solvent Extraction LIX® extractants. The strength of a copper extractant is
Reagents based on the degree to which copper extraction is
driven by the reagent. In simple terms, very strong
Even though a large number of molecules with a wide copper extractants extract substantial amounts of
variety of extractive functionalities have been copper at pH values less than 1.0, while moderate
proposed as extractants to be used for the recovery of strength copper extractants are most useful above a
copper from sulfuric acid leach solutions, only the pH of 1.6-1.8.
hydroxy oximes have been used in commercial copper
SX plants. The basic structure for these copper Ketoxime / salicylaldoxime mixtures are a third “class”of
extractants is shown in Figure 5. copper solvent extraction reagents based not on
structure, but rather on the distinct and advantageous
Extractants having this general structure can be sub- properties the mixtures exhibit. These patented
divided into two distinct classes based on their mixtures16 span the range from moderately strong
structure and properties: the ketoximes, which are copper extractants to very strong copper extractants
normally copper extractants of moderate strength and depending on the ratio of ketoxime to salicylaldoxime.
the salicylaldoximes, which are very strong copper

Figure 5.
General Chemical Structure of the Hydroxy Oximes Used Commercially for Copper Recovery

OH NOH

A
R = C9H19 or C12H25
A = H Salicylaldoximes
A = CH3 or C6H5 Ketoxime

R
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MCT Redbook
Ketoximes: The ketoxime-based reagent LIX 64 was significantly to the amount of crud generated in some
the first hydroxy oxime extractant to be used solvent extraction circuits.18 Another problem
commercially for the extraction of copper from dilute sometimes associated with modified reagents is the
sulfuric acid leach liquor.4 Ketoximes were used contamination of electrolyte due to the excessive
exclusively for about 11 years. The most outstanding entrainment of leach liquor in the loaded organic
feature of the ketoximes, as represented today by LIX stream.
84-I, is the good physical performance they display
under a wide variety of conditions, especially with As a group, salicylaldoximes are less stable than
respect to aqueous solutions that are known to cause ketoximes and within the salicylaldoxime subgroup,
phase separation problems and crud generation when the dodecyl derivative is more stable than the nonyl
in contact with modified copper SX reagents. Examples derivative. In operating circuits at normal
include agitation leach solutions which contain temperatures, reagent degradation with
colloidal silica, some solids and/or residual flocculent. A 5-nonylsalicylaldoxime has been calculated to be equal
second outstanding feature of the ketoxime reagents is to about 10% of the total reagent makeup. While few
their very good chemical stability under conditions degradation results on operating circuits have been
where aldoximes degrade rapidly. Leach solutions published, the degradation in some plants is known to
containing nitrate and chloride ions, such as some of be higher than the calculated value depending on the
those found in the Atacama Desert in Chile, are modifier, the temperature and the acid content of the
examples.17 LIX 84-I shows excellent phase separation, aqueous stripping solution. With heated circuits,
low entrainment losses to the raffinate, and it does not reagent degradation is more significant and should be
promote excessive crud formation. LIX 84-I is only a determined experimentally. Fortunately, overall
moderately strong copper extractant so the number of reagent losses are quite low in a well-operated copper
copper SX plants using LIX 84-I exclusively is limited. SX plant so the losses due to degradation are usually
However, in the circuits that use LIX 84-I, the operator not excessive in any case.
enjoys a low cost, trouble-free copper extractant.
Modified salicylaldoxime reagents such as LIX 622N,
Salicylaldoximes: The salicylaldoximes were LIX 612N-LV and LIX 616N-LV have been used
developed to overcome the perceived shortcomings of successfully in commercial circuits which are designed
the ketoximes. Their outstanding characteristics for them and where the chemistry of the leach solution
include rapid copper transfer kinetics and high requires their use.
extractive strength. In fact, salicylaldoximes are such
strong copper extractants that they cannot be
efficiently stripped with typical copper tankhouse
electrolytes. For this reason, they are normally used in
combination with an equilibrium modifier, and/or with
a ketoxime, to effect efficient stripping with an acidic
copper solution from which high quality copper can be
electrowon.

The use of equilibrium modifiers leads directly to


certain shortcomings in that some modifiers are
known to accelerate reagent degradation. It has also
been reported that equilibrium modifiers contribute

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Copyright© 2007 by Cognis Group
MCT Redbook
Ketoxime-Salicylaldoxime Mixtures: Properties of solutions of high pH since this mixture would strip very
ketoxime-salicylaldoxime mixtures containing no well but still have the extractive strength needed to
added modifier, such as LIX 984 and LIX 984N, reflect achieve high copper recovery. The result would be a
the most desirable properties of the components: the reagent that combines high copper recovery with a
extractive strength and fast kinetics of the salicylal- high copper net transfer. Ketoxime/ aldoxime mixtures
doximes combined with the proven, excellent physical could prove to be a universal reagent system for acid
performance and stability of the ketoximes.18 sulfate copper leach solutions since, in most instances,
a properly tailored mixture will function both physically
An interesting feature of these mixtures is the greater and chemically very well with virtually any leach
than expected copper transfer these mixtures give solution of this type.

Modified Ketoxime-Salicylaldoxime Mixtures:


MAKTM Reagents, a fourth class of oxime extractants
consist of ketoxime-salicylaldoxime mixtures to which
a small amount of equilibrium modifier has been
added. Such blends have been used since 1985 in
several commercial operations and exhibit good
copper transfer and selectivity.

Since all four reagent classes of oxime extractants are


commercially successful, it follows that each class of
extractant meets the reagent requirements previously
given. In reading the successful reagent requirements,
it is obvious that they are somewhat general in nature.
For example, the first requirement says that the
reagent must extract the desired species selectively (in
this case copper), but it says nothing about how much
copper must be extracted, nor the degree of selectivity
the reagent must have. In fact, it is virtually impossible
to be more specific because each leach liquor, plant
and reagent is unique.

because of their lower than expected stripped organic Whereas a given reagent requirement may be critical in
value. It is felt this property results from the ketoxime one situation, in another it may be relatively
component of the mixture functioning as a modifier unimportant. What should be understood is that all
for the salicylaldoxime component in the strip stages three classes of hydroxy oxime reagents possess the
of the circuit. successful reagent requirements to such an extent that
all three classes are commercially successful, yet, no
Since the ketoxime and salicylaldoxime components one reagent is the best for each and every copper
can be mixed in any ratio, a reagent mixture can be leach liquor or copper solvent extraction circuit.
tailored to the needs of almost any leach liquor over a
wide range of pH values. For example, a mixture high
in ketoxime would be most appropriate for leach

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b. Cognis Copper Solvent Extraction LIX® Reagents Copper over iron selectivity can be controlled to some
extent by the mixture and by the addition of a
Cognis produces three oxime extraction molecules: modifier. In some cases, a plant may need very high
5-nonylsalicylaldoxime, 5-dodecylsalicylaldoxime and selectivity, and in other cases, a plant may want to
5-nonyl-2-hydroxyacetophenone oxime. These three transfer some iron to the strip electrolyte. Cognis can
oximes form the basis for a wide range of reagents often formulate a reagent to meet the iron transfer
which are derived by blending the oximes in a variety needs of the plant.
of ways, for example, with diluent, with one another
and/or with a modifier, to give LIX Copper Solvent Cognis makes available both normally formulated
Extraction Reagents with properties that best fit the reagents and concentrated reagents. The concentrated
particular leach solution and plant design under reagents contain the same oxime or oximes as the
consideration. As of February 2006, Cognis is the only normally formulated reagents, but less diluent. This
supplier that produces both aldoxime and ketoxime saves on packaging, shipping and handling costs, but
reagents and is therefore the only supplier that truly results in neat reagent being more viscous.
offers a full line of copper solvent extraction reagents. Concentrated reagents can be supplied by Cognis in
regions with ambient temperatures above 5˚C.
For example, Cognis is the only supplier to offer a line
of low viscosity (LV) reagents that can be used at Table III describes only a limited number of the wide
higher reagent concentrations than reagents available range of oxime based copper solvent extraction
from any other supplier. This offers some plants the reagents available from Cognis.
opportunity to reduce the size of the mixer settler
units. Cognis will work with customers to formulate a reagent
that is best for a particular plant and/or leach liquor.
Cognis is also the only supplier to offer reagents based More information about Cognis oxime copper solvent
on 5-dodecylsalicyaldoxime, an extractant that is extraction reagents, or a more in-depth discussion of
nearly twice as stable to hydrolysis degradation as the copper extraction from dilute sulfuric acid leach
extractant 5-nonylsalicaldoxime.19 Reagents based on solutions, is available by contacting your local Cognis
5-dodecylsalicylaldoxime are particularly suitable for representative.
use in copper SX plants operating at elevated
temperatures, where degradation of
5-nonylsalicylaldoxime is economically significant.

Furthermore, a few operating copper SX plants have


purchased the individual ketoxime and aldoxime
reagents and mixed these reagents in a way that best
matched the needs of the particular leach solution,
plant or season. The ability to purchase the individual
ketoxime and aldoxime reagents gives copper SX plant
operators great flexibility in the operation of their plant
to meet changing conditions, for example, summer
verses winter operation, while still maintaining
excellent physical properties.

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MCT Redbook
Table III. Composition of some Hydroxy Oxime Copper Extraction Reagents from Cognis.

Extractant/Category Composition
LIX® 84-I /Ketoxime A mixture of 2-hydroxy-5-nonylacetophenone oxime in a high
flash point hydrocarbon diluent needed for handling purposes.

LIX® 84-IC / Ketoxime The concentrated version of LIX 84-I

LIX® 860-I /Salicylaldoxime A mixture of 5-dodecylsalicylaldoxime in a high flash point


hydrocarbon diluent needed for handling purposes.

LIX® 860N-I /Salicylaldoxime A mixture of 5-nonlysalicylaldoxime in a high flash point


hydrocarbon diluent needed for handling purposes.

LIX® 984N /Mixture An equal volume mixture of LIX 84-I with LIX 860N-I.

LIX® 973 /Mixture A 7 / 3 volume blend of LIX 860-I with LIX 84-I.

LIX® 937N / Mixture A 3 / 7 volume blend of LIX 860N-I with LIX 84-I

LIX® 622N / Modified Salicylaldoxime A mixture of 5-nonylsalicylaldoxime and tridecanol in a high


flash point hydrocarbon diluent.

LIX® 622N-LV / Modified Salicylaldoxime A mixture of 5-nonylsalicylaldoxime and a proprietary low


viscosity alcohol in a high flash point hydrocarbon diluent

LIX® 612N-LV/ Modified Salicylaldoxime A mixture of 5-nonylsalicylaldoxime and a proprietary low


viscosity modifier in a high flash point diluent.

LIX® 616N-LV/ Modified Salicylaldoxime A mixture of 5-nonlysalicylaldoxime and a proprietary low


viscosity modifier in a high flash point diluent.

LIX® 6422-LV/ Modified Salicylaldoxime A mixture of 5-dodecylsalicylaldoxime and a proprietary low


viscosity modifier in a high flash point diluent.

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2. Ammonia Leach Solutions when used with ammonia leach solutions having a pH
above about 10. LIX 55, a more stable beta-diketone
The extraction of metal from ammonical leach functionality than LIX 54, does not exhibit these same
solutions is a second commercial application for stability problems. Both LIX 54 and LIX 55 are
chelating agents. Ketoxime reagents, LIX 65N and LIX considered special order reagents and require
84-I, and beta-diketone reagents, LIX 54 and LIX 55, significant lead times. Also, LIX 55 is not registered in all
have been used for this application. In one example, countries and therefore has limitations on where it may
the ketoxime reagent LIX 65N was used as the be used.
extractant for a leach solution derived from the
ammonia leaching of copper sulfide concentrates in a
process termed the “Arbiter Process.”20 In another
example, LIX 54 was used as the extractant for copper
from leach liquor derived from the ammonia leaching
of copper-lead dross.21

LIX 54 and LIX 55 are designed for the extraction of


copper from ammoniacal leach liquors. Their ease of
stripping, low ammonia loading, fast kinetics, good
phase separation, high copper loading and low
viscosity when fully loaded, make them ideally suited
for this task.22 However, LIX 54 has stability problems

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Notes:
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C. Cognis Chelating Reagents and Some of
Their Other Possible Uses

LIX 54/LIX 55: These low viscosity beta-diketone


reagents are used for the selective extraction of copper
from ammonia leach solutions at pH about 9.5 or less.
They strip with very low concentrations of residual
sulfuric acid and operate at a high net copper transfer.

LIX 63: This hydroxy oxime has been proposed for


germanium recovery,23 for copper recovery from typical
tankhouse electrolytes,24 in synergistic mixtures with
other reagents for cobalt and nickel recovery25, 26, 27 and
for the separation of molybdenum from uranium in
dilute sulfuric acid solution.28

LIX 26: This reagent is based on an alkylated


8-hydroxyquinoline and has been proposed for the
extraction of gallium from Bayer liquors.29 LIX 860-I: This aldoxime-based reagent, containing no
added modifier, has been proposed as a reagent for
LIX 84-I: This ketoxime based reagent requires about the coextraction and selective stripping of copper and
150 g/l H2SO4 for copper stripping and contains no zinc.33 In addition, under certain conditions, this
added modifier. It is widely used for copper recovery reagent can be used to extract copper efficiently at pH
from dilute sulfuric acid leach solutions. This reagent is values less than 1.0.
particularly important for the recovery of copper from
leach solutions containing nitrate ions where the LIX 6422-LV: This 5-dodecylsalicylaldoxime-based
stability of the ketoxime reagent allows it to be used reagent is designed for the extraction of copper from
under conditions where a modified aldoxime reagent higher temperature leach solutions where enhanced
is not at all suitable.18 LIX 84-I is also used for copper stability is particularly important.
recovery from ammonia leach solutions in a manner
similar to LIX 64N and LIX 65N.30 A similar ketoxime LIX 612N-LV and LIX 616N-LV: These modified, very
based reagent LIX 84-A has applications for the selective, low viscosity, low density reagents are based
recovery of palladium from acid chloride solutions.31 on salicylaldoxime and are designed to extract copper
from acidic leach solutions. Under certain
LIX 84-INS: is a ketoxime based reagent which has circumstances, the low viscosity properties of these
application for the recovery of nickel from ammonia reagents allow them to be used at higher
solutions in a manner similar to LIX 64N.10, 11, 12 concentrations than other salicylaldoxime-based
reagents.
LIX 87QN: This ketoxime-based reagent was
developed specifically for the extraction of nickel from Whereas the above list is impressive, it should not be
ammonia, followed by a stripping operation using a considered as limiting. Cognis is constantly working on
concentrated solution of ammonia and carbon the development of new chelating functionalities as
dioxide.32 well as on new applications for existing chelation-type
extractants.
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MCT Redbook
D. Capital Costs for Copper SX-EW

It is difficult to have a formula by which to predict


capital costs for solvent extraction-electrowinning
plants. Material costs, local site conditions, local labor
markets, the type of construction, the nature of the
feed and the final plant designs are important variables
in predicting capital costs. While Cognis tries to keep
current in these areas, capital cost estimates are best
left to engineering companies who deal with them
frequently. Should a prospective user of copper solvent
extraction need capital cost estimates, Cognis will be
pleased to offer the names of several engineering
companies with experience in this area.

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E. Laboratory Evaluation Program for a 1. Extraction and Strip Isotherms
Copper Leach Solution
Experience tell us that LIX 984N, a mixed
Assuming a metal containing solution is available, what aldoxime-ketoxime reagent, is a good reagent for the
is the next step? The first thing is that the contents of leach liquor under discussion. Previous work shows LIX
the solution must be known, (metals, pH, NH3, chloride, 984N transfers about 0.24 to 0.30 g/l Cu per volume %
nitrate, etc.) as well as whether that solution is typical in a 2 extraction – 1 strip stage circuit, where ~ 90 %
of the feed solution to be treated. The evaluation of a copper recovery was obtained. Since the leach liquor
feed solution which is not typical of the solution to be of interest has a pH of 1.8, assume that copper transfer
treated can, at times, be a wasted effort. Once the will be in the middle to lower end of the range. The
solution contents are known, judgments about which following simple calculation then gives the
metals can be approximate reagent concentration which should be
separated should suitable:
be made based on
the extraction 2.50 g/l Cu x (0.90) / 0.26g/l Cu per v/v% reagent
isotherms = 8.7 v/v% reagent
available. If data on
some of the An organic solution containing 8.7 v/v% LIX 984N in a
contained metals is suitable diluent was prepared and then vigorously
not available, the contacted once for about three minutes in a separatory
reagent(s) to be funnel with the feed solution at an organic /aqueous
used should be (O/A) ratio of about 1. After the phases have separated
screened against and the aqueous phase is discarded, the copper-
these metals. Once loaded organic phase is vigorously contacted three
this is done, it times, for about one minute each contact, with fresh
should be known pregnant strip solution (the aqueous solution expected
which metals are to exit the strip stage of the circuit, 50 g/l Cu and 160
considered g/l H2SO4 in this case), also at an O/A=1. This results in
desirable to recover, and which metals are possible to an organic solution which closely approximates the
recover by solvent extraction under the given set of stripped organic (S.O.) to be expected in a continuous
conditions. The circuit development work can now circuit operation having one strip stage. The newly
begin with the realization that all parts of the total prepared stripped organic and the leach solution are
metal recovery scheme must fit together in a workable then equilibrated at various organic to aqueous
manner. volume ratios by vigorous contact for 3-10 minutes in
separatory funnels or by rapid stirring in mixer boxes.
For example, consider a solution obtained from a After phase separation, the respective organic and
typical copper leach operation containing 2.5 g/l Cu(II) aqueous layers are filtered and saved for analysis. The
and 1.30 g/l total Fe at a pH of 1.80. The overall goal of organic layer is analyzed for copper (and perhaps iron)
the laboratory evaluation program is to determine the and the aqueous layer for copper only. The data is
conditions required so that about 90% copper recovery shown in Table IV (on page 23) and is plotted as
is realized. It is also important to generate data on illustrated in Figure 6.
copper over iron selectivity.

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MCT Redbook
Figure 6. Equilibrium Extraction Isotherm and First Approximation McCabe-Thiele Diagram

5.0

L.O.
4.0

Feed = 2.50 g/l Cu


Organic g/l Copper

3.0

2.0
S.O.

1.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Raff. = 0.22
Aqueous g/l Copper
Organic: 8.7 v/v% LIX 984N
Aqueous: 2.50 g/l Cu, 1.30 g/l Fe (Total), pH=1.80

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Stripping isotherm data is generated in a similar
fashion by equilibrating the stripping aqueous phase Table IV. Equilibrium Extraction and
(S.E.), in this instance a typical copper electrowinning Stripping Data for LIX® 984N
tankhouse electrolyte containing ~30 g/l Cu and 190 Analysis in g/l Cu
g/l H2SO4, with copper loaded organic (L.O.) at various
Extraction
O/A ratios (Table IV, Figure 7).
O/A Organic Aqueous
10/1 2.04 0.07
5/1 2.28 0.09
2/1 2.96 0.17
3/2 3.26 0.26
1/1 3.70 0.51
1/2 4.19 1.24
1/5 4.35 1.94

S.O. 1.80
Leach Solution 2.50

Stripping
O/A Organic Aqueous
10/1 1.76 51.3
5/1 1.38 43.2
2.5/1 1.21 37.7
1/1 1.07 33.8
1/2 1.01 32.3
1/4 0.98 31.2

L.O. 3.90
Isotherms are unique to the conditions under which S.E. 30.7
they are generated. If one of the parameters is
changed, for example, the reagent concentration, the
copper concentration of the aqueous phase, the pH of
the leach liquor, the acid concentration of the strip
liquor, the temperature,67 etc., then a different isotherm
will be generated. In instances where the change in
one or two of the parameters is very small, it may not
be necessary to run a second isotherm.

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MCT Redbook
Figure 7. Equilibrium Strip Isotherm and One-Stage McCabe-Thiele Diagram

60

Loaded Organic = 3.90 g/l Cu


P.E.
50
Aqueous g/l Copper

40

S.E.
30
S.O. = 1.77

20
1.0 1.5 2.0 2.5 3.0 3.5 4.0

Organic g/l Copper


Organic: 8.7 v/v% LIX 984N
Aqueous: 30.7 g/l Cu, 190 g/l H2SO4

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2. McCabe-Thiele Diagrams loaded organic of 4.17 g/l Cu are predicted. The
construction of a true equilibrium McCabe-Thiele
Properly generated extraction and stripping isotherms diagram is an iterative process. With the example
represent equilibrium conditions and, as such, predict under discussion, the second step of iteration is all that
the best extraction and the best stripping which can is needed to produce a near equilibrium McCabe-
be obtained. These isotherms can be used to set the Thiele diagram. This will not always be the case.
staging in a circuit. Consider, for example, the
extraction isotherm in Figure 5 and suppose that the The construction of an equilibrium McCabe-Thiele
stripped organic entering into the last extraction stage diagram depicting one stage of stripping is very simple
contains 1.80 g/l Cu and that the advance flow rates of (Figure 7). A horizontal line is drawn from the loaded
the leach solution and the organic phase are equal. organic line (3.90 g/l Cu) to the isotherm line at the
Knowing this, an operating line can be constructed by value of the pregnant electrolyte (P.E.) desired, 51 g/l
starting at the point where the stripped organic Cu in this case. Then a vertical line is dropped from the
intersects the isotherm and drawing the line up and to point where the P.E. line intersects the isotherm line to
the right with a slope equal to the ratio of the aqueous the horizontal axis. This gives the stripped organic (S.O.)
/ organic flow rates (one in this instance) until the to be expected (1.77 g/l Cu). Next, the strip electrolyte
operating line intersects the vertical line representing (S.E.) line, 30.7 g/l Cu, is drawn horizontally from the
the copper content of the feed. Next, a horizontal line vertical axis of the graph to the L.O. line. A line is now
to the isotherm curve and then a vertical line to the drawn from the point of intersection of the S.O. and S.E.
operating line are drawn creating a “step”. This process lines to the intersection of the loaded organic and
is repeated, creating a second step and completing a pregnant electrolyte lines. This is the operating line.
two-stage “McCabe-Thiele”diagram. Each triangle
represents a single stage of extraction. In this system, a
raffinate of 0.22 g/l Cu and a loaded organic of 4.30 g/l
Cu are predicted in two stages of extraction. The
inverse of the slope of the operating line is the advance
organic / aqueous flow rate.

Even though the McCabe-Thiele diagram shown in


Figure 6 does not represent true equilibrium, but only a
first approximation, it is still quite useful. For example, if
a third stage of extraction were to be added to the
McCabe-Thiele diagram in Figure 6, (note the dotted
line) a near perfect equilibrium McCabe-Thiele diagram
would result. In addition, a more accurate two-stage
McCabe-Thiele extraction diagram can be drawn by
taking the two-stage McCabe-Thiele construction as
shown in Figure 6 and choosing as the point from
which a new operating line is to be drawn a distance
about 1/2 way between the isotherm line and the
raffinate line. When this is done, and then a second two
stage McCabe-Thiele diagram constructed as
described above, a raffinate of about 0.15 g/l Cu and a

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MCT Redbook
The slope of the operating line (20.3/2.13 = 9.50) is 3. Continuous Copper SX Circuit
equal to the ratio of the advance organic flow to the
advance aqueous flow needed across the strip stages Today many companies opt to treat dump leach
to obtain the desired pregnant strip solution. liquors in 2 extraction - 1 strip (2E-1S) stage plants
rather than 2E-2S or 3E-2S plants. For this reason, a 2E-
A two-stage McCabe-Thiele strip diagram, constructed 1S circuit was set up and operated at the advancing
as described above for extraction, predicts a stripped O/A ratios shown in the McCabe-Thiele diagrams in
organic of 1.12 g/l Cu when building a pregnant Figures 6 and 7. A mixer retention time of 2.6 minutes
electrolyte of 51 g/l Cu and operating at an O/A of was used simply because most copper SX plants have
7.3/1. two or three minute mixers, depending on the leach
solution conditions, mixer design and company
One of the important decisions the designer or builder philosophy.
of an SX plant must make is to decide on the staging
requirements. The capital cost of a stage must be In order to run a circuit properly, resulting in good
weighed against the benefits the stage provides. For metallurgy and maximum information, several things
example, consider the benefit of a second strip stage are important. Flow rates must be accurately set and
for the example cited above. Two stages of stripping continually monitored. Mixer dispersions should have
will give a stripped organic of 1.12 g/l Cu and result in a an O/A ratio near one in order to get proper mixing,
net copper transfer for the organic (the difference thus, recycles should be employed where needed. The
between the loaded and stripped organic) of about mixing turbines must rotate fast enough for good
2.78 g/l Cu, while one stage of stripping gives a copper mixing, but, not so fast that heavy entrainment
net transfer of about 2.13 g/l Cu. Because of this results.34 Another important feature of running a good
difference in net copper transfer, the one-strip stage circuit is frequent sampling with rapid and accurate
circuit requires a reagent concentration about 1.3 times analyses. This allows the operator to monitor the circuit
greater than the two-strip stage circuit in order to have closely, easily observing circuit behavioral differences
equal copper extraction performance. Therefore, the as operating parameters are changed. Once an
organic losses expected in a one-strip stage plant operator has changed operating conditions, the circuit
should be about 1.3 times greater than those in a two- should be allowed to run until circuit equilibrium is
strip stage plant. By comparing the capital cost for a established. A circuit is in equilibrium when there is a
second strip stage with the increased operating cost good metal balance and a good metal-acid balance
(due to higher reagent usage) for the one-strip stage across the whole circuit, as well as across each stage.
plant, a purely economic decision on the strip stage The metal extracted from the aqueous phase in an
requirements can be made. The increased reagent extraction stage in a given amount of time is equal to
concentration needed with one strip stage compared the acid equivalent gained by that same aqueous
to having two strip stages will depend on the leach phase in the given amount of time, and also equal to
liquor, copper recovery and the particular reagent. the metal loaded by the organic in that stage in the
same given amount of time. In a stripping stage, the
metal stripped from the organic phase in a given
amount of time is equal to the metal gained, and to
the acid equivalent lost, by the strip aqueous phase in
that stage in the same given amount of time. When at
equilibrium, the analysis for copper and acid do not
change as the circuit runs as long as the flows, the

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leach solution, the barren electrolyte and the organic Table V. Circuit Profile Data with 8.7 v/v%
phase do not change.
LIX® 984N in Escaid 110
Obviously, in order to balance metal and acid values, Sample Organic Aqueous
solution analyses and solution flow rates must be
g/l Cu g/l Fe g/l Cu g/l Fe
known. Furthermore, solution samples for a given
stage should be taken from the rear of the respective Extraction
settler for that stage. When possible, it is best to pull Stage One 4.08 0.0020 1.31
samples at those points easiest to access and least Extraction
likely to upset the circuit. Stage Two 2.88 0.0038 0.28

It is important to realize that circuit behavior will reflect Strip Stage 1.80 N.D. 51.2 0.026
the interdependence of the extraction and stripping
Strip Aqueous 30.7 0.010
operations. For example, a loss of stripping efficiency
will result in a higher stripped organic which in turn Leach Aqueous 2.50 1.30
leads to a higher raffinate. The circuit must then be
operated with a slightly higher reagent concentration,
or a slightly higher advance organic to aqueous ratio in Because of the design of mixers currently used in
extraction, in order to maintain copper recovery. copper solvent extraction plants, metal transfer in an
Alternatively, a slightly lower recovery must be extraction stage is usually about 85% to 95% of
accepted. theoretical while metal transfer in a strip stage is
usually > 95% of theoretical. For this reason, the values
predicted by equilibrium McCabe-Thiele diagrams for
the aqueous and organic phases exiting a given stage
are seldom realized in an operating circuit. For
example, compare the organic and aqueous values
which are predicted by the McCabe-Thiele diagram in
Figure 5 with the values generated in a continuous
laboratory circuit using the same aqueous, organic and
strip aqueous solutions (Table V, Figure 8).

The circuit produced a raffinate of 0.28 g/l Cu and a


loaded organic of 4.08 g/l Cu as compared to the
raffinate of 0.22 g/l Cu and the loaded organic of 4.24
g/l Cu predicted by the first approximation McCabe-
Thiele extraction diagram (Figure 6). The stripped
organic of 1.80 g/l Cu is close to the 1.77 g/l Cu pre-
dicted by the McCabe-Thiele strip diagram (Figure 7).

The natural question arises: Why perform the work


required for an equilibrium isotherm when the circuit
will not produce the predicted results? There are
several good reasons. First of all, generating an
isotherm helps to develop a “feel”for the system.
27
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MCT Redbook
Figure 8. Equilibrium Extraction Isotherm and Continuous Laboratory Circuit Data
y
5.0

L.O.
4.0

Feed = 2.50 g/l Cu


Organic g/l Copper

3.0

2.0
S.O.
Raff. = 0.28

1.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0

Aqueous g/l Copper


Organic: 8.7 v/v% LIX 984N
Aqueous: 2.5 g/l Cu, 1.3 g/l Fe (Total), pH = 1.8

Secondly, if the system has any unusual metallurgical good, the selectivity for copper over iron is high (in the
behavior characteristics, the isotherm will usually above circuit, it is about 1100/1 on a transfer basis), and
reflect them. In addition, a good idea of the actual there is little tramp metal contamination. More
circuit results can be obtained by drawing in the complicated feed solutions are evaluated in a manner
operating line as previously described. However, similar to that described above, but the extraction and
instead of filling in the horizontal and vertical lines to stripping isotherms and the staging in the circuit can
reflect 100% mixer efficiency, draw the horizontal lines be, and often are, more complex. With complex metal
in to represent only 95% efficiency. When this is done extraction systems, the initial circuit may have to be
using Figure 6, a two-stage raffinate of 0.28 g/l Cu is modified several times before the best recovery
predicted – a value identical to that realized in the scheme is worked out.
circuit operation.

The feed chosen for the above example is typical of


many copper leach operations and represents one of
the simplest feeds to treat. Copper recovery is very
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MCT Redbook
F. Isocalc®TM Computer-Generated The Isocalc® TM program includes a combination of
McCabe-Thiele Diagrams for Copper chemical modeling of the extraction and stripping
processes and mathematical manipulation of the data
The Cognis Isocalc® TM (Total Metallurgy) computer points. A stripped organic value from either chemical
simulation program has been developed as a tool to modeling or a manually input stripped organic value
provide plant operators with fast and accurate must be used as a starting point for each extraction
simulations of virtually any copper solvent extraction isotherm.
processes involving sulfuric acid leaching followed by
copper extraction with a phenolic oxime type Once the program has generated either an equilibrium
extractant. The functions of Isocalc® TM include: extraction or stripping curve, it allows for the
construction of a McCabe-Thiele diagram for a wide
• From the description of a common (or complex) number of plant configurations, including the now
copper leach solution and the stripping conditions, common series parallel configurations and Cognis’new
extraction and stripping isotherms are calculated Optimum Series-Parallel™ configuration. Any
based on comprehensive chemical modeling. combination of 1 extract by 1 strip [1E, 1S] to [4E, 4S]
McCabe-Thiele diagrams can then be constructed stages can be modeled in the series mode. In the
for many solvent extraction plant configurations. series-parallel mode, any combination of [1E (series), 1E
(parallel), 1S] to [4E (series), 4E (parallel), 3S] stages can
• Laboratory generated extraction and/or strip be modeled.
isotherm data can be manually entered instead of
relying on the chemical models provided. This is The organic / aqueous ratios of each circuit can be
useful for reagent compositions that do not varied independently and stage efficiencies can be
perform exactly the same as new or fresh Cognis’ varied over a wide range for each stage in the
LIX® Reagents. This is often the case with “aged” configuration, independent of the other stages. Stage
plant organics. McCabe-Thiele diagrams can also efficiencies are usually correlated with the type of
be developed for these extraction and stripping mixers being used in a plant, the temperature of the
isotherms. circuit, and the extraction kinetics of the extractant
relative to the temperature. The effect of changing any
• From a chemical model or a lab-generated one or more variables in the configuration can be
extraction isotherm developed for an operating quickly and accurately determined through to final
plant, plant operating data or profiles can be copper recovery.
inserted into the program and stage efficiencies
will be accurately calculated. The chemical model for the equilibrium extraction
curves is based on the equilibrium constants for several
• Results from each isotherm/McCabe-Thiele important chemical reactions in the process. By using
diagram can be saved as project files and later these chemical criteria for the model, it is possible to
retrieved for use again in another simulation. take into account most of the variables commonly
found in a copper solvent extraction process.
• Accurate comparisons of different plant
configurations and operating conditions can be
realized.

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EXAMPLE: Isocalc® TM Results versus consisting of 2 extraction stages and 1 stripping stage.
Laboratory Generated Data The efficiency of the extraction mixers was 95% and a
51.2 g/l Cu rich electrolyte was produced from a lean
The Isocalc® model can be used to predict the electrolyte consisting of 30.7 g/l Cu and 190 g/l H2SO4.
metallurgical results that will be obtained in a
laboratory evaluation or in a commercial SX plant. The same operating parameters used in the laboratory
Take the example we used in the Laboratory Evaluation evaluation above (PLS values, LIX 984N concentration,
Program for a Copper Leach Solution on page 21. In electrolyte values, staging and mixer efficiencies), plus
this example, 8.7 V/V% LIX 984N produced a raffinate estimated total sulfate and sulfate activity values, were
of 0.28 g/l copper from a leach solution (PLS) entered into the Isocalc® program. A comparison of the
containing 2.50 g/l Cu at pH 1.8 in a laboratory circuit extraction isotherms and circuit profiles are below.

The laboratory versus Isocalc® results in


Table VI: Extraction Isotherm Comparison Tables VI and VII, while not identical,
are similar. They demonstrate that the
Extraction Laboratory Isotherm Isocalc Isotherm
Isocalc® program is a reliable tool and
Organic Aqueous Organic Aqueous that it can be used to generate
O/A
g/l Cu g/l Cu g/l Cu g/l Cu representative isotherms, construct
10/1 2.04 0.07 2.047 0.064 McCabe-Thiele diagrams and predict
5/1 2.28 0.09 2.287 0.085 copper recovery rates in solvent
extraction circuits.
2/1 2.96 0.17 2.956 0.196
3/2 3.26 0.26 3.268 0.303 Figure 9 is the Isocalc® text outputs of
1/1 3.70 0.51 3.705 0.599 the extraction and stripping data and
1/2 4.19 1.24 4.128 1.338 the Isocalc® profile results for this
1/5 4.35 1.94 4.299 2.001 comparison. Figure 10 is The McCabe-
S.O. 1.80 1.803 Thiele extraction diagram and Figure
11 is The McCabe-Thiele diagram for
Leach Solution (PLS) 2.50 2.50 stripping.

Table VII: Circuit Profile Comparison


Laboratory Profile Isocalc Profile
Organic Aqueous Organic Aqueous
Stage g/l Cu g/l Cu g/l Cu g/l Cu
Ext. Stage #1 4.08 1.31 4.049 1.355
Ext. Stage #2 2.88 0.28 2.904 0.255

Strip Stage 1.80 51.2 1.803 51.2

31
Copyright© 2007 by Cognis Group
MCT Redbook
Figure 9. Isocalc® TM Extraction and Stripping Isotherm Data, and Profile Results.

Isocalc® TM Ver. 8.00


© Copyright 2006 Cognis Corporation
Isotherm Point Calculations and Graphics / McCabe-Thieles
NOTICE: Please read Cognis’ Disclaimer of Warranty and Limitation of Liability statements

Extraction Data
Client: LIX® Reagent Customer
Project: New Copper Property
Reagent Selected: LIX® 984N Reagent Volume Percent: 8.7%
PLS g/l Cu: 2.5 PLS pH: 1.80
PLS g/l SO4: 90 PLS SO4 Activity: 12.5%
Stripped Organic, g/l Cu: 1.803 Max Load, g/l Cu: 4.380
Number of Strip Stages: 1 Spent Elec., g/l Cu: 30.7
Spent Elec., g/l H2SO4: 190 Preg. Elec., g/l Cu: 51.2
Temperature: 25˚C
Others Parameters / Information:

Extraction Isotherm Points Strip Isotherm Points

Org., g/l Cu Aq., g/l Cu Aq., g/l Cu Org., g/l Cu


O/A=10.0 2.047 0.064 30.700 1.000
O/A=5.0 2.286 0.085 34.800 1.170
O/A=2.0 2.955 0.196 38.900 1.330
O/A=1.5 3.268 0.302 43.000 1.470
O/A=1.0 3.704 0.599 47.100 1.590
O/A=0.5 4.128 1.338 51.200 1.700
O/A=0.2 4.299 2.001
O/A=0.1 4.342 2.246

================== McCabe-Thiele Calculations ==================

Net Transfer: 0.258 g/l Cu per 1 vol. % LIX® 984N


Series Circuit Recovery: 89.810%
Loaded Organic is 92.43% of Max Load

PLS Spent. Elec.


2.500 g/l Cu Raffinate Preg. Elec. 30.7 g/l Cu
pH = 1.80 0.255 g/l Cu 51.2 g/l Cu 190 g/l H2SO4

1.355 g/l Cu
O/A= O/A=
1.0 9.131
Mixer Eff Mixer Eff Mixer Eff
95% 95% 98%
2.904 g/l Cu Stripped Org.
E1 E2 S1
1.803 g/l Cu
Loaded Org.
4.049 g/l Cu

32
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MCT Redbook
Figure 10. Isocalc® TM McCabe-Thiele Extraction Diagram

5
8.70 v/v% LIX 984N
Key Extration
Data
Feed = 2.5 g/l Cu
4 pH = 1.8
L.O. = 4.049 g/l Cu
S.O = 1.803 g/l Cu
S.E. = 30.7 g/l Cu
S.E. Acid = 190 g/l
Organic g/l Copper

3 P.E. = 51.2 g/l Cu


Recovery = 89.81%
Series Extration
E1-S = 95.0%
2 E2-S = 95.0%
O/A = 1.0
Raff = 0.255 g/l Cu
NOTICE: Please read
Cognis’ Disclaimer of
Warranty and Limitation
1 Liability Statement.

0
0 0.5 1 1.5 2 2.5 3
Aqueous g/l Copper

While the Isocalc® computer program predicts circuit c) crud generation – the term “crud “ or “gunk”is used
behaviors associated with the copper extraction / to describe an interfacial material, usually a solid
stripping equilibrium, it does not predict copper over stabilized emulsion, which is present in almost all
iron selectivity nor does it address the physical solvent extraction circuits. Crud often contains finely
properties of a circuit such as: divided solids (either carried into the circuit with the
leach liquor or precipitated in the circuit), some stable
a) phase separation – how fast the aqueous/organic
emulsion, bulk leach solution and bulk organic,
dispersion exiting a mixer separates into discreet
colloidal silica and, at times, bacteria. Crud is a very
organic and aqueous phases,
difficult thing to describe as the composition of crud in
b) entrainment – the very small droplets of one phase one plant may be quite different from crud in another
carried in the other phase after primary phase plant.
separation has taken place,

33
Copyright© 2007 by Cognis Group
MCT Redbook
Figure 11. Isocalc® TM McCabe-Thiele Stripping Diagram

70
8.70 v/v% LIX 984N
Key Strip Data
65 L.O. = 4.049 g/l Cu
P.E. = 51.2 g/l Cu
60 S.E. = 30.7 g/l Cu
S.E. Acid = 190 g/l
S1-S = 98.0%
55 O/A + 9.13
S.O = 1.803 g/l Cu
Aqueous g/l Copper

Temp = 25˚C
50 NT = 0.258 g/l/Vol%
NOTICE: Please read
45 Cognis’ Disclaimer of
Warranty and Limitation
Liability Statement.

40

35

30

25

20
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6
Organic g/l Copper

As previously mentioned, the Isocalc® program should distribution. Under certain conditions, your Cognis
be used in conjunction with, but not as a total solvent extraction specialist will be happy to run
substitute for, laboratory evaluations. As such, it can Isocalc® programs for your projected sulfuric acid
save a lot of time by very quickly providing information copper leach solutions.
on “what if”type questions, which is very useful during
the early stages of a project. For more information on Cognis’Isocalc® TM solvent
extraction modeling program, call your local Cognis
A version of the program is available for Cognis representative.
customers but it is not available for general

34
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MCT Redbook
II. Ion-Pair Extractants stripping agents which deprotonate the amine give
the best stripping in the fewest stages.
A second class of extractants is based on the principle
of ion association whereby a large, positively charged The equation below shows stripping with Na2CO3:
organic moiety causes the extraction of an anionic
metal complex into the organic phase, with c. 2[R3NH+B-]org + [Na2+CO3=]aq
concomitant expulsion of a common anion into the
aqueous phase. Cognis Corporation markets two 2[R3N]org + H2Oaq + CO2 + 2[Na+B-]aq
classes of compounds which fall into this general
classification.
The greatest commercial acceptance for Alamine-type
A. Alamine® Series reagents has been in uranium recovery, however, any
metal capable of forming anionic complexes in
Alamine reagents contain a basic nitrogen capable of aqueous solution is a candidate for extraction by an
forming amine salts with a wide variety of inorganic amine type extractant. Figure 12 shows some of the
and organic acids. Tertiary amines of the general extraction data which has been generated using
formula R3N, where R represents a variety of Alamine 336 and/or similar amines.35 The data is far
hydrocarbon chains, find the widest use in metal from all-inclusive, but it does show the wide variety of
recovery processing by solvent extraction. The metal-aqueous systems which are amenable to
equations below are representative of the extraction treatment with amine type extractants.
chemistry of the Alamine Series of Reagents:
B. Aliquat® Series
a. [R3N]org + [HA]aq [R3NH+A-]org The Aliquat Series of Reagents is based on the
b. [R3NH+A-]org + [B-]aq [R3NH+B-]org + [A-]aq
quaternization of the respective Alamine reagent by
methyl chloride. Because a quaternary amine is always
positively charged, anion extraction with Aliquat
Equation “a”represents amine salt formation and reagents is not pH dependent like it is with the tertiary
equation “b”represents true ion exchange. The extent amines. As a result, some basic metal leach solutions
to which B- will exchange for A- is a function of the may be successfully treated by Aliquat-type reagents
relative affinity of the two anions for the organic cation without pH adjustment. The biggest disadvantage of
and the relative stability of the anions in the aqueous using an Aliquat reagent is that these reagents will not
medium. Typically, extraction favors larger lower- deprotonate, therefore, stripping is usually more
charged anions over smaller more highly charged difficult than with the parent amine-type reagent.
anions. Since tertiary amines form salts with a wide
variety of acids, the choice of reagents for a liquid ion
exchange process is quite large, i.e., the bisulfate salt,
the chloride salt, etc., of any of the Alamine reagents.

Amine-type extractants can be stripped with a wide


variety of inorganic salt solutions such as NaCl, Na2CO3,
and (NH4)2SO4. The choice of stripping agent depends
on the overall recovery process, but in general, basic

35
Copyright© 2007 by Cognis Group
Figure 12 . Tertiary High Molecular Weight – Amine Extraction of the Elements (a)

Li Be B C N O F
Na Mg AI Si P S CI

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
IV V VI III II II II
b v bk b b b bh

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I
III IV V VI VII IV I
hj vc bcdg c abcdlm b bh

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At
III IV V III IV
h bc cg b b

Fr Ra Ac

* Elements 58-71 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
III III III III III III III
h h h h h h

† Elements 90-103 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No 103


IV V IV VI IV VI IV VI III III III III III
abcdh abcd ab ab ab ab ab abf hj hj hj hj hj
cd
ef
gi

Key Blocked elements are strongly extracted by one contact with .1M amine from the acid systems shown below:

Element a—HNO3 d—H3PO4 g—(COOH)2 j—NH4SCN l—HBr


Valence b—HCI e—HF h—LiCI, LiCI, LiCI—HCI, CsCI k—H2CrO4 m—HI
System c—H2SO4 f—CH3COOH i—various organic acids

(a) Taken from “Standard Methods of Chemical Analysis,” Volume II A, Sixth Edition, page 190. Van Nostrand Reinhold Company, 1963.

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MCT Redbook
C. Laboratory Evaluation Program for
Ion-Pair Extractants Still, the goal of the laboratory evaluation program
remains the same: to develop the best conditions for
Laboratory evaluation programs with amine-type the extraction, stripping and final product recovery
extractants are carried out much like those described consistent with the overall metallurgical flowsheet.
earlier for chelating-type reagents. Amine systems tend
to be more complicated than chelating systems for a An example which illustrates the importance of the
variety of reasons: variables cited above is the separation of Co, Fe and Ni
from an acidic chloride solution. Refer to Figure 13 and
a. the large number of aqueous anionic systems where note that Ni(II) is only slightly extracted at 200 g/l
an amine extractant may be applicable, chloride ion, Co(II) and Fe(II) are strongly extracted at
150-200 g/l chloride ion and Fe(III) is strongly extracted
b. protonated amines and quaternary amines must be at 50 g/l chloride ion. As a result, an excellent Co, Ni,
paired with an anion and as a result these reagents and Fe separation can be effected by taking an alloy of
are often not very selective, the metals into a concentrated HCl solution, oxidizing
the iron to ferric, co-extracting the Co(II) and Fe(III)
c. the large variety of potential stripping agents as while leaving the Ni in the original solution, and then
compared to copper loaded oximes, where for selectively stripping the Co(II) from the Fe(III) with
example, stripping with sulfuric acid is the norm, water. This flowsheet has been studied in our
laboratory. Several slightly different flow sheets have
d. the three variables: pH, the oxidation state of the also been reported.36, 37 The best flowsheet for this type
metal and the concentration of the anion, of feed is dependent upon the relative amounts of Co,
contributing to the anionic metal complex, all of Ni and Fe present.
which are important in metal separation schemes
with amines. In general, the use of organic phase modifiers,
normally polar oxygen containing organic molecules
such as long chain alcohols, is required with amines in
order to keep the amine metal complexes soluble,
prevent third phase formation and/or to have
acceptable phase separation.

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MCT Redbook
Figure 13. Alamine® 336 Extraction Isotherms from Chloride Solutions at 40˚C and pH=2

100 Mo
Zn
Fe3+

80
Extraction (E), %

60
Fe2+
Cu Co

40
Sn Mn

20

Ni, Cr
0
100 200 300
[CL-], g/l.

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MCT Redbook
D. Present and Possible Future Uses of Future growth in use of these reagents may lie in the
Amine Extractants areas of:

One of the best ways to illustrate the value of amines a) reclaiming metals from spent catalysts.52
as ion-pair metal extractants is to list the high purity b)niobium, tantalum, titanium and zirconium
amines commercially available from Cognis separations,53
Corporation and some of their known uses: c) inorganic acid purification,54
d)separation of cobalt, copper and zinc from nickel.55
1. Alamine®300 (tri-n-octylamine): cobalt extraction
from chloride leach solutions.38

2. Alamine®308 (tri-isooctylamine): cobalt-nickel


separation from hydrochloric acid liquors.39

3. Alamine®336 [tri-(C8C10)amine]: uranium recovery


from sulfuric acid leach liquors40 or sulfuric acid
solutions arising from eluting ion exchange
resins41,42 cobalt-nickel separations from hydrochloric
acid,43 iron extraction from aluminum chloride
solutions,44 vanadium extraction,45 chromium
extraction,46 platinum group metals separations47
and tungsten recovery.

4. Alamine®310 (tri-isodecylamine): uranium and


vanadium extraction from acidic sulfate leach liquors
and platinum group metals separations.47

5. Alamine®304 (trilaurylamine): uranium and


molybdenum extraction from acidic leach liquors,
the advantage being that the molybdenum amine
complex is highly soluble.

6. Aliquat®336 [tri-(C8C10)methyl ammonium chloride]:


vanadium extraction,45 separation of platinum
group metals,47, 48 rare earth extractions,49 rhenium
recovery,50 and arsenic extraction from refinery
electrolytes.51

7. Aliquat®336 Nitrate: the nitrated salt of Aliquat 336, a


specialty product for rare earth separations.

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MCT Redbook
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III. Neutral or Solvating Type Extractants It takes little imagination to see that the above list is
only a brief representation of the organic compounds
A third class of extractants are known as neutral or that could function as solvating extractants. In general,
solvating type extractants. Extractants of this class are extractions with solvating extractants are limited by:
basic in nature and will coordinate to certain neutral 1) the metal’s ability to form neutral complexes with
metal complexes by replacing waters of hydration, anions, 2) the co-extraction of acid at high acid
thereby causing the resulting organo-metal complex concentrations, and 3) the solubility of the organo-
to become organic soluble and aqueous insoluble. metal complex in the organic carrier.
Solvating extractants have an atom capable of
donating electron density to a metal in the formation An important extractant of this type is tri-n-
of an adduct and are classified according to that ability: octylphosphine oxide, (C8H17)3PO, called TOPO. The
extraction characteristics of TOPO with a wide variety
R3PO > (RO)3PO > R2CO > ROH > R2O of metals have been investigated56 and are
summarized in Figure 14. One important commercial
trialkylphosphine oxides > trialkylphosphates > application of TOPO in solvent extraction is its
ketones > alcohols > ethers. synergistic combination with di-2-ethylhexyl-
phosphoric acid (DEHPA) for the extraction of uranium
from wet process phosphoric acid.57, 58

Other important extractants in this class are


triutylphosphate (TBP), di-butyl butylphosphonate
(DBBP), 2,2'-dibutoxy diethyl ether (di-butyl carbitol)
and methyl isobutyl ketone (MIBK). Di-butyl carbitol
and MIBK are used for the extraction of gold from acid
chloride solutions.8

It is of interest to note that many of the equilibrium


and phase modifiers commonly used in solvent
extraction come from this class of extractants. This is
not a surprise since both require a group having the
ability to donate electron density and, in some cases, to
be a hydrogen bond acceptor and/or donor.

41
Copyright© 2007 by Cognis Group
Figure 14 . Tri-n-Octyphosphine Oxide (TOPO) – Extraction of the Elements (a)

Li Be B C N O F
Na Mg AI Si P S CI

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
IV V VI III II II III IV III
ac a ac abc a a a a a a

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I
IV V VI VII II III IV III V
ab a abc acde a a a aa

Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At
IV V IV III II III IV
ab a a a a b b

Fr Ra Ac†

* Elements 58-71 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
IV
bc

† Elements 90-103 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No 103


IV VI IV IV VI
ab abcd ab bc ab ab

Key Blocked elements are extracted from the acid systems shown below:
Element a—HCI
Valence b—HNO3
System c—H2SO4
d—HBr
E—H3PO4

(a) Taken from “Standard Methods of Chemical Analysis,” Volume II A, Sixth Edition, page 192. Van Nostrand Reinhold Company, 1963.

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MCT Redbook
IV. Organic Acid Extractants
A fourth class of extractant is the so-called acid
extractants. The chemistry of this type of extractant
has some characteristics which resemble chelating
extractants and some which are similar to neutral or
solvating extractants. Di-2-ethylhexyl phosphoric acid
(DEHPA), shown below, is representative of this class of
extractant.

(C8H170)2POH base metals. This is unfortunate since it limits the use of


these reagents for two reasons:
Di-2-ethylhexylphosphoric acid (D2EHPA)
1. insufficient selectivity for most base metal systems,
Reagents which belong to this class are the organo-
phosphoric, -phosphonic and -phosphinic acids, their 2. iron is so strongly extracted that stripping the iron
respective mono- and di-thio derivatives, can be a problem.
organosulfonic acids and carboxylic acids.
In spite of these limitations, acid extractants have
The following equation shows the dual behavioral found commercial use for metal recovery. DEHPA has
characteristics: been used for the recovery of uranium,3, 60 vanadium,3, 60
and zinc.59, 61 While all three types of acidic organo-
phosphorous compounds have been used for the
O
selective extraction of cobalt over nickel,62, 63 the
phosphinic acid type extractants such as LIX® 272 find
4(RO)2POH + Zn2+ the widest use in this application. The active extractant
in LIX 272 is bis(2,4,4-trimethylpentyl)phosphinic acid.
[(RO)2PO2]2Zn[(RO)2PO2H]2 + 2H+
It is the reagent of choice for the separation of cobalt
from nickel in both sulfate and chloride matrices.
Note that two of the DEHPA molecules lose a proton Depending on the pH, a number of other metals can
much like a chelating extractant while two other also be extracted. The typical order of selectivity is:
DEHPA molecules solvate the zinc similar to solvating Fe(III)(pH0.50= <1.5)< Zn (pH0.50= 2.37)< Cu (pH0.50=
type extractants. The pH extraction characteristics of 3.93)<Mn (pH0.50= 4.15)< Co (pH0.50= 4.42) < Mg (pH0.50=
DEHPA with respect to several metals are shown in 5.49)< Ca (pH0.50= 5.63) < Ni (pH0.50= 6.42).
Figure 15.59

One of the more interesting characteristics of the


extraction behavior of phosphorous-based acid
extractants is their strong affinity for iron(III) over other

43
Copyright© 2007 by Cognis Group
MCT Redbook
Figure 15. Metal Extraction by Di-2-ethyhexyl phosphoric acid as a function of pH.

100 Zn Cd
Ca Mn
Co
Cu
Fe(III) Ni
80 Mg
Extraction %

60

RO O
40
P
RO OH
20

0
0 1 2 3 4 5 6 7 8
Equilibrium pH

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V. Ligand Substitution Two organic mono-oxime molecules displace two
chloride ions from the inner coordination sphere of the
Ligand substitution extractants are similar to neutral or palladium and in the process the Pd complex becomes
solvating extractants in that they donate an electron organic soluble and water insoluble.
pair to a metal ion, but they are different in that these
extractants form inner shell complexes with metals Other reagents of this type include dialkyl sulfides (R2S)
and, in doing so, will displace other ligands. For such as di-n-hexyl sulfide which has been used to
example, consider the extraction of Pd from an acidic extract palladium by INCO and Lohnro.8
palladium chloride solution by a mono-oxime as
described by the following equation:64 Cognis does not currently market reagents of this type,
but has research interests in this area.

2R2C=NOH + PdCl4=
(R2C=NOH)2PdCl2 + 2Cl-

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REAGENTS IN DEVELOPMENT, GOLD
At the time this edition of the Red Book was published,
development work on several new extraction reagents
and/or metal recovery processes was taking place in
our laboratories. A brief discussion about one of these
developments follows. Inquiries from interested parties
about the progress of these developments are invited.

Gold Extraction
Cognis is developing a reagent for the extraction of
gold from typical cyanide leach solutions which can be
stripped with an aqueous solution of 2-4 w/v% NaOH
and 0.5 w/v% of NaCN. The selectivity of this reagent
for metal cyanide complexes has the following order:

Au ~ Zn ~ Hg > Ag > Ni >> Cu ~ Fe.65

The recovery of gold from clarified cyanide leach


solutions may offer certain advantages over existing
gold recovery processes, particularly:

1. where very high gold recovery is needed or,

2. in the case of leach solutions carrying either high


levels of copper or organic compounds which foul
carbon.

In addition, the gold inventory carried in the SX-EW


recovery process is less than that in typical carbon in-
column or Merrill Crowe recovery processes.

The functionality is also available as a solid ion


exchange resin called Aurix® 100.66 This resin has shown
excellent gold extraction kinetics and high gold
loading in laboratory and pilot plant tests. It has also
been shown to be resistant to breakage in typical resin
in leach or resin in pulp applications. Aurix 100 may
show significant advantage over activated carbon for
gold extraction from preg robbing pulps or from bio-
leach liquors which foul carbon.

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SOLVENT EXTRACTION DILUENTS CONCLUSION
The discussion to this point has been centered on the The potential of solvent extraction is well documented
reagents used for metal extraction. In most commercial by the wide variety of metal-containing solutions
SX plants, however, the diluent used as a carrier for which are amenable to recovery, purification, and
both the reagent and the reagent metal complexes is concentration by solvent extraction. However, much
present in far larger amounts than the reagent. work in both reagent synthesis and process
Furthermore, the diluent can alter both the chemical development remains. Cognis plans to continue as an
and physical properties of an SX system. Given this, a industry leader in this field via its vigorous research and
brief discussion on diluents is appropriate. development program. This program includes close
working relationships with existing and potential
In many cases, the role of the diluent on the chemistry customers in a joint effort to solve problems of
of the system is minor, and the choice of diluent is common interest in metals recovery. Efforts in the area
made on the diluent’s physical properties such as of technical service to existing and potential customers
phase separation, flash point and the solubility of the have made a significant contribution to the overall
reagent and the reagent metal complexes. It is success of Cognis in solvent extraction. Cognis realizes
fortunate that with many of the large SX systems, for it does not have all the answers nor it is aware of all the
example, the copper-oxime system, the above holds problems. But, Cognis firmly believes that by
true. In other cases, where the diluent has a major role cooperating with the customer we can become aware
in the chemistry of the system, the choice of diluent of, and help find solutions to, many of these problems.
depends on both chemical and physical properties. In Cognis’50+ years of experience in solvent extraction is
either case, efforts to choose a proper diluent, and to an important asset to our problem-solving ability.
monitor the quality of continuing supplies of the
diluent, is important. These efforts must be included as Information provided in this technical literature is
part of any good laboratory evaluation program. believed to be accurate. However, Cognis assumes no
liability and makes no warranty or representation
It should be noted that in this discussion, the function that the information is correct or complete. Final
of the diluent is assumed to be separated from that of determination of suitability of any material and
the modifier. In real systems, this is not a valid issues of patent infringement are the sole
assumption, but solvent-modifier interactions are responsibility of the user who alone knows the
complex and for reasons of brevity this topic will not conditions of intended use.
be discussed.

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COGNIS QUALITY CONTROL... and other useful procedures
This section, containing six commonly used Cognis procedures, has been included to help customers and
potential customers with their plant operations and laboratory evaluations. The procedures included in this
section are:

I. Standard Cognis Quality Control Test for LIX® Oxime Reagents . . . . . . . . . . . . . . . . . . . . . . . .55
A. Introduction
B. Equipment and Reagents
1. Test Vessel
2. Sample Device
C. Organic Phase Preparation
1. For Normal Formulated LIX Reagents
2. For Concentrated Reagents except LIX 860-IC
3. For LIX 860-IC
D. Aqueous Phase Preparation
1. Standard Extraction Aqueous Phase
2. Standard Strip Aqueous Phase
E. Extraction Kinetics, Extraction Isotherm Point, Extraction Phase Separation
and Extraction Cu/Fe Selectivity
F. Strip Kinetics, Strip Isotherm Point and Strip Phase Separation
G. Maximum Copper Loading
H. Calculations

II. Analysis of Copper in Organic Solvent Extraction Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . .59


A. Introduction
B. Equipment and Instrument Settings
C. Reagents
D. Analysis

III. Analysis of Copper in Aqueous Leach Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .61


A. Introduction
B. Equipment and Instrument Settings
C. Reagents
D. Analysis
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IV. Cognis Quality Control Test for LIX® Nickel Oxime Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . .63
A. Introduction
B. Equipment and Reagents
1. Test Vessel
2. Sample Device
C. Preparation
1. Organic Preparation
2. Standard Extraction Aqueous Phase
3. Standard Strip Aqueous Phase
D. Extraction Kinetics, Extraction Isotherm Point, Extraction Phase Separation
and Extraction Ni/Zn Selectivity
E. Strip Kinetics, Strip Isotherm Point and Strip Phase Separation
F. NH3 Loading
G. Maximum Nickel Loading
H. Calculations

V. Clay Treatment Test Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .67


A. Introduction
B. Equipment and Solutions
C. Clay Treatment Procedure
D. Extraction and Strip Test Procedure
E. Calculations

VI.Direct Colorimetric Determination of Uranium on Amine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .69


A. Introduction
B. Direct Colorimetric Determination of Uranium on Amine
1. Solutions
C. General Procedure
1. Chromogenic Solution
2. Equipment: Spectrophotometer
3. Procedure
D. Calculations
The above is not a complete list of Cognis procedures. Please contact your Cognis Representative if you have any
questions regarding these procedures and the other procedures available through Cognis.
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I. Standard Cognis Quality Control Test C. Organic Phase Preparation
for LIX® Oxime Reagents
1. For Normal Formulated LIX Reagents
A. Introduction Prepare a 500 ml solution of exactly 10 v/v % LIX
reagent in the diluent Escaid 100 or its approved
The standard Cognis Quality Control Test for LIX oxime- equivalent. If v/v dilution is not convenient, w/v
based reagents is designed to be a relatively simple dilutions can be calculated and made using the density
and easy way to ensure that these Cognis LIX reagents of the LIX reagent lot being tested.
meet rigid specifications for those properties critical to
the performance of these reagents as copper 2. For Concentrated Reagents except LIX 860-IC
extractants. Reagent specifications are tied to the Prepare a 500 ml solution of exactly 7.143 v/v % LIX
specific conditions of the Cognis Standard Quality reagent in the diluent Escaid 100 or its approved
Control Test and, for this reason, it is very important to equivalent. If v/v dilution is not convenient, w/v
strictly adhere to the test equipment, reagents, dilutions can be calculated and made using the density
conditions and procedures described in this bulletin. of the LIX reagent lot being tested.

3. For LIX 860-IC


B. Equipment and Reagents Prepare a 500 ml solution of exactly 8.00 v/v % LIX 860-
IC in the diluent Escaid 100 or its approved equivalent.
1. Test Vessel If v/v dilution is not convenient, w/v dilutions can be
The test vessel is a PVC box I.D. 3 1/2 X 3 1/2 X 6 inches calculated and made using the density of the LIX
(8.9 X 8.9 X 15.4 cm), clean and free of soap or reagent lot being tested.
detergent residue. The polypropylene impeller is 1.75
inches (4.45 cm) in diameter with 6 slots, 0.125 inches
(0.32 cm) deep and 0.125 inches wide, the top of the
hub is 1 cm above the top of the impeller, and the
shaft is 316L stainless steel, 23 cm long. The mixer
speed is adjusted to 1750 ± 25 rpm. While Cognis uses
Stirrer Type RZRI available from Caframo (Wiarton,
Ontario, Canada N0H 2T0), any good constant speed
stirrer capable of maintaining 1750 ± 25 rpm is
acceptable. The test vessel and the impeller are
available to Cognis customers free of charge from
Cognis Corporation.

2. Sample Device
When sampling the emulsion it is important that no
additional mixing occur. A large bore sampling tube
should be used. A 10 ml volumetric pipette with the tip
cut off or a 10 ml serological pipette with the sample
drawn through the large end are satisfactory devices.

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D. Aqueous Phase Preparation ml of sample emulsion from the top 2 cm of the test
vessel and transfer the sample into a small beaker or
1. Standard Extraction Aqueous Phase separatory funnel. After the phases have separated,
The extraction aqueous phase contains 6 ± 0.1 g/l filter the organic sample through Whatman 1PS or
Cu+2, 3 ± 0.1 g/l Fe+3 (both as sulfates) at a pH of 2.0 ± equivalent filter paper, label as the E30 sample and save
0.1. for analysis. Continue mixing for a total of 300 seconds
at which time the stirrer is stopped. Immediately start a
2. Standard Strip Aqueous Phase stopwatch and determine the time required for
The strip aqueous phase contains 35 ± 0.7 g/l Cu (as complete separation of the phases. Phase separation is
the sulfate) and 160 ± 2 g/l H2SO4. considered complete when only a monolayer of
bubbles remains at the interface. Sample the organic
All solutions are prepared from reagent grade phase, filter the organic sample through Whatman 1PS
chemicals dissolved in D.I. water. or equivalent filter paper, label as the E300 sample and
All solution temperatures are equilibrated to 23 ± 1˚C save for analysis. Refer to the copper aqueous and
before use. organic procedures for analysis.

Before and after each test, all equipment should be For LIX 84, LIX 84N, LIX 84-I and LIX 84-IC a 60-second
rinsed several times with DI water followed by kinetic sample (E60) is taken as follows: starting at 59
methanol or acetone and completely dried before seconds, smoothly remove 10-15 ml of sample
each use. Failure to adequately rinse and dry the emulsion from the top 2 cm of the test vessel and
equipment can result in erroneous results. transfer the sample into a small beaker or separatory
funnel. After the phases have separated, filter the
E. Extraction Kinetics, Extraction Isotherm organic sample through Whatman 1PS or equivalent
Point, Extraction Phase Separation filter paper, label as the E60 sample and save for analysis.
and Extraction Cu/Fe Selectivity Continue mixing for a total of 300 seconds at which
time the stirrer is stopped. Immediately start a
Vigorously contact 400 ml of the organic phase with stopwatch and determine the time required for
400 ml of strip aqueous phase for two minutes in a complete separation of the phases. Phase separation is
separatory funnel. After the phases have separated, considered complete when only a monolayer of
filter the organic phase through Whatman 1PS or bubbles remains at the interface. Sample the organic
equivalent filter paper. Add 350 ml of filtered organic phase, filter the organic sample through Whatman 1PS
into the test vessel and adjust the impeller so that it is or equivalent filter paper, label as the E300 sample and
centered in the test vessel and the top of the save for analysis. Refer to the copper aqueous and
polypropylene hub of the impeller is at the surface organic procedures for analysis.
level of the organic phase. Start the stirrer and adjust
the impeller speed to 1750 ± 25 rpm and then over 5
seconds smoothly add 350 ml of the extraction
aqueous phase. Start the stopwatch immediately at the
end of the aqueous addition.

For all LIX reagents except LIX 84, LIX 84N, LIX 84-I and
LIX 84-IC, a 30-second kinetic sample (E30) is taken as
follows: starting at 29 seconds, smoothly remove 10-15

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F. Strip Kinetics, Strip Isotherm Point and Spectroscopy (AAS) for Cu. The E300 sample is also
Strip Phase Separation assayed by AAS for Fe. All results are expressed in units
of g/L. AAS procedures used by Cognis Corporation to
The organic and aqueous phases from the extraction determine copper and iron in organics are available
test above are transferred to a separatory funnel and upon request.
the phases allowed to completely separate. The
aqueous phase is withdrawn and discarded. Loaded H. Calculations
organic (325 ml) is carefully transferred to a graduated
cylinder making sure no aqueous transfers with the 1. Extraction isotherm point, Cu = E300
organic. The strip aqueous (325 ml) is added to a clean
test vessel. Adjust the impeller height as previously
described, start the stirrer and adjust the speed to 2. Strip isotherm point, Cu = S30 - S300
1750 ± 25 rpm. Over a period of 5 seconds, add the
loaded organic. Start the stopwatch immediately after
the addition of the organic. Starting at 29 seconds, 3. Extraction kinetics, % = E30 E
x 100 or 60 x 100
smoothly remove 10-15 ml of sample emulsion from E300 E300
the top 2 cm of the test vessel and drain into a small 4. Extraction Cu/Fe selectivity = E300 (Cu)
beaker or separatory funnel. Filter the organic phase
through Whatman 1PS paper or equivalent and label E300 (Fe)
as the S30 sample. Continue stirring for a total of 300 5. Strip Kinetics, % = E300 (Cu) - S30 (Cu)
seconds, stop the stirrer and allow the phases to x 100
E300 (Cu) - S300 (Cu)
separate measuring the phase separation time as
previously described. Sample the organic phase, filter 6. Net Transfer, Cu = E300 - S300
the organic sample through Whatman 1PS or
equivalent filter paper, label as the S300 sample and save
for analysis. Refer to the copper aqueous and organic
procedures for analysis.

G. Maximum Copper Loading

Take an aliquot of the diluted LIX reagent and an equal


volume of standard extraction aqueous and contact
them vigorously for 2 minutes in a separatory funnel.
Allow the phases to separate and discard the aqueous
phase. Add fresh standard extraction aqueous and
repeat the contact. Continue until a total of 4 contacts
have been made. After the last contact, filter the
organic sample through Whatman 1PS or equivalent
filter paper, label as the Max Load sample and save for
analysis.

Organic samples E30 or E60, E300, S30 and S300 and the Max
Load sample are assayed by Atomic Absorption

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II. Analysis of Copper in Organic Solvent concentrations of solvent extraction reagents in the
Extraction Solutions diluent causes the burners in some instruments to
rapidly clog. If all samples are diluted at least 1:10 in the
A. Introduction diluent matrix used to prepare the standards, no matrix
effects are observed. For samples containing copper at
Copper can be determined directly by atomic such low concentrations that a 1:10 dilution is not
absorption spectroscopy in organic solvent extraction possible the matrix of the standards should be
solutions. The instrument must be equipped to handle matched to the samples or the technique of standard
organic solutions and the standards and samples must additions should be used. Preparation of organic
be diluted in an appropriate diluent. working standards and dilution of samples is best
accomplished with an automated diluter such as the
The manufacturer of the instrument should be Microlab® 500 available from The Hamilton Company,
consulted for instructions on setting up the instrument P.O. Box 10030, Reno, NV 89502 USA, telephone
for the direct analysis of organics. Usually, the o-ring (702) 858-300, fax (702) 856-7259 or equivalent. The
seals in the nebulizer/spray chamber must be changed use of manual pipettes and volumetric flasks requires
to materials that are compatible with organic solutions. the calibration of the pipettes with the diluent to
Once this change is made, it is not necessary to change achieve acceptable accuracy. The relatively high
the o-rings back to the original material to analyze coefficient of expansion of organic solutions requires
aqueous solutions. All water must be removed from all standards and samples be diluted at the same
the spray chamber before aspirating organic. A temperature.
convenient way to accomplish this is to ignite the
flame and aspirate deionized H2O for 5 minutes to The 327.4 nm secondary line rather than the 324.7 nm
allow the instrument and burner head to warm up. primary line should usually be used since the
Then aspirate methanol or other similar water-miscible concentration of copper in the samples is in the g/l
organic for 5 minutes to flush all water from the spray range. The air-acetylene flame should be as lean as
chamber and burner. Then aspirate the organic diluent possible. The aspirated organic sample will act as a fuel
for 5 minutes to allow the system to stabilize. The and will give a neutral or fuel rich flame. The
organic should be removed from the spray chamber absorbance and linearity of the standard curve of
before analyzing aqueous solutions or shutting down copper are not very sensitive to the flame conditions
the instrument. Aspirate methanol for 5 minutes to and height of the burner. For most instruments, the
flush all organic from the spray chamber and burner. angle of the burner head should be adjusted so the
Then aspirate deionized H2O for 5 minutes to flush all absorbance of the highest standard is between 0.4 and
methanol from the spray chamber and burner. The 0.6.
instrument is now ready for the analysis of aqueous
solutions or can be shutdown. The following examples are instructions for atomic
absorption spectrometers used in the Cognis Tucson
An organic matrix is necessary for the dilution of laboratory.
samples and standards. Cognis recommends a matrix
of 5 (v/v)% of a LIX® reagent in a petroleum
hydrocarbon approved for use as solvent extraction
diluent. The diluent must be free of all copper. The use
of diluent without a solvent extraction reagent gives
low results with some samples. The use of higher
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MCT Redbook
B. Equipment and Instrument Settings

Perkin-Elmer AAnalyst 300


Slit Width – 0.7 nm
Wavelength – 327.4 nm with no background correction
Burner – Air/acetylene, single slot, 5 cm slot length
Burner Height – The center of the light beam should be about 1 cm above the top of the burner.
The burner height is not critical in copper determination.
Flame – Air-acetylene, oxidizing, fuel lean, blue, air flow 8.0 l/min, fuel flow 0.8 l/min
Lamp Current – 12 ma (refer to lamp manufacturer’s recommend setting)
Integration Time – 3.0 seconds
Replicates – 4

C. Reagents

Organic diluent – 5 v/v% LIX® 984N in a commercially acceptable diluent.


Methanol
Deionized H2O
1000 mg/l Cu Organic Standard – Available from Cognis Corporation, Mining Chemicals Technology,
2430 N. Huachuca Dr., Tucson, AZ 85745 USA. Telephone (520) 622-8891. Fax (520) 624-0912.
Working standards – 60.00 mg/l Cu, 30.00 mg/l Cu, and 10.00 mg/l Cu prepared from the 1000 mg/l Cu Organic standard
and the organic diluent.

D. Analysis

Recall the Copper in Organic method which will set up the AAnalyst 300 using the parameters in the equipment section.
Ignite the flame and aspirate deionized H2O for 5 minutes to allow the instrument and burner head to warm up. While
aspirating the deionized H2O, zero the instrument which will automatically select and turn on the Cu lamp and select the
327.4 nm wavelength. Aspirate methanol for 5 minutes to flush all water from the spray chamber and burner. Aspirate the
organic diluent for at least 5 minutes to allow the system to stabilize. Select continuous graphics from the tool menu and
zero the instrument using the organic diluent as the blank. Aspirate a standard and adjust the angle of the burner so that
the absorbance of the highest standard will be ~ 0.5. Set up a standard curve using the working Cu organic standards. Use
the organic diluent as the blank and the 30.00 mg/l standard as the reslope standard.

Dilute the samples with the organic diluent to get the concentration within the calibration standards. If a dilution of < 1:10
is used for a sample, a matrix effect study should be performed to ensure accuracy of the results. If necessary, the samples
should be reanalyzed using conditions and standards which allow for at 1:10 dilutions, using standard additions
technique, or using standards which have been matrix matched to the samples. Aspirate each sample, read and record
the concentration. Check the blank and standards as necessary to ensure that the calibration has remained constant.

After completing the analyses aspirate methanol for 5 minutes to flush all organic from the spray chamber and burner.
Aspirate deionized H2O for 5 minutes to flush all methanol from the spray chamber and burner. Shut down the
instrument.

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III. Analysis of Copper in Aqueous Leach and Electrolyte Solutions

A. Introduction
The following are instructions for atomic absorption spectrometers used in the Cognis Tucson laboratory. Note that the
327.4 nm secondary line, rather than the 324.7 nm primary line, should be used since the concentration of copper in the
samples is usually in the gram/liter range.

B. Equipment and Instrument Settings

Perkin-Elmer AAnalyst 300


PE Analyst 300 Atomic Absorption Spectrophotometer with Cu lamp and N2O burner.
Slit Width – 0.7 nm
Wavelength – 327.4 nm with no background correction
Burner – adjust so that the center of the light beam ~ 1 cm above the top of the burner.
Flame – Air-acetylene, oxidizing, fuel lean, blue, air flow ~ 7.0, fuel flow ~ 1.0
Lamp Current – 12 ma (refer to manufacturer’s recommend setting)
Integration Time – 3.0 seconds
Replicates – 4
Cal – 1 (nonlinear)
Std 1 – 10.00
Std 2 – 30.00
Std 3 – 60.00
RSLP – 30.00

C. Reagents

Aqueous Diluent – 10 g/L H2SO4 in deionized H2O


Deionized H2O
1000 ppm Cu Aqueous Standard – Available from VWR or other chemical supplier.
60 ppm Cu working standard – Pipet accurately 6.00 ml of 1000 ppm Cu Aqueous Standard into a 100 ml
volumetric flask and dilute to volume with Aqueous Diluent. Mix well.
30 ppm Cu working standard – Pipet accurately 3.00 ml of 1000 ppm Cu Aqueous Standard into a 100 ml
volumetric flask and dilute to volume with Aqueous Diluent. Mix well.
10 ppm Cu working standard – Pipet accurately 1.00 ml of 1000 ppm Cu Aqueous Standard into a 100 ml
volumetric flask and dilute to volume with Aqueous Diluent. Mix well.

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D. Analysis

Set up the PE Analyst 300 AA using the parameters in the equipment section. Aspirate deionized H2O for 5 minutes to
allow the instrument and burner head to warm up. Aspirate the aqueous diluent for 2 minutes to allow the system to
stabilize. Switch the instrument to the Continuous mode and zero the instrument using the aqueous diluent as the blank.
Aspirate the 60 ppm standard and adjust the absorbance to ~0.4 by rotating the burner. Switch the instrument to the
Data mode and set up a standard curve using the 10, 30, and 60 ppm Cu aqueous standards. Use the aqueous diluent as
the blank and the 30 ppm Cu standard as the reslope standard.

Dilute samples with the aqueous diluent to get the concentration within the calibration standards.

Aspirate each sample, read and record the concentration. Check the blank and standards as necessary.

After completing all samples, aspirate deionized H2O for 5 minutes to flush the premix chamber and burner. Shut down
the instrument.

After correcting for dilution, report the results as g/L Cu.

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IV. Cognis Quality Control Test for LIX® C. Preparation
Nickel Oxime Reagents
1. Organic Preparation
A. Introduction Prepare a 500 ml solution of exactly 30 v/v % LIX®
reagent in the diluent Orfom SX-12 or its approved
The standard Cognis Quality Control Test for LIX nickel equivalent. If v/v dilution is not convenient, w/v
oxime reagents is designed to ensure that these Cognis dilutions can be calculated and made using the density
LIX reagents meet rigid specifications for those of the LIX® reagent lot being tested.
properties critical to the performance of these reagents
as nickel extractants. Reagent specifications are tied to 2. Standard Extraction Aqueous Phase
the specific conditions of the standard Quality Control The extraction aqueous phase contains 15 ± 0.1 g/l
Test for LIX nickel oxime reagents, and for this reason, it Ni+2, 1 ± 0.1 g/l Zn+2 (both as sulfates), 32.5 g/l NH3 and
is very important to strictly adhere to the test 25 g/l (NH4)2SO4.
equipment, reagents, conditions and procedures
described in this bulletin. 3. Standard Strip Aqueous Phase
The strip aqueous phase contains 60 ± 0.7 g/l Ni (as the
B. Equipment and Reagents sulfate) and 30 ± 1 g/l H2SO4.

1. Test Vessel 1.0 M NaOH: Weigh 20.0 g NaOH into a 500 ml flask
The test vessel is a jacketed 1 liter beaker equipped and dilute to volume with deionized water which has
with stainless steel baffles, clean and free of soap or been boiled to remove carbon dioxide. Mix well.
detergent residue. The polypropylene impeller is 1.75 Standardize. Protect from CO2 absorption during
inches (4.45 cm) in diameter with 6 slots, 0.125 inches storage to prevent concentration changes.
(0.32 cm) deep and 0.125 inches wide. The top of the
hub is 1 cm above the top of the impeller, and the KHP Buffer Solution: Into a 1 liter volumetric flask,
shaft is 316L stainless steel, 23 cm long. The mixer weigh 51.05 g potassium hydrogen phthalate, KHP.
speed is adjusted to 1650 ± 25 rpm. While Cognis uses Add about 400 ml of deionized water and mix until the
Stirrer Type RZRI available from Caframo (Wiarton, KHP is dissolved. Add the volume of standardized 1.0 M
Ontario, Canada N0H 2T0), any good constant speed NaOH calculated from the following equation: ml
stirrer capable of maintaining 1750 ± 25 rpm is NaOH = 113 / M NaOH. Dilute to volume with
acceptable. The test vessel is maintained at 40 ± 0.5˚C deionized water and mix well. The pH of the buffer
by a recirculating water bath. should be 5.0 ± 0.1.

2. Sample Device 50 g/L potassium oxalate: Weigh 55.4 g K2C2O4·H2O into


When sampling the emulsion, it is important that no a 1 liter flask and dilute to volume with deionized
additional mixing occur. A large bore sampling tube water. Mix well.
should be used. A 10 ml volumetric pipette with the tip
cut off or a 10 ml serological pipette with the sample Before and after each test, all equipment should be
drawn through the large end are satisfactory devices. rinsed several times with DI water followed by
methanol or acetone and completely dried before
each use. Failure to adequately rinse and dry the
equipment can result in erroneous results.

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E. Strip Kinetics, Strip Isotherm Point and
Strip Phase Separation

The organic and aqueous phases from the extraction


test above are transferred to a separatory funnel and
the phases allowed to completely separate. The
aqueous phase is withdrawn and discarded. Loaded
organic is filtered through Whatman 1PS paper or
equivalent filter paper. A 25 ml sample is withdrawn
and set aside for the NH3 loading procedure. The
remaining loaded organic is equilibrated to 40 ± 0.5˚C,
and transferred to a graduated cylinder. The strip
aqueous (325 ml) is added to a clean test vessel. Adjust
D.Extraction Kinetics, Extraction Isotherm the impeller height as previously described, start the
Point, Extraction Phase Separation and stirrer and adjust the speed to 1650 ± 25 rpm. Over a
Extraction Ni/Zn Selectivity period of 5 seconds, add 325 ml of the loaded organic.
Start the stopwatch immediately after the addition of
All solutions used in this procedure must be the organic. Starting at 9 minutes 59 seconds,
equilibrated to 40 ± 0.5˚C before use. Add 400 ml of smoothly remove 10-15 ml of sample emulsion from
organic into the test vessel and adjust the impeller so the top 2 cm of the test vessel and drain into a small
that it is centered in the test vessel and the top of the beaker or separatory funnel. Filter the organic phase
polypropylene hub of the impeller is at the surface through Whatman 1PS paper or equivalent and label
level of the organic phase. Start the stirrer and adjust as the S10 sample. Continue stirring for a total of 20
the impeller speed to 1650 ± 25 rpm and then over 5 minutes, stop the stirrer and allow the phases to
seconds, smoothly add 400 ml of the extraction separate measuring the phase separation time as
aqueous phase. Start the stopwatch immediately at the previously described. Withdraw a 75 ml sample of the
end of the aqueous addition. organic phase, filter through Whatman 1PS or
equivalent filter paper, label a 10 ml aliquot as the S20
Take a 30 second kinetic sample (E30) as follows: sample and save the remainder of the filtered stripped
Starting at 29 seconds, smoothly remove 10-15 ml of organic for interfacial tension analysis.
sample emulsion from the top 2 cm of the test vessel
and transfer the sample into a small beaker or
separatory funnel. After the phases have separated,
filter the organic sample through Whatman 1PS or
equivalent filter paper, label as the E30 sample and
save for analysis. Continue mixing for a total of 300
seconds at which time the stirrer is stopped.
Immediately start a stopwatch and determine the time
required for complete separation of the phases. Phase
separation is considered complete when only a
monolayer of bubbles remains at the interface. Sample
the organic phase, filter the organic sample through
Whatman 1PS or equivalent filter paper, label as the
E300 sample and save for analysis.
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F. NH3 Loading G. Maximum Nickel Loading

Into a 60 ml separatory funnel accurately pipette 20.0 ± Take an aliquot of the diluted reagent and an equal
0.1 ml of filtered loaded organic. Pipette accurately 10.0 volume of standard extraction aqueous and contact
± 0.1 ml of the KHP buffer solution. Shake the them vigorously for 2 minutes in a separatory funnel.
separatory funnel containing the organic and aqueous Allow the phases to separate and discard the aqueous
for 5 minutes. Allow the phases to separate and phase. Add fresh standard extraction aqueous and
remove the aqueous phase. repeat the contact. Continue until a total of 4 contacts
have been made. After the last contact, filter the
Into a titration vessel, accurately pipette 1.00 ± 0.02 ml organic sample through Whatman 1PS or equivalent
of the KHP buffer solution. Add 20 ml of the 50 g/L filter paper, label as the Max Load sample and save for
potassium oxalate solution and mix well. Determine analysis.
the acid content by titration with standardized 0.1 M
NaOH. Calculate the M of H+ using the equation in the Organic samples E30 E300, S10 and S20 and the Max Load
calculation section. sample are assayed by Atomic Absorption
Spectroscopy (AAS) for Ni. The E300 sample is also
Into a titration vessel, accurately pipette an aliquot of assayed by AAS for Zn. All results are expressed in units
the aqueous phase from the separatory funnel. Usually of g/L. AAS procedures used by Cognis Corporation to
2.00 ± 0.02 ml is an appropriate volume. Add 20 ml of determine nickel and zinc in organics are available
the 50 g/L potassium oxalate solution and mix well. upon request.
Determine the acid content by titration with
standardized 0.1 M NaOH. Calculate the M of H+ using H. Calculations
the equation in the calculation section.
Determine the concentration in M of Ni+2 and Zn+2 in 1. Extraction isotherm point, Ni = E300 Ni g/l
the aqueous phase from the separatory funnel that
have been stripped from the organic. Calculate the
acid consumed by the metal stripped from the organic 2. Strip isotherm point, Ni = S20 Ni g/l
using the equations shown below.

M H+ in aqueous = A * B / C 3. Extraction kinetics, % = (E30 / E300) * 100


where A = ml 0.1 M NaOH
B = M NaOH
4. Extraction Ni/Zn selectivity = E300 (Nig/l) / E300 (Zng/l)
C = ml aliquot titrated

M H+ consumed by stripping metal = 2 * D


where D = total M of metals
stripped into the buffer
(
5. Strip Kinetics, % = (E300 Ni - S10 Ni)
)
(E300 Ni - S20 Ni)
* 100

6. Net Transfer, Ni = E300 Ni - S20 Ni


g/L NH3 in organic = (E - F - G) * 17.03 / H
where E = M H+ in KHP buffer
F = M H+ in aqueous
G = M H+ consumed by stripping metal
H = O/A in shake out

63
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V. Clay Treatment Test Procedure
Before and after each test, all equipment should be
A. Introduction rinsed several times with water followed by methanol
or acetone and completely dried before reuse.
During the operation of an SX circuit, the organic
phase can become contaminated with organic C. Clay Treatment Procedure
substances which can adversely affect the phase
separation time, kinetics and the Cu/Fe selectively. Clay Place 400 ml of organic phase into the test vessel and
treatment of the organic phase can sometimes be used adjust the impeller so that it is centered in the test
to remove the contaminant from the organic phase. vessel and the top surface of the impeller disc is 1 cm
below the surface level of the organic phase. If a
To determine if clay treatment will improve the Cognis QC impeller is used, the top of the
performance of the organic, the phase separation time, polypropylene hub of the impeller should be at the
kinetics and the Cu/Fe selectivity are measured before surface level of the organic phase. Begin stirring, set
and after clay treatment. Clay treatment is normally the impeller speed to 1750 ± 25 rpm and over 5
tested initially at the concentration of 1 wt/v%. If the seconds, add the clay. Continue stirring for 60 seconds.
clay treatment is effective at 1 (wt/v) % then lower Then stop the stirrer and immediately filter the treated
concentrations can be tested to determine the organic to remove the clay. Longer mixing times are
minimum concentration necessary for effective usually not necessary. Very long mixing times, > 5
treatment. minutes, usually result in the absorption of some of the
LIX® onto the clay and may also allow some of the
B. Equipment and Solutions contaminants to be released from the clay back into
the organic phase.
Clays that have proven to be effective are acid leached
montmorillinite clays. Montmorillinite powder Grade F
1 available from Engelhard Corporation’s Chemical D. Extraction and Strip Test Procedure
Catalyst Group has been successfully used for many
years by a number of operators. Place 350 ml of stripped organic phase into the test
vessel and adjust the impeller position as described
An efficient mixing chamber and mixer are needed. previously. Begin stirring, set impeller speed to 1750 ±
The equipment used in Cognis' Quality Control 25 rpm and then over 5 seconds, add 350 ml of the
Procedure works well but other equipment can be extraction aqueous phase. A stopwatch is started at
used if this is not available. The Cognis Quality Control the end of the 5 seconds aqueous addition. At 29
extraction and stripping solutions are also used in the seconds, smoothly remove about 10-15 ml of sample
test. If these are not available, PLS and barren emulsion from the stirring test vessel and allow the
electrolyte solutions known to be free of contaminants sample to drain into a small beaker or separatory
can be used. funnel. After the phases have separated, filter the
organic sample through Whatman P/S 1 phase
When sampling the emulsion, it is important that no separation filter paper, label as the E30 sample and
additional mixing occur. A large bore sampling tube save for analysis.
should be used. A 10 ml volumetric pipette with the tip
cut off or a 10 ml serological pipette with the sample Continue mixing for a total of 300 seconds at which
drawn through the large end are satisfactory devices. time the stirrer is stopped and the stopwatch is quickly

65
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reset and started. Determine the time required for E. Calculations
complete separation of the phases. Phase separation is
considered complete when only a monolayer of 1. Extraction kinetics, % = E30 g/l Cu
bubbles remains at the interface. Sample the organic x 100
E300 g/l Cu
phase, filter the organic sample through Whatman 1PS
or equivalent filter paper, label as the E300 sample and 2. Extraction Cu/Fe selectivity = E300 g/l Cu - S300 g/l Cu
save for analysis. E300 g/l Fe - S300 g/l Fe

The organic and aqueous phases from the extraction 3. Strip Kinetics, % = E300 g/l Cu - S30 g/l Cu
x 100
test above are separated in a separatory funnel (discard E300 g/l Cu - S300 g/l Cu
the aqueous phase) and then 325 ml of the loaded
organic is carefully transferred to a graduated cylinder.
Make sure no aqueous transfers with the organic. Filter
if necessary. Next add 325 ml of strip aqueous to a
clean test vessel. Adjust the impeller position as
previously described and begin stirring at 1750 ± 25
rpm. Over 5 seconds, add the loaded organic and then
start the stopwatch. Start the stopwatch immediately
after the addition of the organic. Starting at 29
seconds, smoothly remove 10 - 15 ml of sample
emulsion from the top 2 cm of the test vessel and drain
into a small beaker or separatory funnel. Filter the
organic phase through Whatman 1PS paper or
equivalent and label as the S30 sample. Continue
stirring for a total of 300 seconds, stop the stirrer and
allow the phases to separate measuring the phase
separation time as previously described. Sample the
organic phase, filter the organic sample through
Whatman 1PS or equivalent filter paper, label as the
S300 sample and save for analysis.

Organic samples E30 and E300 from extraction, S30


and S300 from stripping are assayed by Atomic
Absorption Spectroscopy (AAS) for Cu; samples E300
from extraction and S300 from stripping are also
assayed by AAS for Fe. AAS procedures used by Cognis
Corporation to determine copper and iron loaded on
organic are available upon request.

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VI.Direct Colorimetric Determination of 2. Equipment: Spectrophotometer
Uranium on Amine
3. Procedure
A. Introduction 1) Filter the amine sample to be assayed through 1-PS
filter paper.
This is a simple, rapid and accurate method for the
direct colorimetric determination of uranium on amine 2) Transfer 1-3 ml of the amine sample containing 0-
(Alamine® 336 ) extractants. This procedure is linear 800 ppm of uranium and less than 21 mg sulphate to a
from 0-800ppm uranium, the color development is 50 ml volumetric flask.
almost instantaneous and the color is stable for 12
hours. 3) Dilute to the 50 ml mark with chromogenic solution
and mix well. Color development is almost
B. Preparation of Organic Standard and instantaneous and is stable for 12 hours.
Standard Curve
4) Read absorbance at 410 nm using chromogenic
1. Solutions solution as the blank. Note: Use matched cells.
1) 1 g/l uranium aqueous atomic absorption standard.
D. Calculations
2) 6 v/v% Alamine”336 + 4 v/v% decyl alcohol + 90
v/v% kerosene. The optical density of the unknown samples should fall
in the range generated by the standard solutions. If the
Transfer 100 ml of aqueous uranium standard and 100 uranium concentration of the unknown solutions is
ml Alamine solution to a mixer box. Equilibrate the greater than 800 ppm, proper dilutions should be
solutions for three minutes at pH 1.5 using H2SO4 to made prior to the general procedure. For samples in
adjust the emulsion pH. Stop the mixer and allow the the correct concentration range, ppm U is read directly
phases to separate. Discard the aqueous layer and filter from the standard curve. This procedure is linear
the organic phase through 1-PS filter paper. between 0-800 ppm U. The standard curve should pass
through the origin.
This procedure yields a 1 g/l organic uranium standard.
From the 1 g/l organic standard, make a series of
standards ranging from 10-800 ppm U and assay for
uranium following the general procedure.

C. General Procedure

1. Chromogenic Solution
200 mg dibenzoylmethane (1,3-Diphenyl-1, 3-
propanedione) dissolved in 700 ml of industrial
methylated spirit (IMS)*, add 20 ml Alamine 336 and
dilute to 1 liter with IMS.

*IMS = Proprietary Alcohol Solvent, Anhydrous; VWR#


0475-7.
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13
REFERENCES Holmes, J. A.; Deuchar, A. D.; Stewart, L. N.; and Parker, J. D.,
“Design, Construction and Commissioning of the N'Changa
1
Tailings Leach Plant”, International Symposium on Copper
Peligot, E., Ann. Chim. Phys., (3), Vol. 5, 1 (1842).
Extraction and Refining AIME Annual Meeting, Las Vegas, Nevada,
2
February 22-26, 1976.
Morrison G., and Freiser, H, Solvent Extraction in Analytical
Chemistry, John Wiley and Sons, Inc., New York, 1957. 14
Jones, R. L., “Cyprus Bagdad's LIX® Complex”, SME Fall Meeting,
3
Salt Lake City, Utah, September 10-12, 1975.
Ross, A. M., “Solvent Extraction Newcomer to the Colorado
Plateau”, AIME Annual Meeting, New Orleans, Louisiana, February 15
Jenkins, J, Davenport, W.G., Kennedy, B. and Robinson, T.,
27, 1957.
“Electrolytic copper- leach, solvent extraction and electrowinning
4
world operating data”, Proceedings of Copper 99 - Cobre 99
Power, K. L., “Operation of the First Commercial Copper Liquid Ion
International Conference Vol. IV – Hydrometallurgy of Copper,
Exchange and Electrowinning Plant”, AIME Annual Meeting, New
Edited by S.K. Young, D. B. Dreisinger, R.P. Hackl and D.G. Dixon, pp
York, New York, February, 1970.
493 – 566.
5
“New Recovery Process Can Yield Both Electrolytic Nickel and 16
U.S. Patent 4,507,268; March 26, 1985
Copper”, Engineering and Mining Journal, January 1972, p. 94-95.
U.S. Patent 4,544,532; October 1, 1985.
6
Demopoulos, G., and Distin, P A., “Production of Copper Powder 17
Virnig, M., Eyzaguirre, M., Jo, M. and Calderon, J., “Effect of Nitrate
by Reaction Between Hydrogen and Loaded Extractants”, AIME
on Copper SX Circuits: A Case Study,” Proceedings of Copper 99 –
Annual Meeting, Las Vegas, Nevada, February 24-28, 1980.
Cobre 99 International Conference Vol. VI Hydrometallurgy of
7
Copper, Edited by P.A. Riveros, D.G. Dixon, D.B. Dreisinger and J. M.
Feather, A., Clark, P. and Boshoff, G. “Production of High Purity
Menacho, pp. 795 – 810.
Tantalum Oxide by Solvent Extraction”, Proceedings International
Solvent Extraction Conference ISEC “99, Society of Chemical 18
Kordosky, G. A.; Sierakoski, J. M.; and House, J. E., “The LIX®860
Industry, London, pp. 789 – 794.
Series: Unmodified Copper Extraction Reagents”, Proceedings of
8
the International Solvent Extraction Conference (1983), Denver,
Fuwa, A., “Solvent Extraction Technology in Recovery and
Colorado, August 26-September 2, 1983.
Refining of Platinum Group Metals”, Metallurgical Reviews of MMIJ,
Vol. 4, No. 1, (1987) 19
Kordosky, G., “Copper SX Circuit Design and Operation – Current
9
Advances and Future Possibilities”, Technical Proceedings ALTA
De, A. K., Khopkar, S. M., and Chalmers, R. A., “Solvent Extraction of
2003 SX/IX World Summit, Perth, Australia, May 2003.
Metals,” Van Nostrand, London, (1970).
20
10
“In Clean-Air Copper Production, Arbiter Process is First Off the
Merigold, C. R. and Sudderth, R. B., “Recovery of Nickel by Liquid
Mark”, E/MJ, February 1973, p. 74-75.
Ion Exchange Technology”, AIME Annual Meeting, Chicago, Illinois,
February 25-March 2, 1973. 21
Hopkin, W.; Hunter, W. H.; Nakade, K.; Asaro, A.; and Kobayashi, S.,
11
“The Copper Recovery Plants of Commonwealth Smelting Limited
Agarwal, J. C.; Beecher, N.; Hubred, G. L.; Natwig, D. L.; and
and Mitsui Mining and Smelting Co. Limited”, Hydrometallurgy:
Skarbo, R. R., “Metal Separation by Fluid Ion Exchange in the
Research, Development, and Plant Practice, Proceedings 3rd
Processing of Ocean Nodules”, AIME Annual Meeting, Las Vegas,
International Symposium on Hydrometallurgy, K. Osseo-Asare and
Nevada, February 22-26, 1976.
J. D. Miller, Ed., pp. 985-999, 1983.
12
Kordosky, G. A.; Champion, W. H.; Dolegowski, J. R. and Olafson, S. 22
Preliminary report “LIX®54 - A New Reagent for Metal Extractions
M., “The Use of pH Control in Solvent Extraction Circuits”, AIME
From Ammoniacal Solutions”, 1975. Available from Cognis
Annual Meeting, New Orleans, Louisiana, February 19-23, 1979.
Corporation, Tucson, AZ.

23
U.S. Patent 3,883,634; May 13, 1975
U.S. Patent 4,432,952; February 21, 1984
U.S. Patent 4,915,919; April 10, 1990.
69
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MCT Redbook
24 38
Sudderth, R. B.; and Jensen, W. H., “Utilization of LIX®63 in Some Monhemius, A. J. and Burkin, A. R., “Extraction of Cobalt by Tri-n-
Liquid Ion Exchange Systems”, CIMM, 1976 General Meeting, octylamine from Chloride Leach Solutions Containing Other
Montreal, Quebec, Canada, April 21-25, 1974. Anions”, AIME Annual Meeting, Washington, D.C., Feb. 16-20, 1969.

25 39
U.S. Patent 4,081,865, “Solvent Extraction Process for Recovery Magner, J. E., “Cobalt-Nickel Separation by Solvent Extraction”,
and Separation of Metal Values”, April 19, 1977. AIME Annual Meeting, New York, Feb. 15-18, 1960.

26 40
Osseo-Asare, K.; Leaver, H. S.; Davis, P. K.; and Lafferty, J. M., Tunley, T. H. and Faure, A., “The Purlex Process”, AIME Annual
“Extraction of Nickel and Cobalt from Acidic Solutions Using Meeting, Washington, D.C., Feb. 16-20, 1969.
LIX®63-DNNS Mixtures”, AIME Annual Meeting, Denver, Colorado,
41
Feb. 26-March 2, 1978. Faure, A. and Tunley, T. H., “Uranium Recovery by Liquid-Liquid
Extraction in South Africa”, Int. Atomic Energy Symposium, San
27
British Patent 1,470,046, “Process for Liquid-Liquid Extraction of Paulo, Brazil, August, 1970.
Cobalt”, April 14, 1977.
42
Cross, R., “A Note on Solvent Extraction of Uranium at Harmony
28
US Patent 5,229,086 Gold Mine”, J. of South African Inst. of Min. and Met., Nov. 1968,
(196-201).
29
Bhattacharya, B. and Mandal, D.K., “Liquid-liquid Extraction of
43
Gallium with LIX 26”, Sep. Sci. Technol., Vol.38/6, 2003. Baggott, E. R., Fletcher, A. W., and Kirkwood, T. A. W., “Recovery of
Valuable Metals from Nickel-Cobalt Alloy Scrap”, Ninth
30
Merigold, C. R.; Agers, D. W.; and House, J. E., “LIX®64N The Commonwealth Mining and Metallurgical Congress, London,
Recovery of Copper from Ammoniacal Leach Solutions”, Solvent 1969.
Extraction, Soc. Chem. Ind., London (1971), pp. 1351-1355.
44
Eiseke, J. A.; Schultze, L. E.; Berinati, D. J.; and Bauer, B. J., “Amine
31
US Patent 4,331,634 Extraction of Iron from Aluminum Chloride Leach Liquors,” USBM
RI 8188, 1976.
32
Price, M. J. and Reid, J. G., “Queensland Nickel to Commission
45
New Nickel Solvent Extraction Plant”, Tech/News, A Publication of Agers, D. W.; Drobnick, J. L.; and Lewis, C. J.; “The Recovery of
the Mining Chemicals Technology Division of Cognis Corporation, Vanadium from Acidic Solutions by Liquid Ion Exchange”, AIME
September, 1988. Annual Meeting, New York, February 18-22, 1962 and references
therein.
33
U.S. Patent 4,563,256, “Solvent Extraction Process for Recovery of
46
Zinc”, Jan. 7, 1986. “Chromium”, Technical Bulletin CDS 1-61, Cognis Corporation.

34 47
Agers, D. W. and DeMent, E. R., “The Evaluation of New LIX® British Patent 1,418,391; December 17, 1975
Reagents for the Extraction of Copper and Suggestions for the U.S. Patent 3,979,207; September 7, 1976
Design of Commercial Mixer-Settler Plants”, AIME Annual Meeting, U.S. Patent 4,105,442; August 8, 1978.
San Francisco, Calif. 1972 TMS Paper Selection A72-87.
48
U.S. Patent 4,012,481; March 15, 1977
35
Standard Methods of Chemical Analysis, Vol. II A, Sixth Edition, p. U.S. Patent 4,107,261; August 15, 1978.
185, Van Nostrand Reinhold Company, New York, New York.
49
U.S. Patent 3,323,857; June 6, 1967.
36
Brooks, P. T.; and Rosenbaum, J. B., Rep Invest. U.S. Bureau of
50
Mines, 1969, No. 7316. U.S. Patent 3,244,475; April 1, 1966
U.S. Patent 4,185,078; January 22, 1980.
37
Ave, A.; Skjutare, L.; Bjorling, G.; Reinhardt, H.; and Rydberg, J.,
51
“Separation of Iron, Cobalt and Nickel from Scrap Alloy by Solvent U.S. Patent 4,115,512, “Method for Removing Arsenic from
Extraction”, Proceedings of the International Solvent Extraction Copper and/or Nickel Bearing Aqueous Solution by Solvent
Conference (1971) Hague, Netherlands, April 18-24, 1971. Extraction,” Sept. 19, 1978.

70
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MCT Redbook
52 63
Millsap, W. A. and Reisler, N., “Cotter's New Plant Diets on Spent Komasawa, I.; Otake, T. and Ogawa, Y., “The Effect of Diluent in
Catalysts”, E/MJ, May, 1978, pp. 105-107. the Liquid-Liquid Extraction of Cobalt and Nickel Using Acidic
Organophosphorous Compounds”, J. of Chem. Eng. of Japan, 17
53
Merrill, C. C. and Couch, D. E., “Separation of Columbium (4) 1984, pp. 410-417.
Tantalum, Titanium, and Zirconium from Titanium Chlorination
64
Residues”, U. S. Bureau of Mines, RPI 7671, 1972. US Patent 4,705,896, US Patent 4,578,250

54 65
Agers, D. W.; House, J. E.; Drobnick, J. L.; and Lewis, C. J., “The Kordosky, G. A., Sierakoski, J. M., Virnig, M. J. and Mattison, P. L.,
Purification of Inorganic Acids by the Amine Liquid Ion Exchange “Gold Solvent Extraction From Typical Cyanide Leach Solutions”,
Process”, AIME Annual Meeting Dallas, Texas, February, 1963. Hydrometallurgy, 30 (1992) 291-305.

55 66
O'Neill, C. E.; Ettel, V. A.; Oliver, A. J.; and Itzkovitch, I. J., Kordosky, G. A., Kotze, M. H., Mackenzie, J. M. W. and Virnig, M. J.,
“Purification of Nickel-Containing Process Streams by Aliquat®336 “New Solid and Liquid Ion Exchange Extractants for Gold”, XVIII
Thiocyanate”, CIM Conference of Metallurgists, August 22-26, 1976, International Minerals Processing Congress, Sydney, 23-28 May
Ottawa, Ontario, Canada. 1993.

56 67
White, J. C. and Ross, W. J., “Separation by Solvent Extraction with Kordosky, G., Virnig, M., Boley, B., “Equilibrium Copper Strip Points
Tri-n-octylphosphine Oxide”, 1961. Available from Office of as a Function of Temperature and other Operating Parameters:
Technical Services, Department of Commerce, Washington, D.C. Implications for Commercial Copper Solvent Extraction Plants”
Tsinghua Science and Technology, Vol 11(2), April 2006, pages
57
Hurst, F. J.; Crouse, D. J.; and Brown, K.B., “Recovery of Uranium 160-164.
from Wet-Process Phosphoric Acid”, Ind. Eng. Chem. Process Des.
Develop., 11(1), 122-128 (1972).

58
Ross, R. C., “Uranium Recovery from Phosphoric Acid Nears
Reality as a Commercial Uranium Source”, E/MJ, Dec. 1972, p. 80-
85.

59
Cole, P.A., Sole, K.C., “Zinc Solvent Extraction in the Process
Industries”, Mineral Processing & Extractive Metall. Rev., 24: 91 –
137, 2003.

60
Blake, C. A.; Brown, K. B.; and Coleman, D. F., “The Extraction and
Recovery of Uranium (and Vanadium) from Acid Sulfate Liquors
with Di-2-ethylhexylphosphoric Acid and Some Other
Organophosphorous Acids”, USAEC Report ORNL-1903, May 13,
1955.

61
Sudderth, R. B.; Clitheroe, J. B.; and Kordosky, G. A., “The Sulfite
System - A New Hydrometallurgical Process for Zinc”, AIME Annual
Meeting, Denver, Colorado, February 26-March 2, 1978.

62
Preston, J.S., “Solvent Extraction of Cobalt and Nickel by
Organophosphorous Acids I. Comparison of Phosphoric,
Phosphonic and Phosphinic Acid System”, Hydrometallurgy, 9
(1982) pp. 115-133.

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Innovation. Teamwork. Value. Think Cognis.
The Cognis Group, headquartered in
Cognis has been the pioneer in seeking innovative
Dusseldorf, Germany. Cognis ranks
solutions that address the specific and varied requirements
among the world’s leading specialty
of the world’s mining industry. Today, Cognis continues to chemicals companies.
play a leading role in the development of new reagents and
the refinement of process technology for the solvent An international operating company
extraction industry. With its knowledge of chemical with more than 8,500 employees at
processes developed over many decades as well as its approximately thirty service and
understanding of customer needs, Cognis is able to work production sites all over the world, as
closely in collaboration with its industry partners: well as business relations in over one
customers, engineering firms and research organizations. hundred countries, Cognis generates
annual sales of over three billion
The MSPTM Minesite Services Program was developed by euros.
Cognis to facilitate structured and goal-oriented
communications, technical service programs and The Cognis Group supplies metal
extraction reagents and process
product/process development initiatives with our industry
technology to the mining and metal
partners. We work with them to create technically sound
recycling industries. In addition,
and cost effective solutions. All parties, therefore, benefit Cognis supplies its customers with
from knowledge gained as well as the more rapid oleochemical base materials,
development of new concepts, reagents and process additives, formulation and marketing
technology. concepts, and development and
application know-how for numerous
We are a global organization. We think globally. The Cognis industrial markets. These include
“Global Team”has experts located in every strategic mining cosmetics, body care, detergents and
region worldwide. No matter where our customers are cleaners, food, nutrition and health,
located – North or South America, Africa, Europe, Australia paints and coatings, textiles, plant
or Asia – the Cognis team of engineers is ready to provide protection, crude oil production, the
superior service, unmatched reagents and advanced transportation industry, metal
process technology. working, refrigeration and air
conditioning and the fuel and
lubricants industry.
Innovation, teamwork and value. You get all three. All the
time. That’s Cognis.
www.cognis.com

NORTH AMERICA ASIA PACIFIC AFRICA

USA/CANADA/MEXICO: AUSTRALASIA: SOUTH AFRICA:


Elizabeth Martinez Phil Crane Angus Feather
Cognis Corporation Cognis Australia PTY LTD Cognis Corporation
2430 N. Huachuca Drive 4 Saligna Drive Phone/Fax: 27 (0)11 679 4312,
Tucson, AZ 85745 USA Tullamarine VIC 3043, Australia Mobile: 27 (0)83 324 7579
Phone: (520) 622 8891 Phone: 61 3 9933 3500, email: angus.feather@cognis.com
Fax: (520) 624 0912 Mobile: 61 41 837 4842
email: elizabeth.martinez@cognis.com email: phil.crane@cognis.com ZAMBIA:
Gift C. Chisakuta
SOUTH AMERICA CHINA: Cognis Corporation
Forest Li Phone: 26 023 11537,
CHILE: Cognis, Mine Service Manager Mobile: 26 097 875396
Sergio A. Poblete González 15th Floor Xinmao Building email: gift.chisakuta@cognis.com
Cognis B.V. y Cia. Ltda. No.99 Tianzhou Road,
Av. Alonso de Córdova 5151 Cao He Jing Hi-Tech Park, EUROPE
oficina 703 Shanghai 200233 P.R.C.
Las Condes, Santiago, Chile Phone: 86 21 5464 4666, GERMANY:
Fono: (56 2) 201 60 76, Mobile: 86 135 6496 2439 Dr. Werner Schwab
Celular: (56 9) 509 62 08 Fax: 86 21 6485 8898 Cognis Deutschland GmbH & C. KG
Fax: (56 2) 211 95 86 email : forest.li@cognis.com Henkelstrasse 67
email: Sergio.poblete@cognis.com F.M. Geb. C 02, 5th Floor, R 540
Dusseldorf D40589 Germany
PERU: Phone: 49 (0)211 7940 7597,
Jurgen Picardo Mobile: 49 (0)170 45 89 89 3
Cognis Corporation Fax: 49 (0)211 2006 2541
Ricardo Palma 1135 - 102 Faxphone: +49-211-2006-17597
MirafloresLima, Peru email: werner.schwab@cognis.com
Fono: 51 1 4453781,
Celular: 51 1 99921249
email: jurgen.picardo@cognis.com