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Redbook

Mining Solutions
2

Content

1. Introduction 3

2. Solvent Extraction 5

3. Copper Extraction from Acidic Sulfate Solution 8


3.1 Chemistry of Copper Extraction 8
3.2 Development of a Cu SX Process Flow Sheet 13
3.3 Laboratory Development of an SX Circuit 15

4. Copper Extraction from Ammoniacal Solution 21

5. Nickel Extraction from Ammoniacal Solution 23

6. BASF Alamine and Aliquat Reagents 27

7. Extraction of Uranium 31

8. Extraction of Molybdenum and Vanadium 35

9. LIX Reagents Additional Applications 40

10. Appendices 41
10.1 Isocalc Computer Modeling Software 41
10.2 Test Procedures 42
10.3 SX Extractants and Process Auxilliaries 51
10.4 Mixer Settlers 53
10.5 Diluents for Metal Solvent Extraction Applications 55
10.6 Typical Properties of Reagents 56

11. Footnotes 59
3

1. Introduction

The 20th century saw a marked expansion in the requirements


for various metals and global need grew rapidly. Development of
nations such as China and India as well as advances in metal
application technologies has fueled increased demand for
metals.

To meet the needs of modern society for metals in general and higher remains the reagent of choice to this day for the solvent extraction of
purity metals in particular, the mining industry has had to find more uranium. The introduction of Alamine 336 to the mining industry was
effective and efficient methods for processing ores and recovering the followed by the development and introduction of LIX 64 for the
metal values to overcome the challenges associated with decreasing recovery of copper by solvent extraction. The first successful
ore grades and increasingly stringent environmental regulations. The application of the leach-solvent extraction-electrowinning process for
development of hydrometallurgical processing has played a significant the recovery of copper was marked by the startup of the Ranchers
role in helping to overcome these challenges and will provide many of Bluebird Mine copper solvent extraction plant (Design = 5,000tonnes
the new processes required to meet the challenges of the future. Cu/yr) in 19685. This was quickly followed by the commissioning of
Solvent extraction (SX) technology will play an integral role in many of the Cyprus Bagdad copper solvent extraction plant (Design= 6,600
these new processes. tonnes Cu/yr) in 1969.

The first example of the use of liquid-liquid solvent extraction to The Bagdad copper solvent extraction plant is now part of Freeport
recover and purify a metal can be traced back to the extraction of McMoRan and is the oldest operating solvent extraction plant in the
uranyl nitrate into ethyl ether by Peligot in 18421. The analytical world6. This was followed by the commissioning of the Nchanga
chemistry literature contains thousands of references to the use of Tailings Leach Plant (Design = 54,000 tonnes Cu/yr) in 19747. Since
solvent extraction to isolate, purify and concentrate materials to its earliest beginnings, the Mining Solutions group has been
facilitate analysis. This work in analytical chemistry has resulted in the committed to and remains committed to the development of solvent
development of a large pool of fundamental knowledge with regards extraction technology and solvent extraction reagents.
to solution chemistry and organic based extractants2.
The use of copper solvent extraction has grown dramatically since
Starting in the 1950s, solvent extraction was applied on a commercial the late 1960s. There are a total of more than 119 copper solvent
scale to the recovery of uranium, vanadium and molybdenum3. The extraction plants currently operating around the world producing an
Mining Solutions business of BASF, which traces at least a part of its estimated 3.7 MM tons of copper in 2012. Given that total copper
roots to the former General Mills Chemicals, developed Alamine 336 production in 2012 was estimated to be approximately 16.97 MM
and introduced it in 1957 for the recovery of uranium4. Alamine 336 tons8, copper SX represented 22% of the global copper production.
4

The Mining Solutions groups dedication to improving solvent The goal of this book is to familiarize the reader with the
extraction technology has led to a number of industry firsts: fundamental concepts of solvent extraction technology as well
as with the LIX, Alamine and Aliquat solvent extraction
Developed tertiary amines (Alamine reagents) and quaternary reagents and their applications. This booklet will also introduce
amines (Aliquat reagents) for metal extraction4 other reagents, systems and services provided by the Mining
Conceptualized leaching-solvent extraction-electrowinning for Solutions business of BASF. More detailed information about
copper4,7 specific reagents, metals, or process systems is available on
Developed first commercially successful phenolic oxime reagents request.
(LIX reagents) for extraction of copper and nickel.7,9
Developed first alcohol modified aldoxime blend for copper LIX, Alamine, Aliquat and Isocalc* are registered trademarks of
extraction7 BASF SE.
Conceptualized and developed the Picket Fence10
Introduced Clay Treatment11 and scrubbing processes for
cleaning of contaminated circuit organics
Developed non-modified aldoxime/ketoxime blends12,13
Conceptualized and developed use of wash stage technology in
copper solvent extraction14
Conceptualized and developed precipitation/releach flow sheet
for recovery of nickel and cobalt from laterite ores15,16
Conceptualized and developed improved flowsheets
Modified Series Parallel
Optimum Series Parallel17
Split Circuit18
Sequential Circuit19 * Isocalc is a registered trademark in Brazil, Canada, Mexico, Peru and the US
5

2. Solvent Extraction

Solvent extraction (SX) as used in this booklet refers to a liquid-liquid The final metal recovery step will determine the conditions
extraction process for separating species in solution by their under which the metal values will be transferred from the metal
distribution between two immiscible solvents1. In the metal recovery loaded organic to generate a concentrated and purified aqueous
operations of interest, the SX process involves a chemical reaction of metal solution.
the metal species of interest with an organic extractant in an organic
diluent such as a petroleum distillate cut similar to kerosene. The Leaching /
SX/metal recovery are interlocking processes whose
reaction of the metal species with the organic extractant results in a overall success is dependent on the effectiveness of each step. To
hydrocarbon soluble metal complex. The chemistry involves equillibria develop an effective metal recovery process, it is critical to know the
as a result transfer of the metal species into (extraction) and out of nature of the leach solution that is to be treated and the recovery
(stripping) the hydrocarbon phase can be controlled by altering process that will be used to produce the desired metal product. Each
conditions such as the pH of the aqueous. sets criteria within which the solvent extraction process must operate.

As part of a metal recovery process, solvent extraction using BASF The solvent extraction process is conceptually simple:
extractants has three primary objectives:
The metal bearing leach solution (Pregnant Leach Solution, PLS)
Purification of the metals from unwanted impurities. is fed into a mixer along with an immiscible hydrocarbon solution
Extract desired metal(s) away from impurities. of a metal extractant (Barren Organic) where the two solutions
Extract impurities away from desired metal(s). are intimately mixed.
Concentration of the metal values to reduce downstream The resultant emulsion overflows from the extraction mixer into
processing costs. the settler. As it progresses down the settler, the solutions
Conversion of the metal values to a form which simplifies final separate to give a metal loaded organic (LO) solution on top and a
recovery. metal depleted aqueous solution (raffinate) on the bottom.
The raffinate is discharged via an underflow weir and recycled to
In any given solvent extraction process, one, two, or all three leaching. The LO passes over a weir and flows to a second mixer
objectives may be necessary. where it is intimately mixed with a strip solution.
The resultant emulsion overflows from the strip mixer into the
A key point for the reader to understand is illustrated in Figure 1. corresponding settler where it separates into a metal barren
Solvent extraction is only one unit process in a series of unit processes organic (BO) which is returned to extraction and a concentrated
in going from the metal bearing ore to the final metal product. The aqueous solution (Pregnant Strip Solution) of the desired metal in
leaching process delivers a metal bearing solution whose nature will a form from which it can be readily recovered.
vary depending on the actual ore and the conditions required to
achieve effective solubilization of the metal values. The solvent Figure 2 illustrates a copper solvent extraction plant consisting of 2
extraction process must be able to efficiently transfer the metal stages of countercurrent extraction and 2 stages of countercurrent
values from this incoming leach solution into the organic phase. stripping.

Formula 1

Extract
2RH(Organic) + Cu+2(Aqueous)
R2Cu(Organic) + 2H+(Aqueous)
Strip
6

Figure 1: Generalized Metal Recovery Flowsheet Each mixer-settler represents one stage of extraction or stripping. In
Incorporating Solvent Extraction with BASF Reagents. conventional circuit flowsheets, E1 designates the stage into which
the PLS is introduced and S1 designates the stage into which the
loaded organic is introduced. In some cases, wash or scrub
stages may be required to prevent or reduce the transfer of unwanted
species on the organic phase from extraction to strip or vice versa.
ch Solution IX R
eagent
trip S
olution
led
Lea
pe
dL
ou
sS The combination of proper reagent choice, ability to use a variable
yc rip ue
number of mixer-settler stages, adjust flow rates, and use of wash
c

Aq
St
Re

stages allows a great deal of flexibility in designing a plant to meet the


Metal Leaching Metal Extraction Metal Stripping Pure Metal Product requirements for a given metal recovery problem.

To develop a successful flow sheet for the recovery of a metal, it is


Im

important to know the composition of the aqueous feed solution in


d
t
pu

rif
ie
en

e g
M ea Pu
r

eta Co
R n c e n tr a t e d & io n
l Le
a c h S o l u ti o n
Me
tal L o a d e d LIX
M etal S ol
u t terms of the metal species and other species including anions that
are present. With respect to metals, the extractable species can be
Leaching Solvent Final Metal classified into 4 types:
Process Extraction Recovery

1. Metal cations, for example Cu2+, Ni2+, Co2+, Zn2+


2. Complex metal anions such as UO2(SO4)34-, Mo8O264-,
H2V6O172-, CoCl42-
3. Complex metal cations such as MoO22+
4. Neutral metal species such as UO2(NO3)2
Figure 2: Copper Continuous Solvent Extraction Unit

Partially Loaded
Organic
E1 E2

PLS Raffinate

Loaded
Surge Organic
Tank Barren
Organic

S1 S2

Pregnant Lean
Strip Soln Strip Soln
7

The metal species listed above have all been recovered commercially In order to be commercially successful, a metal extractant must meet
in solvent extraction plants at one time or another. It represents only the following criteria at least in part:
a small sample of the many extractable chemical species that may
be present. 1. Have a cost conducive to good process economics.
2. Extract the desired metal(s) with some degree of selectivity from
Metal extractants are divided up into five separate classes dependent the aqueous feed solution.
upon the structure of the extractant, the mechanism of extraction 3. Strip the metal values from the loaded organic into an aqueous
and nature of the metal species extracted: solution which facilitates final metal recovery.
4. Be stable to the operating conditions through many cycles of
Chelating extractants. extraction and stripping.
Ion pairing extractants. 5. Load and strip metal at a rate fast enough to permit use of
Organic acids. economical mixing times.
Extractants that function by ligand substitution. 6. Exhibit good phase separation properties.
Extractants that function by solvation. 7. Be nonflammable with low toxicity, non-carcinogenic, etc.
8. Soluble both as the extractant and as the metal complex in an
BASF markets chelating reagents and ion pairing reagents. Chelating inexpensive organic diluent.
reagents function by forming chemical bonds with a cationic metal 9. Avoid transfer of species from stripping to extraction that might
ion at two sites similar to grasping an object between the ends of interfere with extraction.
ones thumb and index finger. The LIX reagents based on the
phenolic oximes are examples of chelating reagents. Ion pairing While no extractant meets 100% of each of these criteria, successful
extractants function by forming an organic soluble ion pair between reagents possess a good balance of all the properties in the list.
an organic soluble cationic species and a complex anionic metal BASF reagents possess this balance of properties.
species. The Alamine and Aliquat reagents are examples of ion
pairing extractants. The Alamine reagents are based on tertiary Reagent selectivity is often an issue. Very few, if any, extractants
amines having long alkyl chains. They accept a proton from acid demonstrate selectivity for only one metal over a broad range of
solutions to form a cationic ammonium ion which can then pair with conditions. Many extractants, however, are reasonably selective for
an anion in the organic phase. Aliquat reagents are based on one metal over another under a certain set of conditions. The
quaternary amine salts. The Aliquat reagents function similarly to the selectivity is dependent on the conditions and the challenge is to
Alamine reagents; the difference being that the quaternary amine is match the conditions associated with the given leach solution with
always positively charged. Since there is no need to form a cation by the selectivity characteristics of the available reagents. A perfect
protonation, the Aliquat reagents can also extract anionic species match is seldom achieved. One either settles for a reagent that
from alkaline aqueous solutions. performs reasonably well or one tries to alter the leaching process
to produce a leach solution which will allow an extractant to be
Successful reagent selection requires matching the chemical more selective. To do this successfully, one needs a very good
characteristics of the extractant with those of the metal species understanding of the chemistry of the leaching process as well as the
present in the incoming aqueous feed solution. While chemists have chemistry of the extraction process. A BASF technical representative
identified metal extractants for carrying out chemical separations of can help to provide the necessary understanding of the chemistry.
just about all metals in one form or another, the number of extractants
available to carry out commercially viable large scale metal recovery
processes is relatively small.
8

3. Copper Extraction from Acidic Sulfate Solution


3.1 Chemistry of Copper Extraction

All modern commercial copper solvent extraction reagents are based In the process of forming a complex, two hydrogen ions are released
on phenolic oxime type molecules. They can be classified into two into the aqueous solution for every copper ion that is extracted. The
general types, aldoximes and ketoxime. chemistry is summarized in the following equation where RH
represents the extractant (Formula 1).
H H H H

H H O O H H O O H
O O N N O O N N H O
R O N
H H CH3 CH3 Cu
N O R

H O H
R R R R
A key parameter in controlling the equilibrium position of this reaction
R Aldoxime Ketoxime is the acid content of the aqueous phase. Low concentrations of acid
in the aqueous favor extraction and high acid concentrations favor
stripping. This behavior can be represented graphically as a pH
isotherm. Typical pH isotherms for ketoxime and C9 aldoxime are
C9H19 C9 Aldoxime, Ketoxime, 5-Nonyl-2-
represented in Figures 1 and 2.
5-Nonylsalicyl- hydroxyacetophenone
aldoxime Oxime
Figure 1: pH Isotherms for Several Metals with Ketoxime

C12H25 C12 Aldoxime, 100


Cu Ni
5-Dodecylsalicyl-
aldoxime
80
Mo Co
Extraction %

60
They form a complex (I) with copper by loss of the phenolic hydrogen
as a proton and formation of chemical bonds from the phenolic
oxygen (dark red) to the copper ion and from the nitrogen (dark blue) 40
of the oxime to the copper ion. The complex is very non-polar and Fe3+
hydrocarbon soluble. They belong to a group of molecules described
20
as bidentate chelating agents since they grasp the copper ion
between the two sites in a pincer like fashion. The R group is typically Mn Zn
a highly branched hydrocarbon chain consisting of either 9 or 12 0
0 1 2 3 4 5 6 7 8
carbon atoms.
pH

Formula 1

Extract
2RH(Organic) + Cu+2
(Aqueous)
R2Cu(Organic) + 2H+(Aqueous)
Strip
9

These pH isotherms can be used to predict the extraction any extracted Mo(VI) can be removed from the organic if necessary.
characteristics of a reagent under a variety of conditions. For In most cases, only Fe(III) presents a potential problem with regard to
example, it is apparent that copper(II) is strongly extracted by both preparing a pure copper solution from a normal copper leach
reagents at a pH of 2.0 and that the C9 aldoxime extracts copper(II) solution at pH = 2.0 in agreement with the pH isotherms in Figures 1
more strongly than the ketoxime. Ferric iron at a pH of 2.0 is only and 2.
slightly extracted and nickel(II), cobalt(II), zinc(II) and manganese(II)
are not extracted. With the ketoxime at a pH of 5.0, copper(II), iron(III),
nickel(II) and cobalt(II) are all potentially strongly extracted. From a
practical standpoint, extraction of iron(III) at a pH of 5.0 is not
important since iron(III) is only slightly soluble at a pH of 5.0. Table 1: Relative Extraction Power of Ketoxime and Aldoxime
for Metals at pH 2.0
Figure 2: pH Isotherms for Several Metals with C9 Aldoxime
Metal Relative Extractive Power
100
Cu Ni

80
Cu(II) Very strongly extracted
Mo Co Zn
Extraction %

60 Fe(III) Slightly extracted

Mo(VI)1) Moderately extracted


40
Fe3+
V(V)1) Slightly extracted
20
Zn(II) Nil
Mn
0
0 1 2 3 4 5 6 7 8 Sn(II) Nil

pH
Ca(II) Nil

From a comparison of Figures 1 and 2, one can conclude that the C9


Mg(II) Nil
aldoxime extracts all of the metals with the exception of manganese(II)
more strongly than does the ketoxime. In making comparisons of pH
As(III) Nil
isotherms for two different reagents with the same metal or for two
different metals with the same reagent, the pH isotherms must be
Al(III) Nil
determined under exactly the same conditions. A summary of the
general relative extraction behavior for a wide range of metals with
Fe(II) Nil
ketoxime and C9 aldoxime is summarized in Table 1.

Si(IV) Nil
While the data in Figures 1 and 2 suggest that Mo(VI) could be a
problem in a copper solvent extraction circuit using either a ketoxime,
Co(II) Nil
an aldoxime, a blend of a ketoxime with an aldoxime or a modified
aldoxime. It typically is not a problem for two reasons. Copper is
Ni(II) Nil
more strongly extracted than Mo(VI) by the oximes and readily
displaces any extracted Mo(VI) from the organic. If excess copper is
Mn(II) Nil
present, Mo(VI) will not be significantly extracted. Even if Mo(VI) is
extracted by the oximes, it is not readily stripped by an aqueous
solution of sulfuric acid and is therefore not transferred to the copper 1) The chemistry of Mo(VI) and V(V) on the acid side is quite complex.
electrolyte. In addition, Mo(VI) strips readily on the alkaline side so They do not normally present a problem in copper solvent extraction circuits.
10

Consideration of extraction isotherms and selectivity data allow the Figure 3: Effect of Increasing LIX 84-I Content on Stripping
metallurgist to develop metal separation schemes. Where such data of Cu and Cu Net Transfer with Non-modified
is not available for a particular system, one can develop the required Aldoxime/Ketoxime Blends*
information by screening the reagent against the metals most likely to
be found in the aqueous feed solutions of interest under conditions 4
similar to those expected in the solvent extraction process. The Net Transfer@ pH 2.0
3.5
resultant selectivity data holds only at the conditions under which it is
Net Transfer@ pH 1.5
determined. Small changes in the test conditions can result in 3
significant shifts in the extraction isotherms and selectivity.
Cu Conc (g/L)
2.5

These conditions include: 2


The nature of the reagent. Stripped Organic
The nature of the anions present in the aqueous solution. 1.5
The metal and reagent concentrations.
1
The oxidation state of the metal. Increasing Ketoxime Content:
The pH of the aqueous feed solution. 0.5 Weaker Extractant, More readily
Stripped, Higher Net Transfer
The temperature at which extraction occurs.
0
The organic-aqueous contact time. LIX 860N-I LIX 973N LIX 984N LIX 937N LIX 84-I

* Solutions of the reagents were prepared in a hydrocarbon diluent and the concentrations
Modern metallurgists have a broad spectrum of copper extractant
adjusted to give a Cu max load of 5.6 g/L copper under the conditions of the BASF Oxime
formulations based on the aldoximes and ketoxime available to aid
QC procedure. The organics were then contacted twice with an aqueous strip solution
them in developing effective recovery schemes for copper from a
containing 35 g/L Cu and 160 g/L sulfuric acid at an O/A =1 by shaking for 15 minutes.
broad range of leach solutions. As can be seen from a comparison of
The resultant stripped organics were assayed for copper content and then contacted with
the Cu pH isotherms in Figures 1 and 2, the aldoximes by themselves aqueous solutions containing 6 g/L Cu at pHs of 2.0 and 1.5 at an O/A = 1 by shaking for
are much stronger copper extractants than is the ketoxime. While 15 minutes to yield loaded organics. The copper contents of the loaded organics were
their extractive strength is a potential advantage, it is also a problem. determined. The Cu Net Transfer was then determined by subtracting the copper
The aldoximes do not readily give up the extracted copper when concentration of the stripped organic from that of the corresponding loaded organic.
contacted with typical lean electrolyte solutions that are generated by
standard copper tank house operations. As a result, only a relatively
Table 2: Proportions of LIX 84-I and LIX 860N-I in Standard
small percentage of the overall loading capacity is utilized in the
Non-modified Reagents
transfer of copper from extraction to stripping (Net Transfer).

Two approaches have been utilized to increase the net transfer of Reagent % v/v LIX 84-I % v/v LIX 860N-I
reagents formulated with aldoximes. One approach is to combine
the aldoxime, either C9 or C12, with ketoxime. The aldoxime and
ketoxime form a synergistic mixture, i.e. the combination strips more
LIX 84-I1) 100 0
readily than one would expect based on a simple combination of the
properties of the two components1,2. Blending the two components
LIX 937N 70 30
results in no significant impact on copper loading capacity in
extraction while greatly improving stripping. This translates into an
LIX 984N 50 50
increase in copper net transfer capability relative to an aldoxime by
itself. As illustrated in Figure 3 and Table 2, increasing the proportion
LIX 973N 30 70
of ketoxime relative to aldoxime results in increased ease of stripping
(lower residual copper on the stripped organic) consistent with a
LIX 860N-I2) 0 100
decrease in extractive strength. The decrease in extractive strength
is also reflected in the fact that the net transfer capability falls off 1) Ketoxime dissolved in a hydrocarbon diluent.
faster as the acid concentration increases (lower pH). 2) C9 aldoxime dissolved in a hydrocarbon diluent.
11

By blending the aldoxime and ketoxime in varying proportions, BASF Figure 4: Effect of Increasing Ester Modifier Content on
Mining Solutions can tailor a reagent to fit the specific extraction and Stripping of Cu and Cu Net Transfer with Modified Aldoxime
stripping requirements of a particular application. Formulations Reagents*
consisting of mixtures of an aldoxime with ketoxime are classified as
non-modified reagents or blends. 4
Net Transfer@ pH 2.0
3.5
The second approach takes advantage of the fact that the aldoxime
will form complexes by hydrogen bonding with a wide variety of 3
Net Transfer@ pH 1.5
chemical compounds3,4. The most commonly used classes of Cu Conc (g/L)

compounds in commercial formulations are alkyl phenols as well as 2.5

higher molecular weight alcohols and esters. These materials are 2


commonly referred to as thermodynamic modifiers in this application. Stripped Organic
Increasing the relative amount of the thermodynamic modifier results 1.5
in a shift in performance similar to that observed with the ketoxime as
1
illustrated in Figure 4 where LIX 860N-I represents no modifier and Increasing Ester Content:
the level of modifier, an ester, increases as one progresses from LIX 0.5 Weaker Extractant, More readily
Stripped, Higher Net Transfer
654N-LV to LIX 684N-LV, the most heavily modified formulation in
0
the series. Formulations consisting of a mixture of a thermodynamic LIX LIX LIX LIX LIX
modifier with an aldoxime are classified as modified reagents or 860N-I 654N-LV 664N-LV 674N-LV 684N-LV

modified aldoximes. * Procedure was identical to that described for Figure 3.

Table 3: Comparison of Properties for Reagents based on


Ketoximes, Aldoximes, Non-modified Blends and Modified Aldoximes

Property Ketoxime Aldoxime Non-Modified Blend Modified Aldoxime

Extractive Strength Moderate Very Strong Customized Customized

Stripping Very Good Poor Customized Customized

Cu/Fe Selectivity Excellent Excellent Excellent Excellent

Extraction Kinetics Very Good Very Fast Fast Very Fast1)

Phase Separation Fast Fast Fast Fast

Stability Very Good Very Good Very Good Very Good2)

Crud Generation3) Low Low Low Variable4)

1) Formulations based on C9 aldoximes tend to be slightly faster than those 3) Dependent on the composition of the leach liquor and the modifier.
based on C-12 aldoxime. 4) In many cases, the presence of thermodynamic modifiers increases
2) Dependent on the particular thermodynamic modifier used in the formulation. crud formation.
12

One can also blend thermodynamic modifiers with mixtures of Modified aldoxime reagents have excellent metallurgical properties
aldoxime with ketoxime to form a third class of extractant formulations, even at low temperatures, low pHs or when the copper content of
modified aldoxime/ketoxime blends. BASF Mining Solutions has the the leach liquor is very high and high copper recoveries are needed.
capability of offering all three classes of extractant formulations. However, in many cases, the use of a modified aldoxime formulation
carries with it higher entrainment rates and/or greater crud generation
A general comparison of the copper extraction characteristics of resulting in increased carryover of impurities to the electrolyte and
ketoxime, aldoximes, non-modified blends and modified aldoximes higher reagent consumption per ton of copper produced6,7,8.
is summarized in Table 3.
The non-modified aldoxime/ketoxime mixtures also operate well at
Presents the operators of copper solvent extraction plants with a lower pHs, lower temperatures, and with leach liquors having a
wide choice of reagents from which to choose. higher copper content. They tend to be slightly slower kinetically at
lower temperatures depending on the ketoxime content of the
The availability of: formulation as compared to modified aldoxime formulations. They
Pure aldoxime based extraction reagents also tend to be slightly less selective for copper over iron as compared
LIX 860-I, a C12 aldoxime based formulation and to an ester modified aldoxime formulation. In terms of physical
LIX 860N-I, a C9 aldoxime based formulation performance under a wide variety of conditions, they tend to give
Modified aldoxime reagents more stable mixer continuities, lower entrainment of aqueous in the
LIX 622N, and the ester based series: LIX 654N-LV, loaded organic and generate less crud than modified aldoxime
LIX 664N-LV, LIX 674N-LV and LIX 684N-LV formulations. Some of these physical advantages can be attributed
Pure ketoxime based extraction reagents to the fact that these reagents are the lowest density and lowest
LIX 84-I and LIX 8180 viscosity copper solvent extraction reagents available.
Non-modified aldoxime/ketoxime blends
LIX 973N, LIX 984N, and LIX 937N Clearly there is not a single reagent of choice for the extraction of
Modified aldoxime/ketoxime blends copper from sulfuric acid leach liquors. Your BASF Mining Solutions
LIX 1552N-LV technical representative can help you decide on the best reagent for
your needs.
Since ketoxime based reagents are moderately strong copper
extractants, they operate best when the pH of the leach solution is
relatively high (above pH 1.8) and the solution is relatively warm
(20C or higher). Since they strip very well, they can effectively be
used with only one strip stage and they can be used efficiently when
the amount of acid in the lean electrolyte exiting the copper tank
house is relatively low (less than 160 g/L H2SO4). They have also
been effectively used in cases where the leach solution contains
nitrate which will degrade modified aldoximes5.
13

3.2 D
 evelopment of a Cu SX
Process Flow Sheet

Factors for Consideration In addition to copper, leach solutions may contain other metals such
as iron (ferric and ferrous), molybdenum, manganese, aluminum,
magnesium, sodium, and potassium. In addition to sulfate, it may
When developing a process for recovery of copper by solvent
contain anions such as chloride and nitrate. The concentration of
extraction, there are a number of factors to consider:
these impurities will vary widely depending on the ore, available water
sources and evaporation rate. Certain ore bodies in Chile contain
Type of leach and nature of the ore
nitrate. Since nitrate is readily leached, the concentration of nitrate in
Composition of the pregnant leach solution
the resultant leach solutions may be up to 2530 g/L. Due to the lack
Nature of the final copper product and process required to
of fresh water, some operations successfully operate using sea water
produce it
for leaching resulting in up to 90 g/L of chloride in the leach solution.
Operational philosophy
While the presence of nitrate and chloride can cause problems in SX-
EW, methods have been developed to successfully deal with them12.
The primary commercial application for modern phenolic oxime
based copper solvent extraction reagents has been recovery of
The nature of the leach, the ore type and climatic conditions may play
copper from dilute sulfuric acid leach solutions. These solutions
a role in the temperature of the pregnant leach solution delivered to
result from leaching of copper oxide and/or secondary sulfide ores
solvent extraction which in turn will determine the operating
using various leaching technologies including dump, heap, in-situ,
temperatures in extraction and stripping. A typical heap leach solution
thin layer, vat, and agitation1,2,3. The choice of methodology is
will range in temperature from about 20C to about 30C but may
dependent on the nature of the ore and the ore grade. A variety of
drop to 10 15C during harsh winter conditions and /
or high
technologies are currently being investigated for the leaching of
elevations. Colder temperatures will shift the extraction equilibrium to
primary copper sulfide concentrates4,5,6,7. Since leaching is a critical
the left (weaker extraction), affect the extraction kinetics and the
step in the overall process of Leach-SX-EW, BASF strongly
solution viscosities impacting overall extraction efficiencies and
recommends that one thoroughly investigate the leaching
physical performance of the extraction circuit. Vat, agitation and
characteristics of their ore8,9,10,11. If you cannot bring the copper into
concentrate leach solutions can be quite warm resulting in temperatures
solution effectively, it cannot be extracted. Money spent on up front
in extraction of up to 45C. While the higher temperatures will result in
leaching studies typically proves to be a wise investment.
shifting the extraction isotherm to the left13, increasing kinetics and
lowering solution viscosities, hydrolytic degradation of the reagent may
Depending on the leaching technology and ore grade, pregnant
become more of an issue depending on reagent type.
leach solutions may contain from less than 1 g/L copper up to about
50 g/L of copper over a pH range of <1.0 to 3.0. the composition of
Copper is typically recovered as copper cathode but has also been
typical sulfuric acid leach solutions that have been treated by solvent
recovered as copper sulfate crystal14,15,16. Most copper EW tank
extraction are summarized in Table 1.
houses which produce high quality copper cathode operate so that
the lean electrolyte exiting the cell contains from 32 to 40 g/L of copper
Table 1: Typical Sulfuric Acid Leach Solutions
and 150 to 185 g/L of sulfuric acid. Improvements in technology have
allowed current densities to be increased from about 160 amps/m2 to
Leach Type Cu (g/L) pH well over 400 amps/m2 in todays modern tank houses. To insure high
copper quality at these high current densities, the level of copper in the
electrolyte exiting the cells is typically maintained at levels greater than
35 g/L of copper and at times greater than 40 g/L of copper. Based on
Dump, Heap, In-situ <1 to 6 1.3 to 2.2
experience in some tank houses, slightly higher quality copper is
obtained when plating from sulfuric acid concentrations at the lower
Ferric Cure, Thin Layer 3 to 6 1.5 to 2.2
end of the acid concentration range17. The tank house parameters in
terms of copper and acid in the exiting spent electrolyte and incoming
Vat 5 to 50 1.6 to 2.0
rich electrolyte are determined in part by the operating philosophy of
the plant manager. These parameters combined with the strip staging
Agitation 1 to 35 1.4 to 2.0
and nature of the oxime copper extractant will impact how completely
the loaded organic is stripped and how much free reagent will be
Concentrate 25 to 80 <1.0 to >2.0
available to carry out extraction.
14

Along with the evolutions in leaching technologies, reagent them to use a series parallel flow scheme or some other combination
technologies and tank house operations, there have been significant of stages to be able to treat the required additional flow. Making
developments in the understanding of the interaction of reagent and allowance for potential plant alterations during the planning stages
circuit staging which can result in lower costs and more efficient will provide the plant with the flexibility to meet future requirements27.
copper production18,19,20,21. A listing of circuit configurations that have When treating a leach solution containing significant amounts of
been used in commercial operations over the years is summarized in chloride, nitrate, iron, or manganese, the addition of a loaded organic
Table 2. wash stage should also be considered to minimize the transfer of
these impurities to the tank house28.
Table 2: Commercial Solvent Extraction Circuit Configurations
BASF Mining Solutions produces three oximes, C9 aldoxime (LIX
860N-I), C12 aldoxime (LIX 860-I) and ketoxime (LIX 84-I), which
Circuit Type Configuration* Stages
serve as the basis for formulation of a wide range of modified and
per Train
non-modified copper extractants. Deciding on the best reagent
choice for a given application requires having an understanding of
the inherent properties of these oximes29,30. For example in circuits
Series 4E x 3S 7 operating at higher temperatures in extraction, one might want to use
LIX 84-I, mixtures of LIX 84-I with LIX 860-I or a modified C12
Series 4E x 2S 6 aldoxime to take advantage of their stability. The relative stability of
the oximes is: ketoxime >C12 aldoxime >C9 aldoxime. When dealing
Series 3E x 2S 5 with a leach solution containing nitrate, LIX 84-I has proven to be
the most resistant to degradation. In cases where one is faced with
Series 2E x 2S 4 a leach solution containing high levels of copper, recovery will be
limited by the corresponding increase in acid concentration in the
Series 2E x 1S 3 aqueous as the copper is extracted. The logical choice would be a
reagent formulation containing higher levels of an aldoxime or a less
1E x 1S 2 modified aldoxime. Work has shown however that a combination of
a weaker extractant such as LIX 84-I in a circuit having 3 stages of
Series Parallel 2E x 1EP x 1S 4 extraction in series and 1 strip stage can also be effectively used31,32.
When considering reagent choices, contact your local BASF Mining
Series Parallel 2E x 1EP x 2S 5 Solutions technical representative who has the knowledge of the
reagents and experience to assist you in making the best reagent
Cross Flow 1E x 1EP x 1EP x 1S 4 selection for your individual application.

* E represents extraction stage, EP refers to a parallel extraction stage, Figure 1: Sequential Circuit
and S refers to a strip stage
Milled
The most common circuit configurations in use today are 2E x 2S, Ore Solids
Acid
2E x 1S, and 2E x 1EP x 1S. More recent developments include the Water
Tails
use of the Split Circuit concept and Sequential Circuit (Figure 1)
concept to reduce acid consumption and increase copper recoveries Leach 1 S/L 1 Leach 2 CCD
in agitation leach circuits22,23,24,25,26.
Co
Recovery
While many plants opt to employ a simple circuit consisting of 2
SX 1 S/L 2 SX 3
stages of extraction in series and 1 or 2 stages of stripping in series
to minimize capital cost, they may find their production capacity
limited at some point as the grade of the incoming pregnant leach
solution declines due to a drop in ore grade. To maintain production,
SX 2 Neut
they must be able to treat more leach solution. This may require Tails

modifying the piping or adding additional extraction stages to allow


15

3.3 L
 aboratory Development
of an SX Circuit

Given a pregnant leach solution (PLS), how does one develop a phase is discarded after the phases have separated. A portion of the
process for recovering the metals of interest? The first step is to resultant copper loaded organic (LO) is then contacted with vigorous
determine if the solution is typical of what would be expected in shaking three times with fresh rich electrolyte (RE) at an O/A = 1. Rich
normal operation. Work carried out on a non-typical solution is often electrolyte is the aqueous acid strip solution that is expected to exit
wasted effort. The composition of the solution with regard to metals, the strip stage. In this exercise, we will assume that the RE contains
metal concentration, pH, presence of ammonia and its concentration, 50 g/L Cu and 160 g/L of sulfuric acid. The resultant organic will
presence of chloride or nitrate and their concentrations, etc., must closely approximate a stripped organic (SO) one would expect to
be determined. Given the composition, one can then begin to make generate in a continuous circuit having one strip stage. This process
judgments with regard to which metals can be separated based on serves not only to generate a SO for the isotherm determination but
available extraction isotherms. If the data for some of the metals is also serves to wash out any low molecular weight impurities from the
not available, the extractant(s) being considered should be screened manufacturing process.
against these metals. Given this information, one can then determine
a strategy for recovering commercially viable metals by solvent The extraction isotherm is then determined as follows:
extraction under the given set of conditions. With this background,
circuit development work can now begin keeping in mind that all Vigorously contact the freshly prepared SO with leach solution for
parts of the total metal recovery process must fit together in a 310 minutes at various O/A ratios (Typically 10/1 to 1/5).
workable manner. Typically requires 67 points for a good isotherm.
Contacting can be carried out in separatory funnels or by
As an example, consider development of a copper solvent extraction stirring in BASF QC mixer boxes. (When using separatory
circuit to treat a copper heap leach solution containing 2.5 g/L of Cu funnels, longer contact times are recommended to insure that
and 1.30 g/L of total Fe at a pH of 1.80. Assume also that you want true equilibrium is achieved.)
a copper recovery of 90%. If the temperature in extraction is expected to be warm due to
the temperature of the incoming leach solution, contacting
should be carried out in jacketed vessels at the expected
Extraction and Strip Isotherms
temperature and samples of organic and aqueous must be
collected at the expected temperature. For further information,
While a variety of extractants can be used, LIX 984N, a widely used
contact your BASF technical representative.
non-modified blend of aldoxime and ketoxime, is particularly well
After allowing the phases to separate, samples of the respective
suited to treat the leach solution under discussion. Based on previous
organic and aqueous samples are collected, filtered and saved
experience with similar solutions, one can expect LIX 984N to
for analysis. The organic is analyzed for copper (and perhaps
transfer 0.240.30 g/L Cu per 1% v/v in a circuit consisting of 2
iron) while the aqueous is analyzed solely for copper.
stages of extraction and 1 stage of stripping, a common choice in
The data is summarized in Table 1 and is plotted in Figure 1.
modern plants. Since the pH is 1.80, we will assume that the copper
Accurate measurement of the organic and aqueous volumes
transfer will be somewhere in the middle to lower end of the range
used for each shakeout will allow one to calculate a mass
(0.26 g/L of copper/1% v/v LIX 984N). Using the following equation,
balance for each point. Mass balances should be very good
one can then calculate the approximate reagent concentration
for O/A ratios in the range of 5:1 to 1:5. If the mass balance is
required to meet the stated goal of 90% recovery.
poor for one point, the retained samples corresponding to that
shakeout should be re-analyzed. Mass balances at the
extremes of O/A (10/1, 1/10) are typically less precise.
Equation1
For copper extraction with a phenolic oxime type extractant, the
[2.50 g/L Cu x (0.90)]/0.26 g/L Cu per % v/v = 8.7% v/v LIX 984N
plot should result in a smooth curve similar to that shown in
Figure 1. One should also check how the various points are
distributed along the curve. For the best results, it is important
To determine the extraction and strip isotherms, a solution containing
to carefully define the area around the bow in the curve as
8.7% v/v LIX 984N was prepared in a suitable diluent and used in a
accurately as possible. If need be, additional shakeouts might
series of shakeouts with the leach solution and the expected strip
be required at O/A ratios that will generate points in the desired
solution. The organic was first contacted at an organic to aqueous
area of the curve. These samples should be analyzed in a block
volume ratio (O/A) of about 1 with the leach solution by vigorous
along with the previous samples to eliminate analytical
shaking in a separatory funnel for about 3 minutes. The aqueous
variations.
16

Figure 1: Extraction Isotherm Figure 2: Strip Isotherm

5.0 60

4.0 50

Aqueous g/L Copper


Organic g/L Copper

3.0 40

2.0 30

1.0 20
0 0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Aqueous g/L Copper Organic g/L Copper

Table 1: Equilibrium Isotherm Extraction Data Table 2: Equilibrium Isotherm Stripping Data

O/A Organic Aqueous O/A Organic Aqueous


(g/L Cu) (g/L Cu) (g/L Cu) (g/L Cu)

10/1 2.04 0.07 10/1 1.76 51.3

5/1 2.28 0.09 5/1 1.38 43.2

2/1 2.96 0.17 2.5/1 1.21 37.7

3/2 3.26 0.26 1/1 1.07 33.8

1/1 3.70 0.51 1/2 1.01 32.3

1/2 4.19 1.24 1/4 0.98 31.2

1/4 4.35 1.94


LO 3.90

SO 1.80 SE 30.7

Leach Solution 2.50


17

The strip isotherm is then determined as follows: steps representing the staging. Draw a horizontal line from the point
where the operating line intersects the vertical leach solution line to
LO is contacted at various O/As (Typically 10/1 to 1/4) with a the extraction isotherm and then draw a vertical line down from the
typical copper electrolyte from an electrowinning tankhouse. This intersection point of the horizontal line with the isotherm to the
is known as strip electrolyte (SE) or lean electrolyte (LE). In our operating line creating a step. Repeat the process by adding another
example, we have taken a LE containing 30.7 g/L Cu and 190 horizontal line and another vertical line as illustrated in Figure 3 to
g/L sulfuric acid. create a second step which completes the McCabe-Thiele diagram
The organic and aqueous phase are contacted by vigorous for a two stage extraction circuit. Each step represents a single stage
shaking or mixing. The temperature in stripping is typically higher of extraction. This diagram would predict that it is possible to achieve
than in extraction, 3040C, so contacts should be carried out a raffinate of 0.22 g/L of Cu and a LO containing 4.30 g/L of Cu
in temperature controlled jacketed vessels. (Figure 3) with two stages of extraction.
After equilibration, the phases are allowed to settle, samples of
each phase taken and filtered, and then analyzed for copper. Figure 3 does not represent a McCabe-Thiele diagram at true
The data is summarized in Table 2 and plotted in Figure 2. equilibrium. If the diagram represented true equilibrium, the operating
line would intersect with the SO line and the isotherm line at the point
Isotherms are specific for the conditions under which they are where the isotherm line intersects the SO line. The construction of a
determined. Changing one of the parameters, i.e., the reagent McCabe-Thiele diagram at true equilibrium is an iterative process.
concentration, the copper concentration of the aqueous phase, the Assuming that the O/A flow ratio remains unchanged, one would
pH of the leach solution, the acid concentration of the strip solution, draw a new operating line parallel to the first operating line starting
temperature1, etc., will result in a different isotherm. In most cases, from a point approximately one half the distance from the isotherm
small changes in one or two of the parameters result in such small line to the raffinate line. One would then draw in the steps as
changes that it would not necessitate generating a second isotherm. described above. In this particular case, the second iteration step is
all that is required to produce a McCabe-Thiele diagram (Figure 4)
that is essentially at equililbrium. It predicts a raffinate of 0.15 g/L of
McCabe-Thiele Diagrams
Cu and a LO of 4.17 g/L of Cu.
Properly generated extraction and stripping isotherms represent
equilibrium conditions and, as such, predict the best extraction and
stripping which can be obtained. These isotherms can be used to
establish the performance that can be expected with a given staging.
Figure 3: McCabe-Thiele Extraction Isotherm
As an example, consider the extraction isotherm in Figure 1 and
First Approximation
assume:

5.0
The SO entering the last extraction stage contains 1.80 g/L Cu.
The leach solution contains 2.50 g/L of Cu.
LO
The advance flow rates of both SO and leach solution are equal
4.0
(O/A = 1).
Feed = 2.50 g/L Cu
Organic g/L Copper

Draw a horizontal line which intercepts the Y axis at 1.80 g/L Cu


representing the Cu content of the stripped organic and then a 3.0

vertical line intercepting the X axis at 2.50 g/L of Cu representing the


Cu content of the aqueous leach solution. Next add the operating
line. The operating line has a slope which is the inverse of the 2.0 SO
organic/aqueous flow rate. In this case, the slope of the operating
line is 1. Add the operating line by drawing a line with a slope of 1
from the point where the extraction isotherm intersects the horizontal 1.0
0 0.5 1.0 1.5 2.0 2.5 3.0
SO line until it intersects the vertical line representing the copper
content of the leach solution. One can then begin to draw in the Raff. = 0.22 Aqueous g/L Copper
18

Figure 4: McCabe-Thiele Extraction Isotherm Iterative Process A line vertical to the x axis is drawn representing the LO. A vertical line
is then drawn from the y axis at 51 g/L of Cu representing the RE to
5.0 intersect with the LO line. A vertical line is then dropped from the
point where the RE line intersects the strip isotherm line to the x axis.
LO This line represents the expected SO (1.77 g/L Cu). A third line is
4.0 then added representing the SE. The operating line is then drawn
Feed = 2.50 g/L Cu
Organic g/L Copper

from the point where the SO line intersects the SE line to the
intersection points of the LO and RE lines. This is the operating line.
3.0 (See Figure 5) The slope of the operating line (20.3/2.13 = 9.50) is
equal to the ratio of the advance organic flow to advance aqueous
flow needed across stripping to obtain the desired RE.
2.0 SO
A two stage McCabe-Thiele strip diagram is constructed in a fashion
similar to that described for the two stage McCabe-Thiele extraction
1.0
diagram. It predicts a SO of 1.12 g/L of Cu when building a RE of 51
0 0.5 1.0 1.5 2.0 2.5 3.0 g/L of Cu and operating at an O/A flow ratio of 7.3/1.

Raff. = 0.15 Aqueous g/L Copper


Number of Extraction/Strip Stages Required

An important decision in developing a design for an SX plant is to


The construction of an equilibrium McCabe-Thiele diagram for one
decide on the staging requirements. The capital cost of a stage must
stage of stripping is very simple. Consider the stripping isotherm in
be weighed against the potential benefits that the stage provides.
Figure 2 and assume:
Consider the use of one stage of stripping versus two stages of
stripping in the example above:
The LO contains 3.90 g/L of Cu.
The desired rich electrolyte (RE) contains 51 g/L of Cu.
Two strip stages will give a SO containing 1.12 g/L of Cu which
The strip electrolyte (SE) contains 30.7 g/L of Cu.
will translate into a net copper transfer on the
organic of 2.78 g/L of copper (LO = 3.90 g/L Cu minus
SO = 1.12 g/L Cu).
One strip stage will give a SO containing 1.77 g/L of Cu which in
Figure 5: McCabe-Thiele Strip Isotherm Single Stage
turn leads to a net copper transfer of 2.13 g/L Cu.
Due to differences in net copper transfer, a circuit operating with
60
one strip stage will require a reagent concentration approximately
Loaded Organic = 3.90 g/L Cu

1.3 times higher than in the case of a circuit with two strip stages
RE
in order to achieve equivalent performance in terms of copper
50
recovery in extraction.
Aqueous g/L Copper

The expected reagent losses will be about 1.3 times higher for the
1 strip stage plant as compared to the 2 strip stage plant.
40 Comparison of the capital costs for the additional strip stage
versus the increased operating costs due to the increased
SE
reagent usage allow one to make a purely economic decision on
30 the strip stage requirements.

SO = 1.77 The increased reagent concentration needed with one strip stage
20 compared to having two strip stages will depend on the nature of the
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
leach liquor, the desired copper recovery and the particular reagent
Organic g/L Copper under consideration.
19

Continuous Copper SX Circuit

With the development of modern reagent technology, most When at equilibrium, the analysis for copper and acid do not change
companies elect to treat dump leach liquors in SX plants consisting as the circuit runs so long as the flows, the composition of the leach
of two stages of extraction and one stage of stripping (2E-1S plants). solution, the composition of the SE, and the nature of the organic
To determine how such a plant might actually function, a 2E-1S phase do not change.
circuit was set up in the laboratory and operated at the advance O/A
determined in the McCabe-Thiele diagrams in Figure 4 and Figure 5. In order to balance metal and acid values, accurate solution analyses
A mixer retention time of 2.6 minutes was selected simply because and solution flow rates have to be known. In addition, solution
most copper SX plants operate with 23 minutes of mixer retention samples should be taken from the rear of the respective settler for
depending on the leach solution conditions, the mixer design, and that stage. When possible, it is best to pull the samples at those
the company operating philosophy. points easiest to access and least likely to upset the circuit.

To achieve good metallurgical results and maximize the amount of The circuit behavior will reflect the interdependence of the extraction
information collected, several things are important: and stripping operations. For example, a loss of stripping efficiency
will result in a higher copper content on the stripped organic which in
Flow rates must be accurately set and continually monitored. turn will result in less available reagent for extraction and which will
Small changes result in fluctuations in the circuit performance lead to higher raffinates. To compensate for a loss in stripping
requiring additional time to achieve equilibrium. efficiency, one must operate the circuit with either a slightly higher
Proper mixing requires that mixer dispersions be maintained at reagent concentration or a slightly higher organic to aqueous
an O/A near 1. advance ratio in extraction in order to maintain copper recovery.
Recycles should be employed where necessary to maintain Alternatively, one must accept a slightly lower copper recovery.
the appropriate mixer dispersions.
Mixer turbines must turn fast enough to maintain good mixing Metal transfer in an extraction stage is typically between 85% to
and pumping action but slow enough to avoid causing heavy 95% of theoretical while metal transfer in a strip stage is usually
entrainment. >95% of theoretical in modern plants due to the improvements in
The circuit should be sampled frequently and the samples must mixer design. As a result, the values predicted by equilibrium
be rapidly and accurately analyzed shortly after collection. McCabe-Thiele diagrams for the aqueous and organic phases exiting
This allows the operator to closely monitor the circuit and a given stage are seldom achieved in an operating plant. As an
observe changes in circuit behavior as operating parameters example, compare the organic and aqueous values predicted by the
are changed. McCabe-Thiele diagram in Figure 3 with the values generated in a
After changes in an operating parameter, the circuit should be continuous laboratory circuit using the same aqueous feed solution,
allowed to run until overall equilibrium is once again achieved. organic solution and SE solution (Table 3, Figure 6).

A circuit is at equilibrium when there is a good metal balance and a The circuit achieved a raffinate of 0.28 g/L Cu and a loaded organic
good metal-acid balance across the whole circuit as well as across of 4.08 g/L Cu as compared to the raffinate of 0.22 g/L Cu and a
each stage: loaded organic of 4.24 g/L Cu as predicted by the first iteration
At equilibrium in extraction, the metal extracted from the aqueous McCabe-Thiele extraction diagram (Figure 3). The stripped organic of
phase in an extraction stage in a given amount of time is equal to 1.80 g/L Cu is close to the 1.77 g/L Cu predicted by the McCabe-
the acid equivalent gained by that same aqueous phase in the Thiele strip diagram (Figure 5).
given amount of time and the amount of metal loaded by the
organic in that stage in the same given amount of time.
At equilibrium in stripping, the metal stripped from the organic phase
in a given amount of time is equal to the metal gained and the acid
equivalent lost by the strip aqueous phase in that stage in the same
given amount of time.
20

This brings up a critical point. If the circuit gives different results from Figure 6: McCabe-Thiele Extraction Isotherm Circuit Data
those predicted by the McCabe-Thiele diagram at 100 % of
equilibrium, why should one do all of the work required to generate 5.0
the McCabe-Thiele diagram in the first place? There are a number of
good reasons: LO
4.0

Feed = 2.50 g/L Cu


Organic g/L Copper
Generating an isotherm helps to develop a feel for the system.
The isotherm will usually reflect any unusual metallurgical
behavior characteristics of the system. 3.0
While not typically observed in Cu systems, the overall shape
of the isotherm may be more S shaped than the smooth curve
shown when extracting other species with extractants such as 2.0 SO
amines. For example, this may reflect changes in the nature of
the extracted species depending on changes in the
composition of the aqueous depending on degree of
1.0
extraction. 0 0.5 1.0 1.5 2.0 2.5 3.0

Raff. = 0.28 Aqueous g/L Copper


In addition, a good idea of the actual circuit results can be obtained
by drawing in the operating line as previously described for Figure 3.
Instead of drawing in the horizontal and vertical lines to represent
100% of equilibrium, draw the horizontal lines in to represent only
Table 3: Circuit Profile Data with 8.7% v/v LIX 984N
95% efficiency as shown in Figure 6. The resultant McCabe-Thiele
in Escaid 110
two stage extraction diagram predicts a raffinate of 0.28 g/L Cu, a
value identical to that achieved in the circuit run.
Sample Organic Aqueous
The feed chosen for the above example is typical of the leach solution
generated by many copper leach operations and represents one of
g/L Cu g/L Fe g/L Cu g/L Fe
the simplest feeds to treat. Copper recovery is very good, selectivity
for copper over iron is high (A copper to iron of about 1,100/1 on a
transfer basis was achieved in the circuit.) and there is little tramp
metal contamination. More complicated feed solutions are evaluated Extraction 4.08 0.002 1.31
in a similar fashion as described in the above example. The extraction Stage 1
and strip isotherms as well as the circuit staging can, however; be
significantly more complex. With complex metal extraction systems,
Extraction 2.88 0.0038 0.28
the initial circuit may have to be modified several times before the
Stage 2
best recovery scheme is worked out.

Strip Stage 1.80 N.D. 51.2 0.026

LE 30.7 0.010

Aqueous Leach 2.50 1.30


21

4. C
 opper Extraction
from Ammoniacal Solution

The use of ammonia as a leaching agent for copper has been Increasing the ammonia concentration in the aqueous shifts the
practiced on a commercial scale since the early 1900s. In 1916, equilibrium to the right. Ammonia competes with the reagent
Kennecott Copper Company and Hecla Mining Company began to for the metal ion. As illustrated by the ammonia isotherms, extraction
recover copper from gravity plant tailings using an ammoniacal leach. decreases as the ammonia concentration increases. This suggests
The copper was recovered as a copper oxide precipitate after that under some circumstances one might be able to strip the metal
stripping the ammonia from the solution with steam. Ammonia has from the loaded reagent with high concentrations of ammonia.
been used to leach copper from native copper ores, copper oxide
ores and copper sulfide ores including chalcopyrite1,2,3. The use of The ammonia isotherms in Figure 1 show that copper(II) is more
ammonia for the leaching of copper from ores has a number of strongly extracted from an ammoniacal solution than is nickel (II)
advantages: suggesting that it should be possible to selectively extract copper
away from the nickel. The feasibility of such a separation was
It is more selective. demonstrated using LIX 65N8. An alternative separation scheme is
Metals such as iron and manganese are not soluble in the leach suggested by considering the LIX 84-I ammonia isotherms and pH
liquor. isotherms. While copper and nickel are relatively strongly extracted
It can be used to treat ores containing high levels of acid from ammonia by LIX 84-I, the corresponding pH isotherms show
consuming gang and is less corrosive than acid leach systems. that nickel is readily stripped at a pH of 2.53.0 where copper is
It is also well suited for recovery of copper from secondary strongly extracted. Co-extraction of nickel and copper with the same
sources such as scrap copper wire, consumer electronics such organic stream followed by a pH controlled wash to remove small
as printed circuit boards, copper drosses, and smelter flue amounts of co-extracted ammonia and then selectively stripping the
dusts1,4,5,6. nickel and copper loaded organic using pH control to give a copper
free, nickel-rich solution and a copper rich solution containing a small
Due to the volatile nature of ammonia, leaching is typically carried out amount of nickel9,10.
in closed vats to minimize ammonia losses1,3. Recent developments
in use of ammonia for heap leaching suggest that it may become Figure 1: Metal Extraction by LIX 84-I as a Function of Total
practical as well7. Ammonia Concentration

General Mills Mining Chemicals division (now a part of BASF Mining 100
Solutions) demonstrated that copper could be extracted from
ammoniacal leach solutions using LIX 63 and introduced it to the
80
industry in 19634. LIX 63, an alpha hydroxy oxime, was quickly
Metal Extraction (%)

Ni Cu
supplanted by LIX 65N, a hydroxy benzophenone oxime, which
in turn has been replaced by LIX 84-I, a acetophenone oxime 60
(Ketoxime). The variation in extractive behavior for LIX 84-I with
copper, nickel and zinc as a function of total ammonia concentration
40
is summarized in Figure 4. The general equation for extraction of a
metal ion(M) in the +2 state from an ammoniacal solution with LIX Zn
84-I (RH) is shown below (Formula 1). 20

0
0 50 100 150 200 250

Ammonia g/L (NH3/NH4+1 = 2/1)

Formula 1

M(NH3)4+2(Aqueous) + 2 RH (Organic) R2M(Organic) + 2 NH3(Aqueous) + 2 NH4+(Aqueous)


22

While the study of pH isotherms, selectivity data and ammonia amounts of entrained aqueous. This will result in transfer of ammonia
isotherms allows the conceptualization of a metal separation and chloride to the strip circuit leading to the buildup of ammonium
flowsheet, it does not provide one with the specific details on how to sulfate and chloride in the strip solution. Both of these chemical
most effectively carry out the separation in the most efficient, cost- species are undesirable. The excess ammonium sulfate must be
wise manner. Laboratory work is still required to determine the disposed of and high chloride levels can lead to chlorine gas
precise extraction and stripping conditions, circuit staging formation in the electrowinning tankhouse. The stripped organic can
requirements, etc. also transfer sulfuric acid to extraction by entrainment leading to
undesirable buildup of ammonium sulfate in the regenerated etchant.
The manufacture of printed circuit boards (PCB) involves selectively Typically, the aqueous phase in the wash stages would be a dilute
etching copper from the board leaving the desired circuit. Ammoniacal acid stream. By coupling the two wash stages as illustrated, a weak
etchants based on either ammonium chloride or ammonium sulfate acid solution can be generated by scrubbing the stripped organic in
are typically used. As the concentration of copper in the etchant W2 to remove the entrained acid and the resultant weakly acidic W2
increases, the efficiency of the etching process decreases. Typically, aqueous can then be fed to W1 where it contacts the loaded organic.
at about 140 g/L of copper, the etchant is considered to be spent. Scrubbing with dilute acid removes the ammonia from the loaded
The spent etchant can then be regenerated for reuse by extraction of organic. The resultant W1 aqueous can then return to W2. This
the copper. This can be carried out on-site or the spent etchant can arrangement results in an efficient use of fresh water for washing and
be sent off to a central treatment facility. The recovery of copper and reduces reagent consumption11,12.
regeneration of the spent etchant by solvent extraction with LIX 84-I
has been practiced commercially for a number of years and BASF Extraction reagents based on ketoxime such as LIX 84-I and LIX
has had previous experience with a number of these operations 84-IT are favored for the recovery of copper from ammoniacal
globally. A typical layout for a PCB spent etchant copper solvent solutions. Copper is strongly extracted by ketoxime from an
extraction plant is shown in Figure 2. ammoniacal solution and is readily stripped with acid resulting in very
high net transfer. The high extractive strength of aldoxime based
Two wash stages are employed to minimize or prevent transfer of formulations is not required to achieve high recoveries and they are
impurities between extraction and stripping. Due to the high not as readily stripped with acid so net transfers are lower. LIX 84-IT
concentrations of ammonia and ammonium ion in the aqueous feed is based on ketoxime modified with a small amount of an ester
solution, co-extraction of ammonia by LIX 84-I will occur. In addition modifier. Addition of a small amount of modifier reduces ammonia
to the co-extracted ammonia, the loaded organic will contain small co-extraction13.

Figure 2: Basic Layout of a PCB Spent Etchant Cu SX Circuit

Loaded Organic
Raffinate
W1 Aqueous

E1 E3 S1 W1

E2 W2 S2

Spent Strong
Spent Etchant Electrolyte Electrolyte

W2 Aqueous
23

5. N
 ickel Extraction from
Ammoniacal Solution

Use of ammonia to leach nickel sulfide ores was first proposed around the beginning of the 20th century.
The first commercial application of ammonia to the leaching of nickel however was the use of the Caron
Process to treat nickel oxide ores in Nicaro, Cuba starting in 19431. This was followed by the startup in
the mid-1950s of the Sherritt Gordon plant in Fort Saskatchewan, Alberta which used a high pressure
ammonia leach to recover nickel from a sulfide concentrate1,2. In 1970 following the development of LIX
65N, a flowsheet was developed by BASF for the recovery of copper and nickel from an electro-refining
tank house bleed stream. After recovery of the copper, the aqueous copper raffinate was neutralized with
ammonia followed by extraction of the nickel. SEC Corporation adopted the technology and operated a
plant successfully for a number of years3. During this same time frame, BASF published a series of
investigations to refine the recovery of nickel from ammoniacal solutions4,5,6. Queensland Nickel
commissioned the first large scale plant to recover nickel from an ammoniacal leach liquor in 1989 using
LIX 87QN, a modified ketoxime specifically developed for this application7,8.

Figure 1: Production of base metal hydroxide intermediate

Gravity concentration/
Ore pretreatment cyclone/scrubbing

H2SO4 Fe(SO4)2 disproportionates to


Autoclave acid leaching Fe2O3 and H2SO4, Ni, Cu, Co and
Sulfur, steam
Zn leach as sulfates. Cr is Cr2+.

S
Tails CCD
L

Air Hydroxide Precipitation and


CaO or MgO precipitation pH 5.0 removal of iron

Reject or S
recycle to leach L

MgO is the preferred alkali as it


Hydroxide permits use of an ammonium
MgO or CaO
precipitation pH 9.0 carbonate leach. CaO requires
an ammonium sulfate leach.

Rejection of S
Mn2+, SO42+, Cr2+ Belt filter
L

Base metal hydroxide To ammonia


filter cake intermediate leach and SX-EW
24

With the increased interest in the recovery of nickel from laterite ores and The refinery portion (Figure 2) of the process includes:
drawing on its experience in extraction of nickel from ammoniacal
solutions, BASF conceptualized a flowsheet for the recovery of nickel Re-leach of the Mixed Metal Hydroxide Precipitate (MHP) with
from laterite ores. This flowsheet was further developed and implemented ammonia under oxidizing conditions.
by Cawse Nickel Operations9. The basic elements of the front half of the Solvent extraction of the nickel with a ketoxime,
Cawse process (Figure 1) are: LIX 84-INS.
Recovery of nickel cathode.
High Pressure Acid Leaching (HPAL) of the laterite ore. Recovery of cobalt from nickel raffinate by precipitation of cobalt
Solid-Liquid separation. sulfide which can be further refined into high purity cobalt metal.
pH adjustment to remove iron.
Further adjustment of pH to precipitate the base metals
(Ni, Cu, Co, Zn) as crystalline hydroxides.

Figure 2: Ammonia Re-Leach-LIX 84-INS Nickel SX-Electrowinning

Base metal hydroxide


filter cake intermediate

Air/O2
Ammonia leaching
NH3/CO2

S
To acid leach
L

Steam stripping Steam stripping to remove


Steam/air free ammonia and to help
and oxidation
oxidize Mn and Co

Reject or return S Clarification to remove MnO


to acid leach L and other suspended solids
Peroxide to oxidize
all Co2+ to Co3+

Raffinate to Co Nickel SX extraction


recovery H2S PPT with LIX 84-INS

Loaded organic wash


Zn and NH3 removal
Organic bleed
to Co and Cu strip
and reoximation
Nickel electrowinning Nickel stripping

Stripped organic wash


25

The Cawse flowsheet possesses a number of advantages relative to A schematic of the Cawse SX plant is shown in Figure 39. The
other proposed flowsheets for treatment of laterite ores9. They chemistry of extraction and stripping is summarized in the following
include: equations (Formula 1).

Process has been industrially proven having produced Figure 3: Schematic of Cawse SX plant
8,000 ton/year of nickel cathode.
The MHP can either be sold to other nickel producers or further
treated to produce high purity nickel cathode and cobalt sulfide. PLS Raffinate Wash Aq
The MHP can be stockpiled allowing a steady feed to the nickel
refinery portion of the plant when the HPAL is not operating.
E1 E2 E3 SOW
The combination of the hydroxide precipitation step followed by
ammonia re-leach is largely selective for Ni, Co, Cu, and Zn while
rejecting troublesome Mn and Cr. Dil. acid wash Aq.
Use of MgO for the hydroxide precipitation minimizes gypsum
formation downstream from the re-leach of the MHP.
LOW 1 LOW 2
The nickel concentration of the ammonia leach solution can be
controlled (Typically 1020 g/L Ni) to minimize the size of the
nickel SX plant.
Final products are readily marketable high purity nickel cathode
or nickel sulfate and cobalt sulfide. S1 S2 S3 S4
Ammonia is recycled resulting in low ammonia consumption per
ton of nickel produced.
Overall metal recovery is very high due to recycling of
Nickel Electrowinning
intermediates
Process employs only one SX circuit and one extractant type
removing the potential for cross contamination of the circuit
organics.

Formula 1

Extraction 2 RH(Organic) + Ni(NH3)4+2 (Aqueous) R2Ni(Organic) + 2 NH3(Aqueous) + 2 NH4+(Aqueous)

Stripping R2Ni(Organic) + H2SO4 (Aqueous) Ni+2(Aqueous) + SO4-2(Aqueous) + 2 RH(Organic)


26

Successful operation of an ammoniacal nickel SX circuit must take Use conservative settler design, settler flux of 34 m3/
into consideration a number of factors: m2/hr in extraction and 35 m3/m2/hr in stripping, with aqueous
continuous mixing in all stages.
As nickel is extracted, the concentration of ammonia and Use S1 to consume excess acid in aqueous and control pH of
ammonium ion in the aqueous phase increases, effectively rich electrolyte at 3.04.0.
limiting nickel transfer into the organic phase. Use wash stages to remove ammonia/ammonium ion from the
Copper, zinc, cobalt and manganese are typically present in the loaded organic and entrained acid from the stripped organic.
MHP ammoniacal re-leach liquor and will co-extract with the Use 57 minute mixer retention times in stripping and operate
nickel. Cobalt(+2) and manganese(+2) will be converted to higher at 5060C.
oxidation states on the organic making them difficult to strip and Increase extraction mixer retention times slightly when using
resulting in a buildup in concentration over time poisoning the ammonia/ammonium sulfate leach conditions.
organic. Analytical methodology for measurement of ammonia transfer on
Due to the nature of the organic and ammoniacal solutions, the loaded organic, determination of cobalt(+2) concentration in
interfacial tension is quite low relative to the interfacial tensions leach liquor, and determination of the concentration of sodium
observed when extracting copper from acidic sulfate solutions. lauryl sulfate in electrolyte.
Nickel electrowinning limits the pH of the incoming rich
electrolyte to 3.04.0. The treatment of ammoniacal leach solutions containing higher
Ammonia and ammonium ion can be transferred to strip by both copper concentrations than those normally seen in laterite processing
entrainment and chemical loading such as those generated by autoclave leaching of nickel sulfide
Potential for formation of metal amine sulfate salts which may concentrates has been proposed9. Use of pH controlled selective
precipitate in lines or alter chemistries in some fashion. stripping of nickel and copper have shown in the laboratory that a
Nickel stripping kinetics are slow. high purity nickel strip solution containing up to 150160 g/L of
Choice of MHP re-leach solution impacts extraction kinetics. nickel could be obtained13,14.

The technology developed by BASF to address these points


with regard to nickel recovery from ammoniacal leach solutions
includes9,10,11,12:

Control MHP leaching to generate a solution containing


1218g/L nickel followed by steam stripping to reduce the
ammonia content to 2040 g/L.
Depending on copper concentration, treat bleed stream of
stripped organic to control copper level on organic or
alternatively use pH controlled selective strip to recover both high
purity copper and nickel13,14. Maintain oxidizing conditions in
leach to maintain cobalt and manganese in higher oxidation
states which will not load on organic. Employ reductive strip to
remove cobalt and manganese from organic phase coupled with For further information concerning the extraction of nickel from
re-oximation to re-generate oxime hydrolyzed under reductive ammoniacal solutions contact your nearest BASF Mining Solutions
strip conditions. representative.
27

6. B
 ASF Alamine and
Aliquat Reagents

BASF offers a series of tertiary amines (Alamine reagents) and a Table 1: Alamine and Aliquat Extractants
quaternary amine (Aliquat 336) (Table 1) for metal extraction. The R
groups are alkyl hydrocarbon chains which may be branched or
Alamine Reagents
straight chain and which may contain differing numbers of carbon
atoms. Tertiary amines are basic due to the presence of a lone pair of
electrons on the central nitrogen atom. While other types of amines
are known, the tertiary amines find the widest use in metal recovery Alamine 308 R = Iso octyl (Highly Branched C8 Chain)
processing by solvent extraction. BASF currently offers three
Alamine reagents for metal solvent extraction applications but has
Alamine 336 R = Mixed C8 and C10 (Straight Chain)
the capability to produce other tertiary amines if the need should
arise. Aliquat 336 is derived from quaternization of Alamine 336
with methyl chloride. Alamine 304 R = C12 (Straight Chain)

Tertiary amines have the Aliquat 336 has the


general formula: general formula:

R R
Aliquat Reagent

R N R N+ CH3 CI

R R Aliquat 336 R = Mixed C8 and C10 (Straight Chain)

The tertiary amines and quaternary amine are examples of the ion The extent to which the protonated amine will exchange one anion
pair class of extractants. Protonation of the tertiary amine results in for another is dependent on the relative affinity of the two anions for
formation of an organic ammonium cation which then forms a the organic ammonium cation and the relative stability of the two
hydrocarbon soluble ion pair with an anion as illustrated in the anions in the aqueous phase (Formula 2). Typically, extraction favors
following equations (Formula 1). larger anions having a low charge density over smaller anions which

Formula 1

R3N(Organic) + HA(Aqueous) R3NH+A-(Organic)

Formula 2

R3NH+A-(Organic) + B-(Aqueous) R3NH+B-(Organic) + A-(Aqueous)

Formula 3

2 R3NH+B-(Organic) + Na2CO3 (Aqueous) 2 R3N(Organic) + 2 NaB(Aqueous) + CO2 + H2O


28

have a high charge density. The selectivity of extraction will also be Alamine 304 is tridodecyl amine. Its major applications are:
influenced to some extent by the relative amounts of the two anions Recovery of molybdenum from acidic sulfate leach liquors
in the aqueous solution. While the choice of stripping agent depends Extraction of organic acids such as citric acid from fermentation
on the overall recovery process, there are two approaches that can broths8
be used to recover the extracted anion from the organic phase when
using amines. The first is to crowd the desired anion off the organic Aliquat 336 is tri(n-C8, C10 alkyl) methyl ammonium chloride.
phase by contacting the organic with a concentrated aqueous Its uses include:
solution of another anion such as chloride. Alternatively and most Recovery of molybdenum from acidic sulfate leach liquors
typical, the amine is deprotonated by contacting it with an aqueous Recovery of vanadium(+5) from acidic leach liquors
solution of a base such as sodium carbonate as illustrated in For Rare earth separations9
mula3. Removal of arsenic from copper refinery electrolytes10

Stripping with a base typically results in the best stripping and in the In general, any metal capable of forming an anionic complex in an
fewest number of strip stages. In some cases, changes in pH will aqueous solution is a candidate for extraction by tertiary or quaternary
result in changes in the nature of the extracted anionic species amines. Figure 1 summarizes some extraction data for Alamine 336
making stripping more favorable. For example, polymolybdates and/or similar amines for a wide variety of metal aqueous systems11.
which are strongly extracted on the acid side are converted to Oak Ridge National Laboratory has carried out an extensive series of
molybdate at pHs greater than 8.0, which is much less strongly studies with regard to the effect of chloride concentration and pH on
extracted than the polymolybdate. extraction of various elements as their chloride complexes by amines
or quaternary amines12. Figure 1 summarizes the extraction isotherms
The chemistry of extraction and stripping with Aliquat 336 differs for a number of metals as a function of chloride concentration in the
from that of the tertiary amines due to the fact that the quaternary aqueous at pH 2 and 40C.
amine functionality is always positively charged. While the same
considerations of anion size and relative charge determine the relative Figure 1: Extraction Isotherms for Alamine 336 as a Function
ease of extraction of different anions, extraction of anions is not pH of Choride Concentration (pH = 2, 40C).
dependent as it is with the tertiary amines. This can be used to
advantage in some instances such as recovery of a metal from a 100
Mo
basic leach solution. The biggest disadvantage to using a quaternary
Zn Cu
amine type extractant is that it will not deprotonate so it is necessary
80
to use crowding with high concentrations of another anion as a Fe2+
Fe3+
stripping strategy. Co
Extraction %

60
Alamine 308 is a tri-isooctyl amine. Its primary application is:
Separation of cobalt from nickel in acidic chloride systems1,2
40
Recovery of zinc from spent electrolyte solution3 Sn

Alamine 336 is a tri(n-C8, C10 alkyl) amine. 20


Principle applications are: Mn Ni, Cr
Recovery of uranium from acidic sulfate leach solutions
0
Recovery of molybdenum from acidic sulfate leach liquors 0 100 200 300
Recovery of vanadium(+5) from acidic leach liquors
[CL], g/L.
Extraction of tungsten from acidic liquors4
Separation of molybdenum and rhenium5
Recovery of gallium from acidic chloride solutions6
Extraction of gold from acidic thiocyanate leach liquors7
29

Figure 2: Survey of Extraction by High Molecular Weight Tertiary Amines

Li Be B C N O F

Na Mg Al Si P S Cl

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 c 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 5871 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 90103 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No 103

IV V VI VI 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 0.1 M amine from the acid systems shown below:

aHNO3 dH3PO4 gCOOH2 jNH4SCN lHBr

bHCI eHF hLiCI, LiCI, LiCIHCI, CsCI kH2CrO4 mHI

cH2SO4 fCH3COOH ivarious organic acids

(a) Taken from Standard Methods of Chemical Analysis, Volume II A, Sixth Edition, page 190. Van Nostrand Reinhold Company, 1963.
30

Development of a Separation Process

While development of a separation process based on chelating extracted at chloride ion concentrations of 150
200 g/L.
reagents such as the LIX oximes is somewhat straight forward due Furthermore, iron(+3) is still strongly extracted at 50 g/L chloride ion.
to the constraints imposed by the chelation chemistry, amine systems Given these points, one can expect to develop an excellent separation
tend to be more complicated due to: of these metals by first dissolving the mixture into a concentrated
hydrochloric acid solution, oxidizing the iron to the +3 state, co-
The large number of aqueous anionic systems where an amine extracting the cobalt(+2) and iron(+3) with an amine while leaving the
extractant might be applicable. nickel(+2) in the original aqueous solution. The cobalt can then be
Protonated amines and quaternary amines must be paired with selectively stripped off the loaded organic by water. This flowsheet
an anion to maintain charge neutrality in the organic phase which has been studied in a BASF laboratory. Several slightly different
often results in poor selectivity depending on the relative flowsheets for this separation have also been reported13,14. The best
amounts of amine or quaternary amine relative to the targeted choice of flowsheet is dependent upon the relative amounts of
species. cobalt, nickel and iron present.
The large number of potential stripping agents as compared to
copper loaded oximes where stripping with sulfuric acid is the Often, the complex of the protonated amine or quaternary amine
standard. cation with the extracted anion may have only limited solubility in a
The pH, the metal oxidation state and the effects of typical hydrocarbon diluent resulting in the formation of a third phase
concentration of the anionic complexing agent all have an impact and/or phase separation problems. A third phase is a viscous layer
on the chemical behavior of the system. that typically collects at the interface. It is primarily composed of the
precipitated complex. Due to the ionic nature of the complex, the
Development of amine systems can be more of an art form rather third phase is highly polar which makes it a very good solvent for
than a science. Any investigation of a potential separation process polar materials such as the free amine or quaternary amine. The free
should start with a laboratory program whose goal is to develop the extractant (amine or quaternary amine) will distribute from the
best conditions for extraction, stripping and final product recovery hydrocarbon diluent into the third phase resulting in a rapid loss of
consistent with the overall metallurgical flowsheet. loading capacity and net transfer. Addition of a solvation modifier
(phase modifier) such as a long chain alcohol, e.g., isodecanol,
The development of a separation process for cobalt, iron and nickel isotridecanol; to the organic phase is normally employed to prevent
from an acid chloride solution illustrate the importance of the factors third phase formation and /
or phase separation problems.
cited above. Figure 1 shows that nickel(+2) is only slightly extracted Replacement of at least a portion of the hydrocarbon diluent with a
at greater than 200 g/L chloride ion while cobalt(+2) and iron(+3) are high aromatic diluent may also be employed.

For additional information regarding BASF amines and quaternary


amine reagents, contact your local BASF Mining Solutions technical
representative.
31

7. Extraction of Uranium

In 1957, the Mining Solutions unit of BASF (which in part originated Figure 1: General Chemistry of Uranium Processing
from the General Mills Mining Chemicals Division) introduced
Alamine 336, tri(octyl, decyl) amine, to the mining industry for the
H2SO4 UO2 + Fe3+ UO22+ + 2Fe2+
recovery of uranium by solvent extraction from acidic sulfate leach
LEACHING UO2+ + 3H2SO4 UO2(SO4)34- + 6H+
liquors. Alamine 336 was quickly accepted by the industry with the
first application occurring in 1958 with the startup of the Kerr McGee
uranium mill at Grants, New Mexico, USA1. At the peak of the uranium Solvent Pre-protonation
industry in the late 70s, approximately 80% of the production in the Extraction 2 R3N(Organic): + H2SO4(Aqueous)
USA used the Alamine 336 solvent extraction flowsheet. It was this (SX) (R3NH+)2S04-2 (Organic)
ongoing involvement in the uranium industry that eventually led to the
conceptualization and development of the phenolic oximes for the Extraction
recovery of copper from acidic leach liquors. The hydrometallurgical UO2(SO4)34- + 2 (R3NH+)2SO4-2
processing of uranium has been extensively reviewed2,3,4,5. (R3NH+)4UO2(SO4)3-4(Organic) + 2 S04-2(Aqueous)

The general chemistry for the processing of uranium through leaching Stripping
with dilute sulfuric acid, solvent extraction and precipitation to yield (R3NH+)4UO2(SO4)3-4(Organic) + 4 NH4OH(Aqueous)
high grade U3O8 is summarized in Figure 1. Sulfuric acid leaching of 4 R3N(Organic) + (NH4)2UO2(S04)2(Aqueous) +
uranium ores is carried out under oxidizing conditions at a redox (NH4)2S04(Aqueous) + 4 H2O
potential of 400500 mV relative to a saturated calomel electrode.
While ferric ion is the primary oxidant, oxidants such as manganese
Yellowcake Precipitation
dioxide, sodium perchlorate or hydrogen peroxide are employed to
Production 2 (NH4)2UO2(SO4)2 + 6 NH4OH
convert ferrous ion to ferric ion. Under these conditions, uranium is
(NH4)2U2O7 + 4 (NH4)2SO4 + 3 H2O
converted to the +6 valence state and is solubilized as the anionic
uranyl di-sulfate or tri-sulfate complexes. After clarification to remove
Calcination (Heat > 580C)
residual solids, the leach solution is contacted with an organic phase
(NH4)2U2O7 + heat 2U3O8
consisting of Alamine 336, an alcohol such as isodecanol or
isotridecanol as a solvation modifier, and a suitable hydrocarbon
diluent. The alcohol is typically present at about 50 % of the
concentration of the amine. Often, prior to extraction, the organic
phase is contacted with a dilute solution of sulfuric acid to pre- of ammonia addition is required. The presence of excess ammonia
protonate the amine and load the organic with sulfate or bisulfate. will result in the precipitation of ammonium diuranate in the mixers
This ensures that the amine will be protonated in extraction, the pH resulting in crud formation and operational problems. After stripping,
of the aqueous phase will remain approximately constant since no additional ammonia is added to the pregnant strip solution to
acid extraction will occur, and will help to maximize selectivity for precipitate the uranium as ammonium diuranate (ADU). After filtration
uranium. In extraction, the sulfate/bisulfate anion is exchanged for and drying, the ADU is calcined to produce high purity (99% or
an anionic uranyl sulfate complex. Uranium extraction is an anion greater) U3O8.
exchange process. Depending on a variety of factors, there is the
potential for competitive extraction by other anions present in the The process described above involving direct solvent extraction of
leach liquor. To achieve the desired uranium purity, a number of the uranium from the dilute acid leach solution is often described as
scrubbing stages as illustrated in Figure 2 may be employed in the the Amex process (Figure 3) or the Purlex process. An alternative
solvent extraction circuit to remove these unwanted anions from the flowsheet involves pre-concentration of uranium by use of an ion
organic phase and prevent their transfer to stripping. exchange resin followed by extraction of the uranium from the resin
eluate solution with an amine. This is referred to as the Eluex process
Stripping of the loaded organic can be carried out with ammonia, (Figure 4) (Bufflex process in South Africa). The Eluex process takes
strong sulfuric acid solutions, sodium chloride or nitrate solutions. advantage of the use of relatively non-selective ion exchange resins
The use of ammonia/ammonium sulfate is a preferred option6,7,8,9. to treat very dilute solutions to generate a much more concentrated
Stripping is carried out by pH controlled addition of ammonia gas or solution of uranium and then use of the more selective amine solvent
ammonium hydroxide solution to each strip stage10,11. Careful control extraction process to recover a purer uranium concentrate1,12.
32

Figure 2: Typical Uranium SX circuit for Recovery from Acidic Sulfate Leach Liquors12,13

Uranium PLS Raffinate


Extraction

E1 E2 E3 E4

to PLS H2O H2SO4 NH3/(NH4)2SO4 H2O


Organic or leach
scrubbing Loaded
organic Sc1 Sc2 Sc3 Sc4

Uranium
Stripping S4 pH 4.8 S3 pH 4.0 S2 pH 3.8 S1 pH 3.3

NH3

L ADU HX
S precipitation 3040C
Barren strip liquor Liquor
to calciner
regeneration protonation Barren
pH ~11.0 pH ~1.0 organic
Na2CO3/NaOH H2SO4

Each uranium leach, ion exchange and /


or solvent extraction aqueous solution at the organic-aqueous interface triggering
operation is somewhat unique due to differences in the pregnant polymerization of the soluble silica to higher molecular weight
leach solution stemming from the ore and gangue mineralogy, silica species. In addition to reducing the incoming
site water quality, and site specific water balance issues. These solids/soluble silica levels, operating the plant using organic
differences can give rise to a variety of operational challenges 13,14,15,16: continuous mixing will help to minimize crud formation. In
extreme cases where high levels of solids or soluble silica is
Crud Formation present in the incoming feed, the plant operators may elect to
Typical solvent extraction plant design specifications target less by-pass or shut down the solvent extraction process until the
than 20 ppm of solids in the incoming pregnant leach liquor. pregnant leach solution returns to normal.
Incoming solids can interact with the organic phase in the mixer BASF offers a broad product range of floculants and
to form a solid stabilized emulsion, crud. Depending on the coagulants as well as technical expertice to assist plant
level, 100s to 1000s of ppm, and nature of the solids, some operators in solving pregnant leach liquor clarification issues
crud will be formed. In cases where crud formation is mild, it as well as reduce soluble silica levels.
may be responsible for transfer of impurities to final product. In
severe cases, it may result in the need to shut down the plant Poor phase disengagement
and clean out the accumulated crud and solids. The presence Poor phase disengagement can arise from a number of
of dissolved species such as silica may also contribute to crud sources. Many uranium ore deposits contain a range of
formation. The soluble silica can be converted to insoluble silica organic substances such as humic acids. Under the oxidative
precipitates due to changes in the chemical nature of the conditions of the leach, these materials can be converted to
33

carboxylic acids and organic sulfates which are surfactant-like from the vanadium. Once the uranium is recovered, one can
in nature, distribute into the organic phase and build up in adjust the redox potential of the raffinate to about 720 mV at
concentration in the organic phase over time resulting in which point all of the vanadium will be present in the +5
longer phase disengagement times. Carboxylic acids have oxidation state and can be extracted as the polyvanadate.
also been generated by bio-oxidation of the alcohol solvation However, the polyvanadate species are strong oxidants and
modifier and the hydrocarbon diluent. Carboxylic acid will cause degradation of the amine.
contamination of the organic may also result in a reduction of Zirconates will also be co-extracted along with uranium by
uranium from extraction to strip either by reacting with the tertiary amines. Careful control of the scrub stage pH between
amine to reduce extraction capacity or by transferring uranium 2.53.0 as well as use of a bit of uranium to crowd the
from stripping back to extraction. The overall level of these zirconates off the organic will minimize its transfer to strip.
organic contaminants can be reduced by scrubbing a bleed Other contaminants common to uranium circuits can also be
stream of the stripped organic phase with a strongly alkaline controlled using appropriate strategies. A thorough
aqueous carbonate solution (i.e., pH ~1112). understanding of the components in the leach solution is
critical to operating a uranium recovery plant.
Chemical transfer of impurities from extraction to strip.
Under the typical pH of the leach solution, molybdenum will be Amine degradation
present as a polymolybdate anion which is also readily Nitrate is problematic for a couple of reasons. It is preferentially
extracted by tertiary amines such as Alamine 336. Under the extracted over the uranyl sulfate species by tertiary amines
conditions of the ammonia strip, the molybdenum will also and thus suppresses uranium extraction. Under certain
strip and will report to the final uranium product. Depending conditions, the presence of nitrates in the leach solution can
on the pH of the leach solution, its redox potential, and the lead to a high redox potential (550700 mV against standard
presence of other anions such as phosphate, silicate, calomel electrode). Under these conditions, the tertiary amine
arsenate, etc., molybdenum can be present in a number of undergoes very rapid attack by the nitrate and is converted to
reduced polymolybdate or heteropolymolybdate (i.e., the corresponding di-alkyl nitrosamine resulting in loss of
containing Mo5+) species which tend to form complexes with loading capacity and increased phase disengagement
the amine extractant that are poorly soluble in the organic problems. This problem has been most frequently observed in
phase and tend to form sticky third phases or goo which Eluex circuits where the uranium is first concentrated by use of
collect in the settlers at the interface and in the bottoms of the an ion-exchange column. The uranium is then further purified
settlers reducing settling volume. These precipitates may be and concentrated by solvent extraction with a tertiary amine.
orange, yellow, green, blue, or gray in color. The color being The solution has been to control the redox potential to below
dependent on the oxidation state of the molybdenum and 510mV by addition of iron wire to the aqueous weirs in
heteroatoms present . If the formation of these insoluble extraction17,18.
molybdenum third phases is a problem, BASF recommends Tertiary amines are stable to most process conditions such as
the use of Alamine 304-1. The use of diluents having a high acidity and alkalinity at typical temperatures. At temperatures
aromatic content, higher concentrations of alcohol solvation over about 90C, protonated amines will slowly degrade by a
modifiers, and operating at a redox potential high enough to Hoffman elimination type mechanism.
insure that molybdenum is all present in the +6 oxidation state Contact with strong oxidants such as vanadium(+5), hydrogen
will also help to prevent third phase formation. Where sufficient peroxide, etc., will result in oxidative degradation of amines.
molybdenum is present, one can selectively strip the uranium
using an acidified chloride solution and then strip the Acid consuming ores are leached with alkaline carbonate solutions to
molybdenum off the organic using a sodium carbonate solution. generate the uranyl tricarbonate complex. While the uranyl
If vanadium is present, one can selectively recover it by tricarbonate complex can be extracted with Aliquat 336, this
controlling the redox potential of the aqueous. Vanadium(+4) is approach has not been pursued commercially to any large extent14,19.
not extracted by tertiary amines from sulfate solutions while
the vanadium(+5) forms a polyvanadate which is readily Recovery of uranium from copper solvent extraction raffinates by
extracted. At redox potentials below about 600 mV (against solvent extraction with Alamine 336 has also been practiced at BHP
standard calomel electrode), vanadium is present only in the Billitons Olympic Dam Operations and at Anamax Twin Buttes20,21.
+4 oxidation state and the uranium can be extracted away
34

Figure 3: Amex Process Figure 4: Eluex Process

Ore Ore
Sulfuric Acid Oxidant Sulfuric Acid Oxidant

Leaching Leaching
Water Water

S/L Separation Sulfuric


S/L Separation Ammonium Acid
Sulfate
Solids
to tailings
Solids CIX
to tailings SX Ammonium
Sulfate Uranium Barren
Barren Solution
Solution
Solution
Uranium
Rich Solution SX

Uranium Barren
Rich Solution Acid
Ammonia Precipitation
Ammonia
Filtration Precipitation

Tailings Tailings
Filtration

Yellowcake Yellowcake
35

8. E
 xtraction of
Molybdenum and Vanadium

Molybdenum

The primary sources of molybdenum are concentrates derived as Solvent extraction can also provide routes to recover molybdenum
by-products from flotation of copper sulfide ores or directly from from non-traditional sources such as acidic heap and dump copper
molybdenum ores. These concentrates are typically roasted to leach solutions1.
produce a crude molybdenum oxide and a flue dust, which also has
a high molybdenum content. Both can be leached with sulfuric acid The solvent extraction of molybdenum can be a challenging
to produce leach solutions from which molybdenum can be recovered undertaking due to molybdenums complicated and unique chemistry.
via solvent extraction to produce a high purity molybdenum oxide An understanding of the aqueous solution chemistry and solvent
product. Since rhenium is often associated with molybdenum, the extraction chemistry of molybdenum is necessary to successfully
option to recover rhenium using solvent extraction exists as well. operate a molybdenum solvent extraction plant. BASF through its
Molybdenum sulfide concentrates can also be effectively leached predecessor companies has been supplying solvent extraction
using high pressure oxidative leach techniques to produce a feed technology for the recovery of molybdenum since the late 1950s and
solution amenable to processing by solvent extraction. Molybdenum the chemical expertise to understand the unique problems faced by
can also be successfully leached from spent hydrocarbon cracking plant operators when dealing with molybdenum2.
catalysts and recovered using solvent extraction.

Molybdenum Chemistry

Molybdenum can be present as a wide variety of species in an Figure 1: Distribution of molybdenum(+6) species as
aqueous solution3. The oxidation potential of the solution, the nature function of pH
of the other anions and metals that are present as well as their
concentration, the pH of the solution and the concentration of
Isopolymolybdates Mo7O246, Mo8O264
molybdenum all play a role in determining which molybdenum
species are in equilibrium with one another in a given leach liquor.
While molybdenum can exist in a number of oxidation states, it is
predominantly found in the +6 oxidation state in leach liquors derived
from pressure oxidation of concentrates or molybdenum oxide. MoO42

A simplified picture of the primary molybdenum(+6) species of interest


and the pH range over which they form is shown in Figure 1. As the
pH increases from zero to about 1.5, the concentration of the Cationic MoO2+2
molybdenyl cation decrease and the isopolymolybdates become
more important. Between about pH 1.0 to pH 6.0, the Mo7 and the
Mo8 species are of the most interest. At pHs greater than 7.0, the
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
simple molybdate ion predominates. The picture can be further
pH
complicated by the presence of Mo(+5) in the leach liquors. The
presence of other heteroatoms such as P, As, Si, Ti, Zr, and Ge in the
solution can also complicate the chemistry further due to the potential
to form a vast number of heteropolymolybdate species.
36

Molybdenum Extraction

Molybdenum is typically recovered from acidic (pH 1.02.0) sulfate


solutions by extraction with a tertiary amine such as Alamine 336 or
Alamine 304. The chemistry is outlined in Formula 1.

Formula 1

Extraction R3N(Org) + H2SO4(Aq) [R3NH+HSO4-](Org)

Mo8O26-4(Aq) + 4 [R3NH+HSO4-](Org) [(R3NH+)4Mo8O26-4](Org) + 4 HSO4-(Aq)

Stripping [(R3NH+)4Mo8O26-4](Org) + 12 OH-(Aq) 8 MoO4-2 + 4 R3N(Org)+ 8 H2O(Aq)

Due to the fact that polymolybdates are strongly extracted from acidic Figure 2: Mini plant circuit
sulfate leach liquors by tertiary amines allowing one to operate at very
high percentages of molybdenum maximum loading, recoveries are
Feed Rafnate
typically very high in 2 to 3 counter current stages of extraction. Stripping Spent Wash
0.06 g/L 5.56 g/L 0.05 g/L

is accomplished by contacting the loaded organic with ammonia. Very


high concentrations of molybdenum, up to 100 g/L, can be achieved Wash
Water
0.15 g/L 0.07 g/L

in the strip liquor in 1 to 2 stages of stripping using a concentrated W1 E1 E2 E3


ammonia solution and maintaining the pH in stripping between 9.0 to pH 1.5
6.21 g/L 0.69 g/L 0.54 g/L
9.5. The results of a mini plant circuit run in a BASF laboratory is shown
in Figure 2.
Washed SO
0.03 g/L
The feed solution was derived from leaching a flue dust with sulfuric
acid to generate a feed containing 5.56 g/L of molybdenum and LO
6.28 g/L 0.04 g/L 0.03 g/L

Surge S1 S2 W2
3537 g/L of free residual acid. The organic phase consisted of 2%
w/v Alamine 336 in Aromatic 150, a 100% aromatic diluent. Note that p H 9 .7 p H 9 .3 5
64.0 g/L
97.3% recovery of molybdenum was achieved in E1 and 99.1% Spent Wash
1.3 g/L
recovery overall indicating that no more than 2 stages of extraction are Rich Strip Liquor NH 3 Strip Soln
78.2 g/L 65 g/L Wash Water
required in this case. Stripping was highly efficient with 99.4% stripping
achieved in S1.
37

Molybdenum Solvent Extraction


Technical Challenges

One of the more prevalent problems that molybdenum solvent As noted earlier, heteropolymolybdic acids will form species such as
extraction plant operators face is the formation of third phases4,5. in the case of phosphorus, PMo12O40-3, in solution. The amine
These third phases tend to be very thick oils that collect in the organic complexes of these heteropolymolydates tend to vary in color and
phase, at the organic/aqueous interface, and in some instances have limited solubility in the organic phase. A yellow green crystalline
even on the sides and bottom of the settler. Depending on their material has been isolated from a uranium plant and characterized as
chemical composition, they may range from a yellow/green to a dark (R3NH)3[PMo12O40]3(R3NHCl). Figure 4 shows a sample of a yellow
blue/green in color. If a small proportion of the molybdenum is green goo obtained from a molybdenum solvent extraction plant.
present in the +5 oxidation state, the molybdenum amine complex This material had collected on the bottom of the settlers.
tends to have limited solubility in the organic phase, especially if the
diluent is predominantly aliphatic in character. The resultant third Figure 4:
phase tends to be a very dark blue in color, hence it is commonly
referred to as the blue goo. When operating circuits in BASF
laboratories, the formation of the blue goo has been noted in
stripping. Addition of a small amount of hydrogen peroxide to the
strip solution has been used to eliminate it. If the molybdenum in the
feed solution has not been completely converted to the +6 oxidation
state, the solution may be a light blue to dark blue in appearance as
seen in Figure 3. The bottle on the left is a sample of leach solution
containing some molybdenum(+5), a drop of 35% hydrogen peroxide
has been added to the top of the leach solution in the center bottle,
and the bottle on the right was mixed thoroughly after addition of a
couple of drops of 35% hydrogen peroxide. Note the change in color
from a dark blue to a light yellow/green. Adjustment of the redox
potential to 490500 mV (vs SCE) was required to insure complete
conversion of the molybdenum(V) to the molybdenum(VI) in the BASF
laboratory.

Figure 3:

Based on past experience, one sign that third phase formation may
be occurring is the loss of extractive strength due to the loss of amine
as third phase from the circuit organic. This can be quite rapid.

Where the formation of third phases is a problem, BASF recommends


the use of Alamine 304 as the reagent. The alkyl groups of Alamine
304 are 12 carbons in length as compared to the 8 and 10 carbon
chains found in Alamine 336 resulting in improved solubility of the
molybdenum amine complexes6. The use of a diluent having more
aromatic character is also recommended.

Rhenium

Molybdenum is often associated with rhenium and flowsheets for the


separation and recovery of molybdenum and rhenium have been
developed7,8,9. For additional information contact your local BASF
Mining Solutions representative.
38

Vanadium

Vanadium has been recovered by solvent extraction from solutions Figure 5: Distribution of vanadium(V) as a function of pH
such as:
Water leach of salt roasted carnotite ore.
Sulfuric acid leach of carnotite ore. Isopolyvanadates H2V10O284 , HV20O285, H2V2O72
Water leach of salt roasted ferro-phosphorous slag.
By product streams from uranium recovery processes.

Vanadium Chemistry V4O124, H2VO41, HVO42

Similar to molybdenum, vanadium can also be present in a wide


variety of species in an aqueous solution depending on the oxidation
potential, the nature of other anions and metals that are present as Cationic VO2+1
well as their concentrations, the pH of the solution and concentration
of vanadium10. A simplified diagram of the distribution of various
vanadium(V) species as a function of pH is shown in Figure 5.
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0

pH
Vanadium Extraction

Depending on the situation, vanadium(V) can be extracted using


Alamine 336 or Aliquat 336. The chemistry of extraction and
stripping for both reagents is summarized in the following equations:

Formula 1: Alamine 336

Extraction 4 R3N(Org) + H2V10O28-4Aq) + 4 H+(Aq) (R3NH+)4H2V10O28-4(Org)

Stripping (R3NH+)4H2V10O28-4(Org) + 5 NH4OH(Aq) 4 R3N(Org) + (NH4+)5HV10O28-5(Aq) + 5 H2O

Formula 2: Aliquat 336

Extraction 4 R3NCH3+Cl-((Org) + H2V10O28-4(Aq) (R3NCH3+)4H2V10O28-4(Org) + 4 Cl-(Aq)

Stripping

(R3NCH3+)4H2V10O28-4(Org) + 4 NH4CI(Aq) +NH4OH(Aq) 4 R3NCH3+CH(Org) + (NH4+)5HV10O28-5(Aq) + H2O


39

The vanadium is recovered from the pregnant strip solutions by Vanadium Solvent Extraction Technical
addition of additional ammonium hydroxide to promote the Challenges
precipitation of ammonium metavanadate.
The formation of third phases similar to those observed with
To achieve efficient extraction of vanadium with Alamine 336, the molybdenum has been reported when using Aliquat 336 as
pH has to be controlled between about pH 2.5 to 3.511. Above about extractant13. These third phases may be due to the formation of
pH 3.5, there is insufficient acid available to insure that the amine is V(+4)
:V(+5) mixed valence decavanadate complexes due to
adequately protonated to form the ammonium cation. Below pH oxidative attack on the organic phase.
~2.5, extraction begins to decrease because vanadium is primarily
present as the vanadyl cation. As the concentration of the vanadium Vanadium(+5) species are relatively strong oxidants. Once loaded on
decreases in the aqueous, the balance between the anionic species the organic phase, they will carry out an oxidative attack on the
and the cationic species shifts to favor the presence of the anionic amine extractant. Over time, the tertiary amine will be degraded to
species resulting in vanadium recoveries of 9798%. Heating the secondary amines and a variety of other oxidation products.
solution shifts the equilibrium towards the anionic form. Increasing Fortunately, the degraded organic is also a good extractant for
the temperature in extraction to 50C increases vanadium recovery vanadium(+5). In cases where solvent extraction circuits using
to about 99%. The use of heat to decrease the vanadium in the Alamine 336 to recover another metal such as uranium are in
raffinate and increase recovery appears to have a constant effect operation at the same site, BASF recommends that organic from the
irregardless of the intial vanadium concentration in the incoming uranium circuit be used as make up for the vanadium circuit and
pregnant leach solution. In general, the extraction of vanadium with fresh reagent should be added to the uranium circuit to the greatest
Aliquat 336 is less sensitive to pH and does not require fine pH degree practical.
control. In minilab circuit trials, the use of the Aliquat 336 appears to
provide better physical performance. When dealing with chloride
Separation of Vanadium from Uranium
liquors, Aliquat 336 is more selective for the polyvanadate12.

Vanadium is frequently found associated with uranium. Both the


Stripping is also carried out with pH control between 6.0 and 7.8. If
uranium and vanadium are leached with sulfuric acid. Both can be
excess ammonium hydroxide is present, one can begin to trigger the
selectively extracted by controlling the redox potential of the
precipitation of sodium metavanadate in the strip stages resulting in
aqueous14. Uranium leaching is typically carried out at redox potential
emulsions and crud formation.
of 400500 mV (vs standard calomel electrode). This is sufficient to
insure that the uranium is present in the +6 oxidation state and can
be readily extracted as the uranyl sulfate complex using Alamine
336. The vanadium will be present in the +4 oxidation state and will
not form an extractable polyvanadate. If the redox potential of the
uranium raffinate is then increased to above about 610 mV (vs
standard calomel electrode) by addition of a suitable oxidant such as
hydrogen peroxide, the vanadium will be converted to the +5
oxidation state and form polyvanadates which can be extracted.
40

9. L
 IX Reagents
Additional Applications

LIX 63: LIX 63 is an alkyl alpha hydroxy oxime. Proposed uses LIX 7820: A mixture of a weak organic acid with a quaternary
include: amine developed for extraction of anions from solutions having a pH
less than ~10 and stripping efficiently at pHs greater than ~1115.
Germanium recovery1 Proposed uses include:
Copper recovery from typical tankhouse electrolytes2
As part of synergistic blends with other reagents for recovery of Extraction of gold from cyanide leach liquors15
cobalt and nickel3,4,5 Extraction of gold from thiosulfate leach liquors16
Separation of molybdenum from uranium in dilute sulfuric acid Cyanide recovery17
solution6
While the above covers a broad range of potential applications, it
LIX 84-I: A ketoxime based reagent which contains no added should not be considered as limiting. BASF continues to work on the
modifier and is readily stripped of copper with 150 g/L sulfuric acid. development of new extractant chemistries as well as on new
It is more hydrolytically stable than the corresponding aldoximes. applications for existing LIX reagents. If you have an interest in a
Uses include: particular application, you should contact your local BASF Mining
Solutions representative to explore possible solutions to your
Copper recovery from dilute sulfuric acid solution application.
Copper recovery from nitrate containing leach solutions under
conditions where modified aldoximes rapidly undergo
nitration/degradation7
Copper recovery from ammoniacal leach solutions and spent
PCB etchants8,9,10
Recovery of palladium from acidic chloride solutions11
LIX84-INS: A ketoxime based reagent employed in the recovery
of nickel from ammoniacal solutions12

LIX 84-IT: A ketoxime based reagent containing a small amount of


an ester modifier. It was specifically developed for extraction of
copper and nickel from ammoniacal solutions followed by acid
stripping. The presence of the modifier reduces chemical ammonia
transfer from extraction to strip13.

LIX 860N-I and LIX 860-I: Aldoxime based reagents differing in


the size of the alkyl group and containing no modifier. LIX 860N-I is
based on 5-nonylsalicylaldoxime and LIX 860-I is based on
5-dodecylsalicylaldoxime. Due to the presence of the larger dodecyl
side chain, LIX 860-I is more stable than LIX 860N-I and finds
application in copper recovery at higher temperatures. Potential uses
include:

Coextraction and selective stripping of copper and zinc14


Recovery of copper under certain conditions when pH of leach
solution is less than 1.0
41

10. Appendices
10.1 Isocalc* Computer Modeling Software

The BASF Isocalc (Total Metallurgy) computer simulation program The effect of changing any one or more variables in the configuration
was developed as a tool to provide plant operators with fast and can be quickly and accurately determined through to final copper
accurate simulations of virtually any copper solvent extraction recovery.
processes involving sulfuric acid leaching followed by copper
extraction with a phenolic oxime type extractant. The functions of The chemical model for the equilibrium extraction curves is based on
Isocalc include: the equilibrium constants for several important chemical reactions in
the process. By using these chemical criteria for the model, it is
From the description of a common (or complex) copper leach possible to take into account most of the variables commonly found
solution and the stripping conditions, extraction and stripping in a copper solvent extraction process.
isotherms are calculated based on a comprehensive chemical
model. McCabe-Thiele diagrams can then be constructed for A second generation of the Isocalc solvent extraction modeling
many solvent extraction plant configurations. program is currently in development. The new BASF Isocalc EHM
Laboratory generated extraction and/or strip isotherm data can (Enhanced Hydrometallurgy Model) program retains all the
be manually entered instead of relying on the chemical models functionality of the first generation software coupled with an novel,
provided. This is useful for reagent compositions that do not user-friendly processing platform. It offers the user a flexible mass
perform exactly the same as new or fresh LIX Reagents. This is balance package tailored for the LIX stable of reagents. Isocalc
often the case with aged plant organics. McCabe-Thiele EHM offers expanded functionality including many additional
diagrams can also be developed for these extraction and features, some of which are:
stripping isotherms.
From a chemical model or a lab-generated extraction isotherm Greater flexibility in specifying acid and copper tenor ranges for
developed for an operating plant, plant operating data or profiles spent and advance electrolytes.
can be inserted into the program and stage efficiencies will be Capability of handling broader range of circuit configurations and
accurately calculated. flows.
Results from each isotherm/McCabe-Thiele diagram can be Additional general modeling functionality.
saved as project files and later retrieved for use again in another It has complete mass flow functionality allowing for complete
simulation. minerals processing and hydrometallurgy flowsheet modeling.
Accurate comparisons of different plant configurations and The user interface input has been simplified by having all
operating conditions can be realized. inputs on one page at start up with the capability to rerun the
model with any number of stream attribute changes.
The Isocalc program includes a combination of chemical modeling User-selected Isocalc EHM models and outputs can be
of the extraction and stripping processes and mathematical exported into a comprehensive Xcel spreadsheet report.
manipulation of the data points. A stripped organic value from
either chemical modeling or a manually input stripped organic value For additional information about Isocalc EHM contact your local
must be used as a starting point for each extraction isotherm. Once BASF Mining Solutions technical representative.
the program has generated either an equilibrium extraction or
stripping curve, it allows for the construction of a McCabe-Thiele
diagram for a wide number of plant configurations, including the
now common series parallel configurations and BASFs new
Optimum Series-Parallel configuration. Any combination of 1
extract by 1 strip [1E, 1S] to [4E, 4S] stages can be modeled in the
series mode. In the series-parallel mode, any combination of [1E
(series), 1E (parallel), 1S] to [4E (series), 4E (parallel), 3S] stages can
be modeled. The organic/aqueous ratios of each circuit can be
varied independently and stage efficiencies can be varied over a
wide range for each stage in the configuration, independent of the
other stages. Stage efficiencies are usually correlated with the type
of mixers being used in a plant, the temperature of the circuit, and
the extraction kinetics of the extractant relative to the temperature. * Isocalc is a registered trademark in Brazil, Canada, Mexico, Peru and the US
42

10.2 Test Procedures

BASF quality control test of LIX reagents

Quality control test of neat reagents and in process copper solvent Organic from neat concentrated reagent except LIX 860-I
extraction (CuSX) organic for solution health, including phase- Prepare a 500 ml solution of exactly 7.143 % v/v of neat LIX reagent
disengagement-time (PDT), Cu/Fe selectivity and extraction/stripping in the diluent, Shellsol D70 or its approved equivalent. If v/v dilution is
kinetics. not convenient, w/v dilutions can be calculated and made using the
density of the LIX reagent lot being tested.
Background
The standard quality control test for LIX reagents is designed to be Organic from neat concentrated reagent LIX 860-I
a relatively simple and easy way to ensure that these LIX reagents Prepare a 500 ml solution of exactly 8.00 % v/v of neat LIX reagent
meet rigid specifications for those properties critical to the in the diluent, Shellsol D70 or its approved equivalent. If % v/v dilution
performance of these reagents as copper extractants. Reagent is not convenient, w/v dilutions can be calculated and made using
specifications are tied to the specific conditions of the BASF quality the density of the LIX reagent lot being tested.
control test and for this reason it is very important to strictly adhere
to the test equipment, reagents, conditions and procedures Organic from used plant material
described in this method. Prepare a 500 ml solution of plant organic with a maximum copper
loading of 5.6 g/L Cu.
Equipment
The test vessel is a 1-L PYREX glass beaker fitted with a set Standard extraction aqueous phase
of 4 Type 316 stainless steel baffles 4.7 inch (11.95 cm) tall by The extraction aqueous phase contains 6 0.1 g/L Cu+2, 3 0.1 g/L
0.4 inch (0.90 cm) wide with 20 gauge thickness set 0.125 inch Fe+3 (both as sulfates) at a pH of 2.0 0.1.
(0.318 cm) away from the beaker walls), clean and free of soap
or detergent residue. Standard strip aqueous phase
The polypropylene impeller is 1.75 inches (4.45 cm) in diameter The strip aqueous phase contains 35 0.7 g/L Cu (as the sulfate)
with 6 slots, 0.125 inches deep and 0.125 inches (0.32 cm) and 160 2 g/L H2SO4.
wide, the top of the hub is 1 cm above the top of the impeller,
and the shaft is 316 L stainless steel, 23 cm long. All solutions are prepared from reagent grade chemicals dissolved in
The mixer speed is adjusted to 1,750 25 rpm. While BASF D. I. water. All solution temperatures are equilibrated to 23 1 C
uses Stirrer Type RZRI available from Caframo (Wiarton, Ontario, before use.
Canada N0H 2T0), any good constant speed stirrer capable of
maintaining 1,750 25 rpm is acceptable. Before and after each test all equipment should be rinsed several
The test vessel, baffles, and impeller are available to BASF times with DI water followed by methanol or acetone and completely
customers free of charge from BASF. dried before each use. Failure to adequately rinse and dry the
When sampling the emulsion it is important that no additional equipment can result in erroneous results.
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 Procedure
pipette with the sample drawn through the large end are Extraction Kinetics, extraction isotherm point, extraction PDT
satisfactory devices. and extraction Cu/Fe selectivity
Vigorously contact 400 ml of the organic phase with 400 ml of strip
Reagents aqueous phase for two minutes in a separatory funnel. After the
Organic from neat formulated reagent phases have separated, filter the organic phase through Whatman
Prepare a 500 ml solution of exactly 10 v/v % of neat LIX reagent in 1PS or equivalent filter paper. Add 350 ml of filtered organic into the
the diluent, Shellsol D70 or its approved equivalent. If v/v dilution is test vessel and adjust the impeller so that it is centered in the test
not convenient, w/v dilutions can be calculated and made using the vessel and the top of the polypropylene hub of the impeller is at the
density of the LIX reagent lot being tested. surface level of the organic phase. Start the stirrer and adjust the
impeller speed to 1,750 25 rpm and then over 5 seconds smoothly
add 350 ml of standard extraction aqueous phase. Start the stop
watch immediately at the end of the aqueous addition.
43

A 30 second kinetic sample (E30) is taken as follows: Starting at 29 after the addition of the organic. Starting at 29 seconds, smoothly
seconds using the wide end of the pipette, smoothly remove remove 1015 ml of sample emulsion from the top 2 cm of the test
1015ml of sample emulsion from the top 2 cm of the test vessel vessel and drain into a small beaker or separatory funnel. Filter the
and transfer the sample into a small beaker or separatory funnel. organic phase through Whatman 1PS paper or equivalent and label
After the phases have separated, filter the organic sample through as the S30 sample. Continue stirring for a total of 300 seconds, stop
Whatman 1PS or equivalent filter paper, label as the E30 sample and the stirrer and allow the phases to separate measuring the phase
save for analysis. If ketoxime, such as LIX 84-I is being tested a 60 separation time as previously described. Sample the organic phase,
second kinetic sample (E60) is taken in the same manner as E30. filter the organic sample through Whatman 1PS or equivalent filter
Continue mixing for a total of 300 seconds at which time the stirrer is paper, label as the S300 sample and save for analysis. Refer to the
stopped. Immediately start a stopwatch and determine the time copper aqueous and organic procedures for analysis.
required for complete separation of the phases. Phase separation is
considered complete when only a monolayer of bubbles remains at Maximum copper loading
the interface. Sample the organic phase, filter the organic sample Take an aliquot of the diluted LIX reagent and an equal volume of
through Whatman 1PS or equivalent filter paper, label as the E300 standard extraction aqueous and contact them vigorously for 2
sample and save for analysis. Refer to the copper aqueous and minutes in a separatory funnel. Allow the phases to separate and
organic procedures for analysis. discard the aqueous phase. Add fresh standard extraction aqueous
and repeat the contact. Continue until a total of 4 contacts have been
Strip kinetics, strip isotherm point and strip PDT made. After the last contact, filter the organic sample through
The organic and aqueous phases from the extraction test above Whatman 1PS or equivalent filter paper, label as the Max Load
are transferred to a separatory funnel and the phases allowed sample and save for analysis.
to completely separate. The aqueous phase is withdrawn and
discarded. Loaded organic (325 ml) is carefully transferred to a Organic samples E30, E60, E300, S30 and S300 and the Max Load sample
graduated cylinder making sure no aqueous transfers with the are assayed by Atomic Absorption Spectroscopy (AAS) for Cu. The
organic. The standard strip aqueous (325 ml) is added to a clean test E300 sample is also assayed by AAS for Fe. All results are expressed
vessel. Adjust the impeller height as previously described, start the in units of g/L. AAS procedures used by BASF to determine copper
stirrer and adjust the speed to 1,750 25 rpm. Over a period of 5 and iron in organics are available upon request.
seconds add the loaded organic. Start the stopwatch immediately

Calculations

1. Extraction isotherm point Cu = E300

2. Strip isotherm point Cu = S300

E30 E60
3. Extraction kinetics % = x 100 or x 100
E300 E300
E300 (Cu)
4. QC Extraction Cu/Fe selectivity =
E300 (Fe)
E300 (Cu) S30 (Cu)
5. Strip kinetics % = x 100
E300 (Cu) S300 (Cu)

6. Net transfer Cu = E300 S300


44

BASF quality control test


of LIX nickel oxime reagents

Quality control test of neat reagents and in process nickel solvent Standard extraction aqueous phase
extraction (NiSX) organic for solution health, including phase- The extraction aqueous phase contains 15 0.1 g/L Ni+2, 1 0.1 g/L
disengagement-time (PDT), Ni/Zn selectivity and extraction/stripping Zn+2 (both as sulfates), 32.5 g/L NH3 and 25 g/L (NH4)2SO4.
kinetics.
Standard strip aqueous phase
Background The strip aqueous phase contains 60 0.7 g/L Ni (as the sulfate) and
The standard quality control test for LIX reagents is designed to be 30 1 g/L H2SO4.
a relatively simple and easy way to ensure that these LIX reagents
meet rigid specifications for those properties critical to the 1.0 M NaOH
performance of these reagents as copper extractants. Reagent Weigh 20.0 g NaOH into a 500 ml flask and dilute to volume with
specifications are tied to the specific conditions of the BASF quality deionized water which has been boiled to remove carbon dioxide.
control test and for this reason it is very important to strictly adhere Mix well. Standardize. Protect from CO2 absorption during storage to
to the test equipment, reagents, conditions and procedures prevent concentration changes.
described in this method.
KHP Buffer Solution
Equipment Into a 1 liter volumetric flask weigh 51.05 g potassium hydrogen
The test vessel is a jacketed 1 liter beaker equipped with phthalate, KHP. Add about 400 ml of deionized water and mix until
stainless steel baffles, clean and free of soap or detergent the KHP is dissolved. Add the volume of standardized 1.0 M NaOH
residue. calculated from the following equation: ml NaOH = 113/M NaOH.
The polypropylene impeller is 1.75 inches (4.45 cm) in diameter Dilute to volume with deionized water and mix well. The pH of the
with 6 slots, 0.125 inches (0.32 cm) deep and 0.125 inches buffer should be 5.0 0.1.
wide, the top of the hub is 1 cm above the top of the impeller,
and the shaft is 316 L stainless steel, 23 cm long. 50 g/L Potassium Oxalate (K2C2O4)
The mixer speed is adjusted to 1,650 25 rpm. While BASF Weigh 55.4 g K2C2O4 x H2O into a 1 liter flask and dilute to volume
uses Stirrer Type RZRI available from Caframo (Wiarton, Ontario, with deionized water. Mix well.
Canada N0H 2T0), any good constant speed stirrer capable of
maintaining 1,650 25 rpm is acceptable. Before and after each test all equipment should be rinsed several
The test vessel is maintained at 40 0.5C by a recirculating times with DI water followed by methanol or acetone and completely
water bath. dried before each use. Failure to adequately rinse and dry the
When sampling the emulsion it is important that no additional equipment can result in erroneous results.
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 Procedure
pipette with the sample drawn through the large end are
satisfactory devices. Extraction Kinetics, extraction isotherm point, extraction phase
separation and extraction Ni/Zn selectivity
Reagents All solutions used in this procedure must be equilibrated to 40
0.5C. Add 400 ml of organic into the test vessel and adjust the
Organic from neat formulated reagent impeller so that it is centered in the test vessel and the top of the
Prepare a 500 ml solution of exactly 30 v/v % of neat LIX reagent in polypropylene hub of the impeller is at the surface level of the organic
the diluent Orfom SX-12 or its approved equivalent. If v/v dilution is phase. Start the stirrer and adjust the impeller speed to 1,650
not convenient, w/v dilutions can be calculated and made using the 25 rpm and then over 5 seconds smoothly add 400 ml of the
density of the LIX reagent lot being tested. standard extraction aqueous phase. Start the stopwatch immediately
at the end of the aqueous addition.
45

organic phase through Whatman 1PS paper or equivalent and label


Take a 30 second kinetic sample (E30) as follows: Starting at 29 as the S10 sample. Continue stirring for a total of 20 minutes, stop the
seconds, smoothly remove 1015 ml of sample emulsion from the stirrer and allow the phases to separate measuring the phase
top 2 cm of the test vessel and transfer the sample into a small separation time as previously described. Withdraw a 75 ml sample of
beaker or separatory funnel. After the phases have separated, filter the organic phase, filter through Whatman 1PS or equivalent filter
the organic sample through Whatman 1PS or equivalent filter paper, paper, label a 10 ml aliquot as the S20 sample and save the remainder
label as the E30 sample and save for analysis. Continue mixing for a of the filtered stripped organic for interfacial tension analysis.
total of 300 seconds at which time the stirrer is stopped. Immediately
start a stopwatch and determine the time required for complete NH3 Loading
separation of the phases. Phase separation is considered complete Into a 60 ml separatory funnel accurately pipette 20.0 0.1 ml of
when only a monolayer of bubbles remains at the interface. Sample filtered loaded organic. Pipette accurately, 10.0 0.1 ml of the KHP
the organic phase, filter the organic sample through Whatman 1PS buffer solution. Shake the separatory funnel containing the organic
or equivalent filter paper, label as the E300 sample and save for and aqueous for 5 minutes. Allow the phases to separate and remove
analysis. the aqueous phase. Into a titration vessel accurately pipette 1.00
0.02 ml of the KHP buffer solution. Add 20 ml of the 50 g/L potassium
Strip Kinetics, Strip Isotherm Point, and Strip Phase Separation oxalate solution and mix well. Determine the acid content by titration
The organic and aqueous phases from the extraction test above are with standardized 0.1 M NaOH. Calculate the M of H+ using the
transferred to a separatory funnel and the phases allowed to equation in the calculation section. Into a titration vessel accurately
completely separate. The aqueous phase is withdrawn and dis pipette an aliquot of the aqueous phase from the separatory funnel.
carded. Loaded organic is filtered through Whatman 1PS paper or Usually 2.00 0.02 ml is an appropriate volume. Add 20 ml of the
equivalent filter paper. A 25 ml sample is withdrawn and set aside for 50g/L potassium oxalate solution and mix well. Determine the acid
the NH3 loading procedure. The remaining loaded organic is content by titration with standardized 0.1 M NaOH. Calculate the M
equilibrated to 40 0.5C, and transferred to a graduated cylinder. of H+ using the equation in the calculation section. Determine the
The strip aqueous (325 ml) is added to a clean test vessel. Adjust the concentration in M of Ni+2 and Zn+2, in the aqueous phase from the
impeller height as previously described, start the stirrer and adjust separatory funnel that have been stripped from the organic. C alculate
the speed to 1,650 25 rpm. Over a period of 5 seconds add 325ml the acid consumed by the metal stripped from the organic using the
of the loaded organic. Start the stopwatch immediately after the equations shown below.
addition of the organic. Starting at 9 minutes 59 seconds, smoothly
remove 1015 ml of sample emulsion from the top 2 cm of the test
vessel and drain into a small beaker or separatory funnel. Filter the

M H+ in aqueous = A x B/C
where A = ml 0.1 M NaOH
B = M NaOH
C = ml aliquot titrated

M H+ consumed by stripping metal = 2 x D


where D = total M of metals stripped into the buffer

g/L NH3 in organic = (E F G) x 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
46

Calculations
Maximum Nickel Loading
Take an aliquot of the diluted reagent and an equal volume of
1. Extraction isotherm point Ni E300 Ni g/L
standard extraction aqueous and contact them vigorously for 2
minutes in a separatory funnel. Allow the phases to separate and
2. Strip isotherm point Ni = S20 Ni g/L
discard the aqueous phase. Add fresh standard extraction aqueous
and repeat the contact. Continue until a total of 4 contacts have
3. Extraction kinetics % = (E30/E300) x 100
been made. After the last contact, filter the organic sample through
Whatman 1PS or equivalent filter paper, label as the Max Load
4. QC Extraction Ni/Zn = E300 (Ni g/L)/E300 (Zn g/L)
sample and save for analysis.
selectivity
(E300 Ni S10 Ni)
Organic samples E30, E300, S10 and S20 and the Max Load sample % = x 100
5. Strip kinetics
are assayed by Atomic Absorption Spectroscopy (AAS) for Ni. The (E300 Ni S20 Ni)
E300 sample is also assayed by AAS for Zn. All results are expressed
in units of g/L. AAS procedures used by BASF to determine nickel 6. Net transfer Ni = E300 Ni S20 Ni
and zinc in organics are available upon request.

Copper in aqueous solvent extraction solutions


Analysis
Instrument settings
Ignite the flame and aspirate deionized H2O for 5 minutes to
allow the instrument and burner head to warm up.
Slit width 0.7 mm
Aspirate the aqueous diluent for at least 5 minutes to allow the
Wavelength 327.4 nm with no background correction
system to stabilize.
Burner height The center of the light beam should be about
Zero the instrument using the aqueous diluent as the blank.
1 cm above the top of the burner.
Aspirate the highest working standard and adjust the angle
Flame Air-acetylene, oxidizing, fuel lean, blue, air flow
of the burner so that the absorbance of the highest standard
7.0 L/min, fuel flow 1.1 L/min
will be ~ 0.4.
Lamp current 12 ma (refer to lamp manufacturers recom
Set up a standard curve using the working Cu aqueous
mended setting)
standards. Use the aqueous diluent as the blank and the
Integration time 3.0 seconds
30.00mg/L standard as the reslope standard.
Replicates 4
Dilute the samples with the aqueous diluent to get the
concentration within the calibration standards.
Reagents
Aspirate each sample, read and record the concentration.
Aqueous diluent: 10 g/L H2SO4 in deionized H2O
Check the blank and standards as necessary to ensure that
Deionized H2O
the calibration has remained constant.
1,000 mg/L Cu Aqueous standard available from Fisher
After completing the analyses aspirate deionized H2O for 5
Scientific,
minutes to flush all salt from the spray chamber and burner.
PN#- PLCU2-2Y
Shut down the instrument.
Working standards: 60.00 mg/L Cu, 30.00 mg/L Cu, and
10.00mg/L Cu prepared from a 100 mg/L Cu standard. The
100 mg/L Cu standard is prepared from the 1,000 mg/L Cu
aqueous standard and the aqueous diluent
47

Copper in organic solvent extraction solutions

Background
Copper can be determined directly by atomic absorption spectro volumetric flasks requires the calibration of the pipettes with the
scopy in organic solvent extraction solutions. The instrument must diluent to achieve acceptable accuracy. The relatively high coefficient
be equipped to handle organic solutions and the standards and of expansion of organic solutions requires all standards and samples
samples must be diluted in an appropriate diluent. be diluted at the same temperature. The 327.4 nm secondary line
rather than the 324.7 nm primary line should usually be used since
The manufacturer of the instrument should be consulted for the concentration of copper in the samples is in the g/L range. The
instructions on setting up the instrument for the direct analysis of air-acetylene flame should be as lean as possible, in other words an
organics. Usually the o-ring seals in the nebulizer/spray chamber oxygen rich flame. The aspirated organic sample will act as a fuel and
must be changed to materials that are compatible with organic will give a neutral or fuel rich flame. The absorbance and linearity of
solutions. Once this change is made it is not necessary to change the the standard curve of copper are not very sensitive to the flame
o-rings back to the original material to analyze aqueous solutions. All conditions and height of the burner. For most instruments the angle
water must be removed from the spray chamber before aspirating of the burner head should be adjusted so the absorbance of the
organic. A convenient way to accomplish this is to ignite the flame highest standard is between 0.4 and 0.6.
and aspirate deionized H2O for 5 minutes to allow the instrument and
burner head to warm up. Then aspirate methanol or other similar Instrument settings
water miscible organic for 5 minutes to flush all water from the spray
chamber and burner. Then aspirate the organic diluent for 5 minutes Slit width 0.7 mm
to allow the system to stabilize. The organic should be removed from Wavelength 327.4 nm with no background correction
the spray chamber before analyzing aqueous solutions or shutting Burner height The center of the light beam should be about
down the instrument. Aspirate methanol for 5 minutes to flush all 1 cm above the top of the burner
organic from the spray chamber and burner. Then aspirate deionized Flame Air-acetylene, oxidizing, fuel lean, blue, air flow
H2O for 5 minutes to flush all methanol from the spray chamber and 7.0 l/min, fuel flow 1.1 l/min
burner. The instrument is now ready for the analysis of aqueous Lamp current 12 mA (refer to lamp manufacturers recom
solutions or can be shut down. mended setting)
Integration time 3.0
For organic sample preparation, filter each sample through PS1 seconds Replicates 4
paper to remove aqueous entrainment.
Reagents
An organic matrix is necessary for the dilution of samples and Organic diluent: 5 (v/v)% LIX 984N in Conoco 170 exempt
standards. BASF recommends a matrix of 5 % v/v of a LIX reagent solvent
in a petroleum hydrocarbon approved for use as solvent extraction Methanol
diluent. The diluent must be free of all copper. The use of diluent Deionized H2O
without a solvent extraction reagent gives low results with some 1,000 mg/L Cu organic standard (available from BASF Mining,
samples. The use of higher concentrations of solvent extraction 2430 N. Huachuca Dr., Tucson, AZ 85745, USA. Telephone
reagents in the diluent causes the burners in some instruments to +1 520-622-8891, Fax +1 520-624-0912)
rapidly clog. If all samples are diluted at least 1:10 in the diluent Working standards: 60.00 mg/L Cu, 30.00 mg/L Cu, and
matrix used to prepare the standards no matrix effects are observed. 10.00 mg/L Cu prepared from a 100 mg/L Cu standard. The
For samples containing copper at such low concentrations that a 100 mg/L Cu standard is prepared from the 1,000 mg/L Cu
1:10 dilution is not possible the matrix of the standards should be organic standard and the organic diluent
matched to the samples or the technique of standard additions
should be used. Preparation of organic working standards and
dilution of samples is best accomplished with an automated diluter
such as the Microlab Series available from The Hamilton Company,
P.O. Box 10030, Reno, NV 89502, USA, telephone +1 702-858-300,
fax +1 702-856-7259 or equivalent. The use of manual pipettes and
48

Analysis
Ignite the flame and aspirate deionized H2O for 5 minutes to Note: If a dilution of < 1:10 is used for a sample a matrix effect study
allow the instrument and burner head to warm up. should be performed to ensure accuracy of the results. If necessary
Aspirate methanol for 5 minutes to flush all water from the spray the samples should be reanalyzed using conditions and standards
chamber and burner. which allow for 1:10 dilutions, using a standard additions technique,
Aspirate the organic diluent for at least 5 minutes to allow the or using standards which have been matrix matched to the samples.
system to stabilize.
Zero the instrument using the organic diluent as the blank. Aspirate each sample, read and record the concentration.
Aspirate the highest working standard and adjust the angle of Check the blank and standards as necessary to ensure that
the burner so that the absorbance of the highest standard will the calibration has remained constant.
be ~ 0.4. After completing the analyses aspirate methanol for 5 minutes to
Set up a standard curve using the working Cu organic standards. flush all organic from the spray chamber and burner. Aspirate
Use the organic diluent as the blank and the 30.00 mg/L deionized H2O for 5 minutes to flush all methanol from the spray
standard as the reslope standard. chamber and burner.
Dilute the samples with the organic diluent to get the Shut down the instrument.
concentration within the calibration standards.

Clay treatment of LIX reagents

Tests the effectiveness of clay treatment on improving the health of Equipment and solutions
copper solvent extraction (CuSX) circuit organic. Refer to BASF Clays that have proven to be effective are acid leached montmorillinite
quality control test of LIX reagents (Standard QC Test). clays. Lupromin F-20X from BASF has been successfully used for
many years by a number of operators.
Background
During the operation of an CuSX circuit the organic phase can An efficient mixing chamber and mixer are needed. The equipment
become contaminated with organic substances which can adversely used in BASFs Quality Control Procedure works well but other
affect the phase separation time, kinetics, and the Cu/Fe selectivity. equipment can be used if this is not available. The BASF Quality
Clay treatment of the organic phase can sometimes be used to Control extraction and stripping solutions are also used in the test. If
remove the contaminant from the organic phase. these are not available PLS and barren electrolyte solutions known to
be free of contaminants can be used.
To determine if clay treatment will improve the performance of the
organic, the phase separation time, kinetics, and the Cu/Fe selectivity When sampling the emulsion it is important that no additional mixing
are measured before and after clay treatment. Clay treatment is occurs. A large bore sampling tube should be used. A 10 ml
normally tested initially at the concentration of 1 % w/w. If the clay volumetric pipette with the tip cut off or a 10 ml serological pipette
treatment is effective at 1 % w/w then lower concentrations can be with the sample drawn through the large end are satisfactory devices.
tested to determine the minimum concentration necessary for
effective treatment.
49

Before and after each test all equipment should be rinsed several Continue mixing for a total of 300 seconds at which time the stirrer is
times with water followed by methanol or acetone and completely stopped and the stopwatch is quickly reset and started. Determine
dried before reuse. the time required for complete separation of the phases. Phase
separation is considered complete when only a monolayer of bubbles
Procedure remains at the interface. Sample the organic phase, filter the organic
sample through Whatman 1PS or equivalent filter paper, label as the
Clay treatment procedure E300 sample and save for analysis.
Place 400 ml of organic phase into the test vessel and adjust the
impeller so that it is centered in the test vessel and the top surface of The organic and aqueous phases from the extraction test above are
the impeller disc is 1 cm below the surface level of the organic phase. separated in a separatory funnel (discard the aqueous phase) and
If a BASF QC impeller is used the top of the polypropylene hub of the then 325 ml of the loaded organic is carefully transferred to a
impeller should be at the surface level of the organic phase. Begin graduated cylinder. Make sure no aqueous transfers with the organic,
stirring, set the impeller speed to 1,750 25 rpm and over 5 seconds filter if necessary. Next add 325 ml of strip aqueous to a clean test
add the clay. Continue stirring for 60 seconds. Then stop the stirrer vessel. Adjust the impeller position as previously described and begin
and immediately filter the treated organic to remove the clay. Longer stirring at 1,750 25 rpm. Over 5 seconds add the loaded organic
mixing times are usually not necessary. Very long mixing times, > 5 and then start the stopwatch. Start the stopwatch immediately after
minutes, usually result in the absorption of some of the LIX reagents the addition of the organic. Starting at 29 seconds, smoothly remove
onto the clay and may also allow some of the contaminants to be 1015 ml of sample emulsion from the top 2 cm of the test vessel
released from the clay back into the organic phase. and drain into a small beaker or separatory funnel. Filter the organic
phase through Whatman PS1 paper or equivalent and label as the
Extraction and strip test procedure S30 sample. Continue stirring for a total of 300 seconds, stop the
Place 350 ml of stripped organic phase into the test vessel and stirrer and allow the phases to separate measuring the phase
adjust the impeller position as described previously. Begin stirring, separation time as previously described. Sample the organic phase,
set impeller speed to 1,750 25 rpm and then over 5 seconds add filter the organic sample through Whatman PS1 or equivalent filter
350 ml of the extraction aqueous phase. A stopwatch is started at paper, label as the S300 sample and save for analysis.
the end of the 5 seconds aqueous addition. At 29 seconds smoothly
remove about 1015 ml of sample emulsion from the stirring test Organic samples E30 or E60 and E300 from extraction, S30 and S300 from
vessel and allow the sample to drain into a small beaker or separatory stripping are assayed by Atomic Absorption Spectroscopy (AAS) for
funnel. After the phases have separated, filter the organic sample Cu; samples E300 from extraction and S300 from stripping are also
through Whatman PS1 phase separation filter paper, label as the E30 assayed by AAS for Fe. AAS procedures used by BASF Corporation
sample and save for analysis. If LIX 84-I is used take an E60 sample to determine copper and iron loaded on organic are available upon
as opposed to an E30. request.

Calculations

E30 g/L Cu E60 g/L Cu


1. Extraction kinetics % = x 100 or x 100
E300 g/L Cu E300 g/L Cu

E300 g/L Cu S300 g/L Cu


2. QR Extraction
=
Cu/Fe selectivity
E300 g/L Fe S300 g/L Fe

3. Strip kinetics E300 g/L Cu S30 g/L Cu


% = x 100
E300 g/L Cu S300 g/L Cu
50

Direct colorimetric determination


of uranium on amine

This is a simple, rapid and accurate method for the direct colorimetric Transfer 13 ml of the amine sample containing 0800 ppm of
determination of uranium on amine (Alamine 336) extractants. This uranium and less than 21 mg sulphate to a 50 ml volumetric flask.
procedure is linear from 0800 ppm uranium, the color development
is almost instantaneous and the color is stable for 12 hours. Dilute to the 50 ml mark with chromogenic solution and mix well.
Color development is almost instantaneous and is stable for
Preparation of organic standard and standard curve 12 hours.
1) 1 g/L uranium aqueous atomic absorption standard
2) 6 % v/v Alamine 336 + 4 % v/v decyl alcohol + 90 % v/v kerosene Read absorbance at 410 nm using chromogenic solution as the
blank. Note: Use matched cells.
Transfer 100 ml of aqueous uranium standard and 100 ml Alamine
solution to a mixer box. Equilibrate the solutions for 3 minutes at pH Calculations
1.5 using H2SO4 to adjust the emulsion pH. Stop the mixer and allow The optical density of the unknown samples should fall in the range
the phases to separate. Discard the aqueous layer and filter the generated by the standard solutions. If the uranium concentration of
organic phase through 1-PS filter paper. the unknown solutions is greater than 800 ppm, proper dilutions
should be made prior to the general procedure. For samples in the
This procedure yields a 1 g/L organic uranium standard. From the correct concentration range, ppm uranium is read directly from the
1 g/L organic standard, make a series of standards ranging from standard curve. This procedure is linear between 0
800 ppm
10800 ppm uranium and assay for uranium following the general uranium. The standard curve should pass through the origin.
procedure.

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.

2) Equipment
Spectrophotometer

3) Procedure
Filter the amine sample to be assayed through 1-PS filter paper.

* IMS = proprietary alcohol solvent, anhydrous; VWR# 0475-7


51

10.3 S
 X Extractants and
Process Auxilliaries

LIX Reagents

BASF offers a broad range of LIX reagents based on three phe blend. BASF has the capability of formulating an extractant tailored
nolic oximes: C9 aldoxime (5-nonylsalicylaldoxime), C12 aldoxime to best meet the needs of the individual operation. For applications
(5-dodecylsalicylaldoxime) and ketoxime (2-hydroxy-5-nonyl aceto where hydrolytic degradation of the C9 aldoxime may be an issue
phenone oxime). Combining these reagents in various proportions due to higher temperatures, the use of the more stable C12 aldoxime
with one another allows BASF to formulate a series of reagents may be recommended.
having varying extractive strengths for copper. These extractants are
referred to as non-modified blends. BASF also offers blends of the For help in choosing the best reagent formulation for your application,
aldoximes with varying proportions of thermodynamic modifiers contact your local BASF Mining Solutions technical representative.
(modified aldoximes) as well as blends of aldoximes with ketoxime Representative examples of the more common formulations based
and thermodynamic modifiers (modified mixtures). Increasing the on C9 aldoxime are listed in Table 1.
level of the thermodynamic modifier results in decreasing the
extractive strength of the modified aldoxime or the modified mixtures

Table 1:

Relative Non-Modified Blends Modified Aldoximes


Reagent
Strength
LIX 84-I LIX 8180 Ester Modified Alcohol
Based Based Modified

LIX 860N-I LIX 860N-I

LIX 973N LIX 973NS-LV LIX654N-LV LIX 622N

LIX 664N-LV

LIX 984N LIX 9858NS-LV LIX 674N-LV

LIX 946N LIX 684N-LV

LIX 9790N

LIX 8180

LIX 84-I
52

Alamine and Aliquat Reagents

Many of these reagents are also available as concentrates which can BASF offers three tertiary amines and a quaternary amine
result in reduced transportation costs. These are designated with a C (Table 3).
added to the name. Reagents containing C9 aldoxime are designated
by using an N after the number Table 3:

Specialized formulations have also been developed for certain


Reagent Alkyl Application
applications. These are listed in Table 2.
Groups

Table 2:
Tertiary Amines
Reagent Application
Alamine Tri-iso Extraction of cobalt away from
308 C8 acidic nickel solutions
Ketoxime Based

Alamine Tri-n Extraction of uranium,


LIX 84-INS Extraction of nickel from ammonia
336 C8C10 molybdenum, vanadium,
tungsten
LIX 84-IT Reduced ammonia transfer when extracting
copper or nickel from ammoniacal feeds Alamine Tri-n Extraction of molybdenum,
304-1 C12 citric acid
Alpha-Hydroxy Oxime

Quaternary Amine
LIX 63 Component of synergistic mixture systems for
separation of cobalt and nickel; Extraction of
Aliquat Tri-n (C8 Extraction of anionic metal
germanium and gallium
336 C10), Methyl complexes on alkaline side

Quaternary Amine/Weak Acid

LIX 7820 Extraction of anionic species coupled


by stripping with strong caustic;
Gold extraction from cyanide
53

10.4 Mixer Settlers

Efficient solvent extraction requires the dispersion of one immiscible Typical design criteria for a conventional mixer-settler unit for copper
phase as droplets in another immiscible phase. In our case, the SX plants using current oxime reagent technology to treat typical
phases are typically a solution of a metal extractant in a high flash acidic heap or dump leach solutions are as follows:
point petroleum distillate (organic phase) and an aqueous phase. The
stage efficiency is dependent on the rate of mass transfer of the Mixer
material of interest from one phase to the other phase. The rate of O/A in mix box = 0.91.2 (Recycles used if needed)
mass transfer is highly dependent on the rate of diffusion of the Mixer residence time = 2 mins (3 mins if solutions are cold)
various species to the interface and the rate of any chemical reactions Mixer tip speed = 250300 meter/min
that occur at the interface. The amount of interfacial area available for Turbine diameter = 0.50.6 diameter of mixer
mass transfer is dependent on the size of the droplets of the Settler
dispersed phase. Decreasing the droplet size increases the interfacial Specific flow rate (total flow) = 4.06.5 m3/m2/hr;
area resulting in an increase in mass transfer. The droplet size is 3.03.5 m3/m2/hr if cold
determined by a variety of factors including the viscosities of the Organic space velocity = 36 cm/sec
phases, the power input into the mixer, and design of the mixer. Organic depth = 2030 cm
Since the organic and aqueous phases must separate in the settler
in a short period of time, mixing must be controlled so as not to
generate excessive amounts of very fine droplets which will not settle
and which will lead to high entrainments of the dispersed phase in
the other phase. Significant improvements have been made in the
design and control of mixers and settlers since their initial use in the
nuclear industry starting in the early 1950s1,2,3,4,5,6,7,8,9.

Figure 1: Depicts a top view and a side view of a


conventional dual mixer-settler unit.

Organic
Advance
Aqueous Recycle

Adjustable
Aqueous
Weir

Organic
Aqueous Up Comer
Aqueous Recycle
Organic Discharge

Fixed Aqueous
SETTLER Advanced Weir
Advance

Aqueous

Fixed Organic Weir


Aqueous
Advance
54

When dealing with ammoniacal solutions of nickel10, the use of the When extracting uranium from dilute sulfuric acid solutions with
following design criteria is suggested: amines and stripping with ammonia/ammonium sulfate solutions,
suggested design criteria are11,12:
Mixer
O/A in mix box = 0.91.1 (Recycles used if needed) Mixer
Mixer residence time = 3 mins in extraction; O/A in mix box = 0.91.1 (Recycles used if needed)
57 mins in stripping Mixer residence time = 12 mins in extraction; 23 mins in
Mixer tip speed = 250300 meter/min wash; 24 mins in stripping; 23 mins in regeneration
Turbine diameter = 0.50.6 diameter of mixer Mixer tip speed = 250300 meter/min
Settler Turbine diameter = 0.50.6 diameter of mixer
Specific flow rate (total flow) = 34 m3/m2/hr in extraction; Settler
35 m3/m2/hr in stripping Specific flow rate = 34 m3/m2/hr
Organic space velocity = 34 cm/sec Organic space velocity = 24 cm/sec
Organic depth = 2030 cm Organic depth = 3040 cm

Figure 2: Dual Mixer Settler Unit

Adjustable
Aq Weir
No. 1 No. 2 Axial Picket
Pump Mixer Flow Mixer Fence Fixed Org Weir

Organic
Dispersion
Aqueous

Settler
False Bottom Org Aq
Organic In Out Out
Aqueous Recycle
Aqueous In
55

10.5 D
 iluents for
Metal Solvent Extraction Applications

The diluents used in metal solvent extraction applications have The selection of the proper diluent for use with a specific extractant
evolved over the years and are no longer simple kerosene fractions. in a given extraction process is important due to potential effects on
Diluent suppliers have developed ranges of diluents specifically both the chemical and physical properties of the system. Of equal
for use in metal solvent extraction applications. These diluents importance is maintenance of an on-going program to monitor the
typically contain a mixture of paraffinic, aromatic and naphthenic quality of diluent make-up as it is received at the solvent extraction
hydrocarbons. The relative proportions of these different hydrocarbon plant. For help in developing a good laboratory program to select the
classes can be altered to give improved performance for particular appropriate diluent and monitor the quality of the supplied material,
applications. The diluents are also hydrotreated during the contact your local BASF Mining Solutions technical representative.
manufacturing process to ensure that the olefinic content of the
diluent is very low. Olefinic double bonds tend to be reactive sites in For additional information regarding diluents and their applications,
hydrocarbons that can undergo a variety of chemical attacks; see the references on Chapter 10.5.
e.g., oxidation, sulfonation, sulfation; resulting in the formation of
materials that can cause problems with extraction selectivity, phase
disengagement rates, and increased entrainment.

Typical requirements for a diluent are:

High solubility of the extractant, modifier and the extracted metal


complex in the diluent
Low toxicity
Low volatility and high flash point to minimize volatility losses and
fire hazards
Low viscosity and low density to help promote phase separation
Low surface tension
Insoluble in water
Cheap and readily available
56

10.6 Typical Properties of Reagents

Table 1: Physical Properties for Alamine and Aliquat Reagents

Alamine 308 Alamine 336 Alamine 304 Aliquat 336

S.G. (g/cc) 0.81 0.81 (6.7 lbs/gal) 0.82 0.88

Viscosity@4C (cPoise) 53 23 Waxy Solid 6,300

Viscosity@30C (cPoise) 29 11 36 1,450

Viscosity@60C (cPoise) 17 6 12 197

Pour Point (C) 54 54 10 14


(ASTM D97-09)

Fire Point (F) ND 179 254 ND


(ASTM D92)

Flash Point (F) 150 210 190 132


(Pennsky-Marten CC)

Boiling Point (C) 350370 @ 1 atm1 260280 @ 23 mm Hg 220228 @ Decomposes


185 @ 0.3 mm Hg 0.03 mm Hg (Slow onset at
80C @ 1 atm)

Surface Tension 27 29.3 57 29.5


(dyne/cm @ 25C)

Heat Capacity (cal/g/K) 0.406 0.450 0.523 0.550

Conductivity (pS/m) 5.3 5.2 6 High

1) Estimated from data for tri-n-octyl amine.


57

Table 2: Physical Properties for Non-Modified Reagents Standard Formulations

LIX 84-I LIX 984N LIX 860N-I LIX 860-I

S.G. (g/cc) 0.9 0.91 0.91 0.91

Viscosity@4C (cPoise) 131 179 144 228

Viscosity@30C (cPoise) 26 30 26 37

Viscosity@60C (cPoise) 7 8 7 10

Pour Point (C) 56 47 52 42


(ASTM D97-09)

Fire Point (F) 116 116 112 110


(ASTM D92)

Flash Point (C) >77 >77 >77 >77


(Pennsky-Marten CC)

Boiling Point (C) Decomposes Decomposes Decomposes Decomposes

Surface Tension 29.8 30 28.9 77


(dyne/cm @ 25C)

Heat Capacity (cal/g/K) 0.478 0.406 0.430 0.454

Conductivity (pS/m) 214 109 52 47


58

Table 3: Physical Properties for Non-Modified Reagents Concentrate Formulations

LIX 84-IC LIX 984N-C LIX 860N-IC LIX 860-IC

S.G. (g/cc) 0.94 0.94 0.935 0.935

Viscosity@4C (cPoise) 2,353 4,597 3,580 3,185

Viscosity@30C (cPoise) 161 245 208 217

Viscosity@60C (cPoise) 24 30 27 29

Pour Point (C) 20 20 18 25


(ASTM D97-09)

Fire Point (F) 112 122 128 118


(ASTM D92)

Flash Point (C) >77 >77 >77 >77


(Pennsky-Marten CC)

Boiling Point (C) Decomposes Decomposes Decomposes Decomposes

Surface Tension 31 32 31 31
(dyne/cm @ 25C)

Heat Capacity (cal/g/K) 0.406 0.478 0.502 0.430

Conductivity (pS/m) 44 33 21 13
59

11. Footnotes

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