Redbook

Mining Solutions

Content

1. Introduction

2. Solvent Extraction

3. Copper Extraction from Acidic Sulfate Solution

3.1

Chemistry of Copper Extraction

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

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
purity metals in particular, the mining industry has had to find more
effective and efficient methods for processing ores and recovering the
metal values to overcome the challenges associated with decreasing
ore grades and increasingly stringent environmental regulations. The
development of hydrometallurgical processing has played a significant
role in helping to overcome these challenges and will provide many of
the new processes required to meet the challenges of the future.
Solvent extraction (SX) technology will play an integral role in many of
these new processes.

remains the reagent of choice to this day for the solvent extraction of
uranium. The introduction of Alamine 336 to the mining industry was
followed by the development and introduction of LIX 64 for the
recovery of copper by solvent extraction. The first successful
application of the leach-solvent extraction-electrowinning process for
the recovery of copper was marked by the startup of the Ranchers
Bluebird Mine copper solvent extraction plant (Design = 5,000tonnes
Cu/yr) in 19685. This was quickly followed by the commissioning of
the Cyprus Bagdad copper solvent extraction plant (Design= 6,600
tonnes Cu/yr) in 1969.

The first example of the use of liquid-liquid solvent extraction to

recover and purify a metal can be traced back to the extraction of
uranyl nitrate into ethyl ether by Peligot in 18421. The analytical
chemistry literature contains thousands of references to the use of
solvent extraction to isolate, purify and concentrate materials to
facilitate analysis. This work in analytical chemistry has resulted in the
development of a large pool of fundamental knowledge with regards
to solution chemistry and organic based extractants2.

The Bagdad copper solvent extraction plant is now part of Freeport

McMoRan and is the oldest operating solvent extraction plant in the
world6. This was followed by the commissioning of the Nchanga
Tailings Leach Plant (Design = 54,000 tonnes Cu/yr) in 19747. Since
its earliest beginnings, the Mining Solutions group has been
committed to and remains committed to the development of solvent
extraction technology and solvent extraction reagents.

Starting in the 1950s, solvent extraction was applied on a commercial

scale to the recovery of uranium, vanadium and molybdenum3. The
Mining Solutions business of BASF, which traces at least a part of its
roots to the former General Mills Chemicals, developed Alamine 336
and introduced it in 1957 for the recovery of uranium4. Alamine 336

The use of copper solvent extraction has grown dramatically since

the late 1960s. There are a total of more than 119 copper solvent
extraction plants currently operating around the world producing an
estimated 3.7 MM tons of copper in 2012. Given that total copper
production in 2012 was estimated to be approximately 16.97 MM
tons8, copper SX represented 22% of the global copper production.

The Mining Solutions groups dedication to improving solvent

extraction technology has led to a number of industry firsts:
Developed tertiary amines (Alamine reagents) and quaternary
amines (Aliquat reagents) for metal extraction4
Conceptualized leaching-solvent extraction-electrowinning for
copper4,7
Developed first commercially successful phenolic oxime reagents
(LIX reagents) for extraction of copper and nickel.7,9
Developed first alcohol modified aldoxime blend for copper
extraction7
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

The goal of this book is to familiarize the reader with the

fundamental concepts of solvent extraction technology as well
as with the LIX, Alamine and Aliquat solvent extraction
reagents and their applications. This booklet will also introduce
other reagents, systems and services provided by the Mining
Solutions business of BASF. More detailed information about
specific reagents, metals, or process systems is available on
request.
LIX, Alamine, Aliquat and Isocalc* are registered trademarks of
BASF SE.

* Isocalc is a registered trademark in Brazil, Canada, Mexico, Peru and the US

2. Solvent Extraction

Solvent extraction (SX) as used in this booklet refers to a liquid-liquid

extraction process for separating species in solution by their
distribution between two immiscible solvents1. In the metal recovery
operations of interest, the SX process involves a chemical reaction of
the metal species of interest with an organic extractant in an organic
diluent such as a petroleum distillate cut similar to kerosene. The
reaction of the metal species with the organic extractant results in a
hydrocarbon soluble metal complex. The chemistry involves equillibria
as a result transfer of the metal species into (extraction) and out of
(stripping) the hydrocarbon phase can be controlled by altering
conditions such as the pH of the aqueous.
As part of a metal recovery process, solvent extraction using BASF
extractants has three primary objectives:
Purification of the metals from unwanted impurities.
Extract desired metal(s) away from impurities.
Extract impurities away from desired metal(s).
Concentration of the metal values to reduce downstream
processing costs.
Conversion of the metal values to a form which simplifies final
recovery.
In any given solvent extraction process, one, two, or all three
objectives may be necessary.
A key point for the reader to understand is illustrated in Figure 1.
Solvent extraction is only one unit process in a series of unit processes
in going from the metal bearing ore to the final metal product. The
leaching process delivers a metal bearing solution whose nature will
vary depending on the actual ore and the conditions required to
achieve effective solubilization of the metal values. The solvent
extraction process must be able to efficiently transfer the metal
values from this incoming leach solution into the organic phase.

The final metal recovery step will determine the conditions

under which the metal values will be transferred from the metal
loaded organic to generate a concentrated and purified aqueous
metal solution.
Leaching
/
SX
/
metal recovery are interlocking processes whose
overall success is dependent on the effectiveness of each step. To
develop an effective metal recovery process, it is critical to know the
nature of the leach solution that is to be treated and the recovery
process that will be used to produce the desired metal product. Each
sets criteria within which the solvent extraction process must operate.
The solvent extraction process is conceptually simple:
The metal bearing leach solution (Pregnant Leach Solution, PLS)
is fed into a mixer along with an immiscible hydrocarbon solution
of a metal extractant (Barren Organic) where the two solutions
are intimately mixed.
The resultant emulsion overflows from the extraction mixer into
the settler. As it progresses down the settler, the solutions
separate to give a metal loaded organic (LO) solution on top and a
metal depleted aqueous solution (raffinate) on the bottom.
The raffinate is discharged via an underflow weir and recycled to
leaching. The LO passes over a weir and flows to a second mixer
where it is intimately mixed with a strip solution.
The resultant emulsion overflows from the strip mixer into the
corresponding settler where it separates into a metal barren
organic (BO) which is returned to extraction and a concentrated
aqueous solution (Pregnant Strip Solution) of the desired metal in
a form from which it can be readily recovered.
Figure 2 illustrates a copper solvent extraction plant consisting of 2
stages of countercurrent extraction and 2 stages of countercurrent
stripping.

Formula 1

Extract
2RH(Organic) + Cu+2(Aqueous)

R2Cu(Organic) + 2H+(Aqueous)
Strip

Figure 1: Generalized Metal Recovery Flowsheet

Incorporating Solvent Extraction with BASF Reagents.

Aq

Metal Stripping

en

pu

Im
e

eta

l Le
a c h S o l u ti o n

Leaching
Process

Me

tal L o a d e d LIX

g
ea

Solvent
Extraction

Pure Metal Product

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

important to know the composition of the aqueous feed solution in
terms of the metal species and other species including anions that
are present. With respect to metals, the extractable species can be
classified into 4 types:

Metal Extraction

olution
trip S
sS
ou
ue

rif
Pu
Co
n c e n tr a t e d & io n
t
u
M etal S ol

ie

Metal Leaching

eagent
IX R
dL
pe
rip

St

Re
c

ch Solution
Lea
led
yc

Each mixer-settler represents one stage of extraction or stripping. In

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.
The combination of proper reagent choice, ability to use a variable
number of mixer-settler stages, adjust flow rates, and use of wash
stages allows a great deal of flexibility in designing a plant to meet the
requirements for a given metal recovery problem.

Final Metal
Recovery

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

2. Complex metal anions such as UO2(SO4)34-, Mo8O264-,
H2V6O172-, CoCl423. 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
Tank

Organic

Barren
Organic

S1

S2

Pregnant
Strip Soln

Lean
Strip Soln

The metal species listed above have all been recovered commercially
in solvent extraction plants at one time or another. It represents only
a small sample of the many extractable chemical species that may
be present.
Metal extractants are divided up into five separate classes dependent
upon the structure of the extractant, the mechanism of extraction
and nature of the metal species extracted:

Chelating extractants.
Ion pairing extractants.
Organic acids.
Extractants that function by ligand substitution.
Extractants that function by solvation.

BASF markets chelating reagents and ion pairing reagents. Chelating

reagents function by forming chemical bonds with a cationic metal
ion at two sites similar to grasping an object between the ends of
ones thumb and index finger. The LIX reagents based on the
phenolic oximes are examples of chelating reagents. Ion pairing
extractants function by forming an organic soluble ion pair between
an organic soluble cationic species and a complex anionic metal
species. The Alamine and Aliquat reagents are examples of ion
pairing extractants. The Alamine reagents are based on tertiary
amines having long alkyl chains. They accept a proton from acid
solutions to form a cationic ammonium ion which can then pair with
an anion in the organic phase. Aliquat reagents are based on
quaternary amine salts. The Aliquat reagents function similarly to the
Alamine reagents; the difference being that the quaternary amine is
always positively charged. Since there is no need to form a cation by
protonation, the Aliquat reagents can also extract anionic species
from alkaline aqueous solutions.
Successful reagent selection requires matching the chemical
characteristics of the extractant with those of the metal species
present in the incoming aqueous feed solution. While chemists have
identified metal extractants for carrying out chemical separations of
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.

In order to be commercially successful, a metal extractant must meet

the following criteria at least in part:
1. Have a cost conducive to good process economics.
2. Extract the desired metal(s) with some degree of selectivity from
the aqueous feed solution.
3. Strip the metal values from the loaded organic into an aqueous
solution which facilitates final metal recovery.
4. Be stable to the operating conditions through many cycles of
extraction and stripping.
5. Load and strip metal at a rate fast enough to permit use of
economical mixing times.
6. Exhibit good phase separation properties.
7. Be nonflammable with low toxicity, non-carcinogenic, etc.
8. Soluble both as the extractant and as the metal complex in an
inexpensive organic diluent.
9. Avoid transfer of species from stripping to extraction that might
interfere with extraction.
While no extractant meets 100% of each of these criteria, successful
reagents possess a good balance of all the properties in the list.
BASF reagents possess this balance of properties.
Reagent selectivity is often an issue. Very few, if any, extractants
demonstrate selectivity for only one metal over a broad range of
conditions. Many extractants, however, are reasonably selective for
one metal over another under a certain set of conditions. The
selectivity is dependent on the conditions and the challenge is to
match the conditions associated with the given leach solution with
the selectivity characteristics of the available reagents. A perfect
match is seldom achieved. One either settles for a reagent that
performs reasonably well or one tries to alter the leaching process
to produce a leach solution which will allow an extractant to be
more selective. To do this successfully, one needs a very good
understanding of the chemistry of the leaching process as well as the
chemistry of the extraction process. A BASF technical representative
can help to provide the necessary understanding of the chemistry.

3. Copper Extraction from Acidic Sulfate Solution

3.1 Chemistry of Copper Extraction

All modern commercial copper solvent extraction reagents are based

on phenolic oxime type molecules. They can be classified into two
general types, aldoximes and ketoxime.

H
O

O N

O
N

H
O

O N

O
N

In the process of forming a complex, two hydrogen ions are released

into the aqueous solution for every copper ion that is extracted. The
chemistry is summarized in the following equation where RH
represents the extractant (Formula 1).

H
R

CH3

O
Cu

CH3
N

Aldoxime

Ketoxime

C9H19

C9 Aldoxime,
5-Nonylsalicylaldoxime

Ketoxime, 5-Nonyl-2hydroxyacetophenone
Oxime

C12H25

O
O

H
R

A key parameter in controlling the equilibrium position of this reaction

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
represented in Figures 1 and 2.

Figure 1: pH Isotherms for Several Metals with Ketoxime

C12 Aldoxime,
5-Dodecylsalicylaldoxime

100

Ni

Cu

80
Co

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)
of the oxime to the copper ion. The complex is very non-polar and
hydrocarbon soluble. They belong to a group of molecules described
as bidentate chelating agents since they grasp the copper ion
between the two sites in a pincer like fashion. The R group is typically
a highly branched hydrocarbon chain consisting of either 9 or 12
carbon atoms.

Extraction %

Mo
60

40
Fe3+
20

Zn

Mn
0

4
pH

Formula 1

Extract
2RH(Organic) + Cu

+2

R2Cu(Organic) + 2H+(Aqueous)

(Aqueous)

Strip

These pH isotherms can be used to predict the extraction

characteristics of a reagent under a variety of conditions. For
example, it is apparent that copper(II) is strongly extracted by both
reagents at a pH of 2.0 and that the C9 aldoxime extracts copper(II)
more strongly than the ketoxime. Ferric iron at a pH of 2.0 is only
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.

any extracted Mo(VI) can be removed from the organic if necessary.

In most cases, only Fe(III) presents a potential problem with regard to
preparing a pure copper solution from a normal copper leach
solution at pH = 2.0 in agreement with the pH isotherms in Figures 1
and 2.

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

100

80
Mo
Extraction %

Metal

Relative Extractive Power

Cu(II)

Very strongly extracted

Fe(III)

Slightly extracted

Mo(VI)1)

Moderately extracted

V(V)1)

Slightly extracted

Zn(II)

Nil

Sn(II)

Nil

Ca(II)

Nil

Mg(II)

Nil

As(III)

Nil

Al(III)

Nil

Fe(II)

Nil

Si(IV)

Nil

Co(II)

Nil

Ni(II)

Nil

Mn(II)

Nil

Ni

Cu

Co

Zn

60

40
Fe3+
20
Mn
0

pH

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

aldoxime extracts all of the metals with the exception of manganese(II)
more strongly than does the ketoxime. In making comparisons of pH
isotherms for two different reagents with the same metal or for two
different metals with the same reagent, the pH isotherms must be
determined under exactly the same conditions. A summary of the
general relative extraction behavior for a wide range of metals with
ketoxime and C9 aldoxime is summarized in Table 1.
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,
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
more strongly extracted than Mo(VI) by the oximes and readily
displaces any extracted Mo(VI) from the organic. If excess copper is
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
electrolyte. In addition, Mo(VI) strips readily on the alkaline side so

1) The chemistry of Mo(VI) and V(V) on the acid side is quite complex.
They do not normally present a problem in copper solvent extraction circuits.

10

These conditions include:

The nature of the reagent.
The nature of the anions present in the aqueous solution.
The metal and reagent concentrations.
The oxidation state of the metal.
The pH of the aqueous feed solution.
The temperature at which extraction occurs.
The organic-aqueous contact time.
Modern metallurgists have a broad spectrum of copper extractant
formulations based on the aldoximes and ketoxime available to aid
them in developing effective recovery schemes for copper from a
broad range of leach solutions. As can be seen from a comparison of
the Cu pH isotherms in Figures 1 and 2, the aldoximes by themselves
are much stronger copper extractants than is the ketoxime. While
their extractive strength is a potential advantage, it is also a problem.
The aldoximes do not readily give up the extracted copper when
contacted with typical lean electrolyte solutions that are generated by
standard copper tank house operations. As a result, only a relatively
small percentage of the overall loading capacity is utilized in the
transfer of copper from extraction to stripping (Net Transfer).
Two approaches have been utilized to increase the net transfer of
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
readily than one would expect based on a simple combination of the
properties of the two components1,2. Blending the two components
results in no significant impact on copper loading capacity in
extraction while greatly improving stripping. This translates into an
increase in copper net transfer capability relative to an aldoxime by
itself. As illustrated in Figure 3 and Table 2, increasing the proportion
of ketoxime relative to aldoxime results in increased ease of stripping
(lower residual copper on the stripped organic) consistent with a
decrease in extractive strength. The decrease in extractive strength
is also reflected in the fact that the net transfer capability falls off
faster as the acid concentration increases (lower pH).

Figure 3: Effect of Increasing LIX 84-I Content on Stripping

of Cu and Cu Net Transfer with Non-modified
Aldoxime/Ketoxime Blends*
4
Net Transfer@ pH 2.0

3.5

Net Transfer@ pH 1.5

3
Cu Conc (g/L)

Consideration of extraction isotherms and selectivity data allow the

metallurgist to develop metal separation schemes. Where such data
is not available for a particular system, one can develop the required
information by screening the reagent against the metals most likely to
be found in the aqueous feed solutions of interest under conditions
similar to those expected in the solvent extraction process. The
resultant selectivity data holds only at the conditions under which it is
determined. Small changes in the test conditions can result in
significant shifts in the extraction isotherms and selectivity.

2.5
2
Stripped Organic
1.5
1

Increasing Ketoxime Content:

Weaker Extractant, More readily
Stripped, Higher Net Transfer

0.5
0

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
adjusted to give a Cu max load of 5.6 g/L copper under the conditions of the BASF Oxime
QC procedure. The organics were then contacted twice with an aqueous strip solution
containing 35 g/L Cu and 160 g/L sulfuric acid at an O/A =1 by shaking for 15 minutes.
The resultant stripped organics were assayed for copper content and then contacted with
aqueous solutions containing 6 g/L Cu at pHs of 2.0 and 1.5 at an O/A = 1 by shaking for
15 minutes to yield loaded organics. The copper contents of the loaded organics were
determined. The Cu Net Transfer was then determined by subtracting the copper
concentration of the stripped organic from that of the corresponding loaded organic.

Table 2: Proportions of LIX 84-I and LIX 860N-I in Standard

Non-modified Reagents
Reagent

% v/v LIX 84-I

% v/v LIX 860N-I

LIX 84-I1)

100

LIX 937N

70

30

LIX 984N

50

50

LIX 973N

30

70

LIX 860N-I2)

100

1) Ketoxime dissolved in a hydrocarbon diluent.

2) C9 aldoxime dissolved in a hydrocarbon diluent.

11

The second approach takes advantage of the fact that the aldoxime
will form complexes by hydrogen bonding with a wide variety of
chemical compounds3,4. The most commonly used classes of
compounds in commercial formulations are alkyl phenols as well as
higher molecular weight alcohols and esters. These materials are
commonly referred to as thermodynamic modifiers in this application.
Increasing the relative amount of the thermodynamic modifier results
in a shift in performance similar to that observed with the ketoxime as
illustrated in Figure 4 where LIX 860N-I represents no modifier and
the level of modifier, an ester, increases as one progresses from LIX
654N-LV to LIX 684N-LV, the most heavily modified formulation in
the series. Formulations consisting of a mixture of a thermodynamic
modifier with an aldoxime are classified as modified reagents or
modified aldoximes.

Figure 4: Effect of Increasing Ester Modifier Content on

Stripping of Cu and Cu Net Transfer with Modified Aldoxime
Reagents*
4
Net Transfer@ pH 2.0

3.5
3
Cu Conc (g/L)

By blending the aldoxime and ketoxime in varying proportions, BASF

Mining Solutions can tailor a reagent to fit the specific extraction and
stripping requirements of a particular application. Formulations
consisting of mixtures of an aldoxime with ketoxime are classified as
non-modified reagents or blends.

Net Transfer@ pH 1.5

2.5
2

Stripped Organic

1.5
1
0.5
0

Increasing Ester Content:

Weaker Extractant, More readily
Stripped, Higher Net Transfer
LIX
860N-I

LIX
654N-LV

LIX
664N-LV

LIX
674N-LV

LIX
684N-LV

* 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

based on C-12 aldoxime.
2) Dependent on the particular thermodynamic modifier used in the formulation.

3) Dependent on the composition of the leach liquor and the modifier.

4) In many cases, the presence of thermodynamic modifiers increases
crud formation.

12

One can also blend thermodynamic modifiers with mixtures of

aldoxime with ketoxime to form a third class of extractant formulations,
modified aldoxime/ketoxime blends. BASF Mining Solutions has the
capability of offering all three classes of extractant formulations.
A general comparison of the copper extraction characteristics of
ketoxime, aldoximes, non-modified blends and modified aldoximes
is summarized in Table 3.
Presents the operators of copper solvent extraction plants with a
wide choice of reagents from which to choose.
The availability of:
Pure aldoxime based extraction reagents
LIX 860-I, a C12 aldoxime based formulation and
LIX 860N-I, a C9 aldoxime based formulation
Modified aldoxime reagents
LIX 622N, and the ester based series: LIX 654N-LV,
LIX 664N-LV, LIX 674N-LV and LIX 684N-LV
Pure ketoxime based extraction reagents
LIX 84-I and LIX 8180
Non-modified aldoxime/ketoxime blends
LIX 973N, LIX 984N, and LIX 937N
Modified aldoxime/ketoxime blends
LIX 1552N-LV
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.

Modified aldoxime reagents have excellent metallurgical properties

even at low temperatures, low pHs or when the copper content of
the leach liquor is very high and high copper recoveries are needed.
However, in many cases, the use of a modified aldoxime formulation
carries with it higher entrainment rates and/or greater crud generation
resulting in increased carryover of impurities to the electrolyte and
higher reagent consumption per ton of copper produced6,7,8.
The non-modified aldoxime/ketoxime mixtures also operate well at
lower pHs, lower temperatures, and with leach liquors having a
higher copper content. They tend to be slightly slower kinetically at
lower temperatures depending on the ketoxime content of the
formulation as compared to modified aldoxime formulations. They
also tend to be slightly less selective for copper over iron as compared
to an ester modified aldoxime formulation. In terms of physical
performance under a wide variety of conditions, they tend to give
more stable mixer continuities, lower entrainment of aqueous in the
loaded organic and generate less crud than modified aldoxime
formulations. Some of these physical advantages can be attributed
to the fact that these reagents are the lowest density and lowest
viscosity copper solvent extraction reagents available.
Clearly there is not a single reagent of choice for the extraction of
copper from sulfuric acid leach liquors. Your BASF Mining Solutions
technical representative can help you decide on the best reagent for
your needs.

13

3.2 D
 evelopment of a Cu SX
Process Flow Sheet

Factors for Consideration

When developing a process for recovery of copper by solvent
extraction, there are a number of factors to consider:
Type of leach and nature of the ore
Composition of the pregnant leach solution
Nature of the final copper product and process required to
produce it
Operational philosophy
The primary commercial application for modern phenolic oxime
based copper solvent extraction reagents has been recovery of
copper from dilute sulfuric acid leach solutions. These solutions
result from leaching of copper oxide and/or secondary sulfide ores
using various leaching technologies including dump, heap, in-situ,
thin layer, vat, and agitation1,2,3. The choice of methodology is
dependent on the nature of the ore and the ore grade. A variety of
technologies are currently being investigated for the leaching of
primary copper sulfide concentrates4,5,6,7. Since leaching is a critical
step in the overall process of Leach-SX-EW, BASF strongly
recommends that one thoroughly investigate the leaching
characteristics of their ore8,9,10,11. If you cannot bring the copper into
solution effectively, it cannot be extracted. Money spent on up front
leaching studies typically proves to be a wise investment.
Depending on the leaching technology and ore grade, pregnant
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
typical sulfuric acid leach solutions that have been treated by solvent
extraction are summarized in Table 1.

Table 1: Typical Sulfuric Acid Leach Solutions

Leach Type

Cu (g/L)

pH

Dump, Heap, In-situ

<1 to 6

1.3 to 2.2

Ferric Cure, Thin Layer

3 to 6

1.5 to 2.2

Vat

5 to 50

1.6 to 2.0

Agitation

1 to 35

1.4 to 2.0

Concentrate

25 to 80

<1.0 to >2.0

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
contain anions such as chloride and nitrate. The concentration of
these impurities will vary widely depending on the ore, available water
sources and evaporation rate. Certain ore bodies in Chile contain
nitrate. Since nitrate is readily leached, the concentration of nitrate in
the resultant leach solutions may be up to 2530 g/L. Due to the lack
of fresh water, some operations successfully operate using sea water
for leaching resulting in up to 90 g/L of chloride in the leach solution.
While the presence of nitrate and chloride can cause problems in SXEW, methods have been developed to successfully deal with them12.
The nature of the leach, the ore type and climatic conditions may play
a role in the temperature of the pregnant leach solution delivered to
solvent extraction which in turn will determine the operating
temperatures in extraction and stripping. A typical heap leach solution
will range in temperature from about 20C to about 30C but may
drop to 10

15
C during harsh winter conditions and
/
or high
elevations. Colder temperatures will shift the extraction equilibrium to
the left (weaker extraction), affect the extraction kinetics and the
solution viscosities impacting overall extraction efficiencies and
physical performance of the extraction circuit. Vat, agitation and
concentrate leach solutions can be quite warm resulting in temperatures
in extraction of up to 45C. While the higher temperatures will result in
shifting the extraction isotherm to the left13, increasing kinetics and
lowering solution viscosities, hydrolytic degradation of the reagent may
become more of an issue depending on reagent type.
Copper is typically recovered as copper cathode but has also been
recovered as copper sulfate crystal14,15,16. Most copper EW tank
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
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
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
experience in some tank houses, slightly higher quality copper is
obtained when plating from sulfuric acid concentrations at the lower
end of the acid concentration range17. The tank house parameters in
terms of copper and acid in the exiting spent electrolyte and incoming
rich electrolyte are determined in part by the operating philosophy of
the plant manager. These parameters combined with the strip staging
and nature of the oxime copper extractant will impact how completely
the loaded organic is stripped and how much free reagent will be
available to carry out extraction.

14

Along with the evolutions in leaching technologies, reagent

technologies and tank house operations, there have been significant
developments in the understanding of the interaction of reagent and
circuit staging which can result in lower costs and more efficient
copper production18,19,20,21. A listing of circuit configurations that have
been used in commercial operations over the years is summarized in
Table 2.

them to use a series parallel flow scheme or some other combination

of stages to be able to treat the required additional flow. Making
allowance for potential plant alterations during the planning stages
will provide the plant with the flexibility to meet future requirements27.
When treating a leach solution containing significant amounts of
chloride, nitrate, iron, or manganese, the addition of a loaded organic
wash stage should also be considered to minimize the transfer of
these impurities to the tank house28.

Table 2: Commercial Solvent Extraction Circuit Configurations

Circuit Type

Configuration*

Stages
per Train

Series

4E x 3S

Series

4E x 2S

Series

3E x 2S

Series

2E x 2S

Series

2E x 1S

1E x 1S

Series Parallel

2E x 1EP x 1S

Series Parallel

2E x 1EP x 2S

Cross Flow

1E x 1EP x 1EP x 1S

* E represents extraction stage, EP refers to a parallel extraction stage,

BASF Mining Solutions produces three oximes, C9 aldoxime (LIX

860N-I), C12 aldoxime (LIX 860-I) and ketoxime (LIX 84-I), which
serve as the basis for formulation of a wide range of modified and
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
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
aldoxime to take advantage of their stability. The relative stability of
the oximes is: ketoxime >C12 aldoxime >C9 aldoxime. When dealing
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
a leach solution containing high levels of copper, recovery will be
limited by the corresponding increase in acid concentration in the
aqueous as the copper is extracted. The logical choice would be a
reagent formulation containing higher levels of an aldoxime or a less
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
extraction in series and 1 strip stage can also be effectively used31,32.
When considering reagent choices, contact your local BASF Mining
Solutions technical representative who has the knowledge of the
reagents and experience to assist you in making the best reagent
selection for your individual application.

Figure 1: Sequential Circuit

and S refers to a strip stage

The most common circuit configurations in use today are 2E x 2S,

2E x 1S, and 2E x 1EP x 1S. More recent developments include the
use of the Split Circuit concept and Sequential Circuit (Figure 1)
concept to reduce acid consumption and increase copper recoveries
in agitation leach circuits22,23,24,25,26.
While many plants opt to employ a simple circuit consisting of 2
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,
they must be able to treat more leach solution. This may require
modifying the piping or adding additional extraction stages to allow

Acid

Milled
Ore Solids
Water

Leach 1

Tails
S/L 1

Leach 2

CCD
Co
Recovery

SX 1

S/L 2

SX 2

SX 3

Neut

Tails

15

3.3 L
 aboratory Development
of an SX Circuit

Given a pregnant leach solution (PLS), how does one develop a

process for recovering the metals of interest? The first step is to
determine if the solution is typical of what would be expected in
normal operation. Work carried out on a non-typical solution is often
wasted effort. The composition of the solution with regard to metals,
metal concentration, pH, presence of ammonia and its concentration,
presence of chloride or nitrate and their concentrations, etc., must
be determined. Given the composition, one can then begin to make
judgments with regard to which metals can be separated based on
available extraction isotherms. If the data for some of the metals is
not available, the extractant(s) being considered should be screened
against these metals. Given this information, one can then determine
a strategy for recovering commercially viable metals by solvent
extraction under the given set of conditions. With this background,
circuit development work can now begin keeping in mind that all
parts of the total metal recovery process must fit together in a
workable manner.
As an example, consider development of a copper solvent extraction
circuit to treat a copper heap leach solution containing 2.5 g/L of Cu
and 1.30 g/L of total Fe at a pH of 1.80. Assume also that you want
a copper recovery of 90%.

Extraction and Strip Isotherms

While a variety of extractants can be used, LIX 984N, a widely used
non-modified blend of aldoxime and ketoxime, is particularly well
suited to treat the leach solution under discussion. Based on previous
experience with similar solutions, one can expect LIX 984N to
transfer 0.240.30 g/L Cu per 1% v/v in a circuit consisting of 2
stages of extraction and 1 stage of stripping, a common choice in
modern plants. Since the pH is 1.80, we will assume that the copper
transfer will be somewhere in the middle to lower end of the range
(0.26 g/L of copper/1% v/v LIX 984N). Using the following equation,
one can then calculate the approximate reagent concentration
required to meet the stated goal of 90% recovery.

Equation1
[2.50 g/L Cu x (0.90)]/0.26 g/L Cu per % v/v = 8.7% v/v LIX 984N

To determine the extraction and strip isotherms, a solution containing

8.7% v/v LIX 984N was prepared in a suitable diluent and used in a
series of shakeouts with the leach solution and the expected strip
solution. The organic was first contacted at an organic to aqueous
volume ratio (O/A) of about 1 with the leach solution by vigorous
shaking in a separatory funnel for about 3 minutes. The aqueous

phase is discarded after the phases have separated. A portion of the

resultant copper loaded organic (LO) is then contacted with vigorous
shaking three times with fresh rich electrolyte (RE) at an O/A = 1. Rich
electrolyte is the aqueous acid strip solution that is expected to exit
the strip stage. In this exercise, we will assume that the RE contains
50 g/L Cu and 160 g/L of sulfuric acid. The resultant organic will
closely approximate a stripped organic (SO) one would expect to
generate in a continuous circuit having one strip stage. This process
serves not only to generate a SO for the isotherm determination but
also serves to wash out any low molecular weight impurities from the
manufacturing process.
The extraction isotherm is then determined as follows:
Vigorously contact the freshly prepared SO with leach solution for
310 minutes at various O/A ratios (Typically 10/1 to 1/5).
Typically requires 67 points for a good isotherm.
Contacting can be carried out in separatory funnels or by
stirring in BASF QC mixer boxes. (When using separatory
funnels, longer contact times are recommended to insure that
true equilibrium is achieved.)
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
temperature and samples of organic and aqueous must be
collected at the expected temperature. For further information,
contact your BASF technical representative.
After allowing the phases to separate, samples of the respective
organic and aqueous samples are collected, filtered and saved
for analysis. The organic is analyzed for copper (and perhaps
iron) while the aqueous is analyzed solely for copper.
The data is summarized in Table 1 and is plotted in Figure 1.
Accurate measurement of the organic and aqueous volumes
used for each shakeout will allow one to calculate a mass
balance for each point. Mass balances should be very good
for O/A ratios in the range of 5:1 to 1:5. If the mass balance is
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.
For copper extraction with a phenolic oxime type extractant, the
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 carefully define the area around the bow in the curve as
accurately as possible. If need be, additional shakeouts might
be required at O/A ratios that will generate points in the desired
area of the curve. These samples should be analyzed in a block
along with the previous samples to eliminate analytical
variations.

16

Figure 2: Strip Isotherm

5.0

60

4.0

50

Aqueous g/L Copper

Organic g/L Copper

Figure 1: Extraction Isotherm

3.0

2.0

1.0

0.5

1.0

1.5

2.0

2.5

40

30

20

3.0

Aqueous g/L Copper

0.5

1.0

1.5

2.0

2.5

3.0

Organic g/L Copper

Table 1: Equilibrium Isotherm Extraction Data

Table 2: Equilibrium Isotherm Stripping Data

O/A

Organic
(g/L Cu)

Aqueous
(g/L Cu)

O/A

Organic
(g/L Cu)

Aqueous
(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

Leach Solution

SE
2.50

30.7

3.5

4.0

17

Isotherms are specific for the conditions under which they are
determined. Changing one of the parameters, i.e., the reagent
concentration, the copper concentration of the aqueous phase, the
pH of the leach solution, the acid concentration of the strip solution,
temperature1, etc., will result in a different isotherm. In most cases,
small changes in one or two of the parameters result in such small
changes that it would not necessitate generating a second isotherm.

McCabe-Thiele Diagrams
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.
As an example, consider the extraction isotherm in Figure 1 and
assume:
The SO entering the last extraction stage contains 1.80 g/L Cu.
The leach solution contains 2.50 g/L of Cu.
The advance flow rates of both SO and leach solution are equal
(O/A = 1).
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
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
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
SO line until it intersects the vertical line representing the copper
content of the leach solution. One can then begin to draw in the

Figure 3 does not represent a McCabe-Thiele diagram at true

equilibrium. If the diagram represented true equilibrium, the operating
line would intersect with the SO line and the isotherm line at the point
where the isotherm line intersects the SO line. The construction of a
McCabe-Thiele diagram at true equilibrium is an iterative process.
Assuming that the O/A flow ratio remains unchanged, one would
draw a new operating line parallel to the first operating line starting
from a point approximately one half the distance from the isotherm
line to the raffinate line. One would then draw in the steps as
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
Cu and a LO of 4.17 g/L of Cu.

Figure 3: McCabe-Thiele Extraction Isotherm

First Approximation
5.0
LO
4.0

Feed = 2.50 g/L Cu

LO is contacted at various O/As (Typically 10/1 to 1/4) with a

typical copper electrolyte from an electrowinning tankhouse. This
is known as strip electrolyte (SE) or lean electrolyte (LE). In our
example, we have taken a LE containing 30.7 g/L Cu and 190
g/L sulfuric acid.
The organic and aqueous phase are contacted by vigorous
shaking or mixing. The temperature in stripping is typically higher
than in extraction, 3040C, so contacts should be carried out
in temperature controlled jacketed vessels.
After equilibration, the phases are allowed to settle, samples of
each phase taken and filtered, and then analyzed for copper.
The data is summarized in Table 2 and plotted in Figure 2.

steps representing the staging. Draw a horizontal line from the point
where the operating line intersects the vertical leach solution line to
the extraction isotherm and then draw a vertical line down from the
intersection point of the horizontal line with the isotherm to the
operating line creating a step. Repeat the process by adding another
horizontal line and another vertical line as illustrated in Figure 3 to
create a second step which completes the McCabe-Thiele diagram
for a two stage extraction circuit. Each step represents a single stage
of extraction. This diagram would predict that it is possible to achieve
a raffinate of 0.22 g/L of Cu and a LO containing 4.30 g/L of Cu
(Figure 3) with two stages of extraction.

Organic g/L Copper

The strip isotherm is then determined as follows:

3.0

2.0

1.0

SO

0.5

Raff. = 0.22

1.0

1.5

Aqueous g/L Copper

2.0

2.5

3.0

18

Figure 4: McCabe-Thiele Extraction Isotherm Iterative Process

5.0

Feed = 2.50 g/L Cu

Organic g/L Copper

LO
4.0

3.0

2.0

1.0

SO

0.5

1.0

1.5

2.0

2.5

3.0

Aqueous g/L Copper

Raff. = 0.15

The LO contains 3.90 g/L of Cu.

The desired rich electrolyte (RE) contains 51 g/L of Cu.
The strip electrolyte (SE) contains 30.7 g/L of Cu.

Figure 5: McCabe-Thiele Strip Isotherm Single Stage

Loaded Organic = 3.90 g/L Cu

60

Aqueous g/L Copper

RE
50

40
SE
30
SO = 1.77
0.5

1.0

1.5

2.0

2.5

Organic g/L Copper

A two stage McCabe-Thiele strip diagram is constructed in a fashion

similar to that described for the two stage McCabe-Thiele extraction
diagram. It predicts a SO of 1.12 g/L of Cu when building a RE of 51
g/L of Cu and operating at an O/A flow ratio of 7.3/1.

Number of Extraction/Strip Stages Required

The construction of an equilibrium McCabe-Thiele diagram for one

stage of stripping is very simple. Consider the stripping isotherm in
Figure 2 and assume:

20

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
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.
This line represents the expected SO (1.77 g/L Cu). A third line is
then added representing the SE. The operating line is then drawn
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.
(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.

3.0

3.5

4.0

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

decide on the staging requirements. The capital cost of a stage must
be weighed against the potential benefits that the stage provides.
Consider the use of one stage of stripping versus two stages of
stripping in the example above:
Two strip stages will give a SO containing 1.12 g/L of Cu which
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
turn leads to a net copper transfer of 2.13 g/L Cu.
Due to differences in net copper transfer, a circuit operating with
one strip stage will require a reagent concentration approximately
1.3 times higher than in the case of a circuit with two strip stages
in order to achieve equivalent performance in terms of copper
recovery in extraction.
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.
Comparison of the capital costs for the additional strip stage
versus the increased operating costs due to the increased
reagent usage allow one to make a purely economic decision on
the strip stage requirements.
The increased reagent concentration needed with one strip stage
compared to having two strip stages will depend on the nature of the
leach liquor, the desired copper recovery and the particular reagent
under consideration.

19

Continuous Copper SX Circuit

With the development of modern reagent technology, most
companies elect to treat dump leach liquors in SX plants consisting
of two stages of extraction and one stage of stripping (2E-1S plants).
To determine how such a plant might actually function, a 2E-1S
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.
A mixer retention time of 2.6 minutes was selected simply because
most copper SX plants operate with 23 minutes of mixer retention
depending on the leach solution conditions, the mixer design, and
the company operating philosophy.

When at equilibrium, the analysis for copper and acid do not change
as the circuit runs so long as the flows, the composition of the leach
solution, the composition of the SE, and the nature of the organic
phase do not change.

To achieve good metallurgical results and maximize the amount of

information collected, several things are important:

The circuit behavior will reflect the interdependence of the extraction

and stripping operations. For example, a loss of stripping efficiency
will result in a higher copper content on the stripped organic which in
turn will result in less available reagent for extraction and which will
lead to higher raffinates. To compensate for a loss in stripping
efficiency, one must operate the circuit with either a slightly higher
reagent concentration or a slightly higher organic to aqueous
advance ratio in extraction in order to maintain copper recovery.
Alternatively, one must accept a slightly lower copper recovery.

Flow rates must be accurately set and continually monitored.

Small changes result in fluctuations in the circuit performance
requiring additional time to achieve equilibrium.
Proper mixing requires that mixer dispersions be maintained at
an O/A near 1.
Recycles should be employed where necessary to maintain
the appropriate mixer dispersions.
Mixer turbines must turn fast enough to maintain good mixing
and pumping action but slow enough to avoid causing heavy
entrainment.
The circuit should be sampled frequently and the samples must
be rapidly and accurately analyzed shortly after collection.
This allows the operator to closely monitor the circuit and
observe changes in circuit behavior as operating parameters
are changed.
After changes in an operating parameter, the circuit should be
allowed to run until overall equilibrium is once again achieved.
A circuit is at equilibrium when there is a good metal balance and a
good metal-acid balance across the whole circuit as well as across
each stage:
At equilibrium in extraction, the metal extracted from the aqueous
phase in an extraction stage in a given amount of time is equal to
the acid equivalent gained by that same aqueous phase in the
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.

In order to balance metal and acid values, accurate solution analyses

and solution flow rates have to be known. In addition, solution
samples should be taken from the rear of the respective settler for
that stage. When possible, it is best to pull the samples at those
points easiest to access and least likely to upset the circuit.

Metal transfer in an extraction stage is typically between 85% to

95% of theoretical while metal transfer in a strip stage is usually
>95% of theoretical in modern plants due to the improvements in
mixer design. As a result, the values predicted by equilibrium
McCabe-Thiele diagrams for the aqueous and organic phases exiting
a given stage are seldom achieved in an operating plant. As an
example, compare the organic and aqueous values predicted by the
McCabe-Thiele diagram in Figure 3 with the values generated in a
continuous laboratory circuit using the same aqueous feed solution,
organic solution and SE solution (Table 3, Figure 6).
The circuit achieved a raffinate of 0.28 g/L Cu and a loaded organic
of 4.08 g/L Cu as compared to the raffinate of 0.22 g/L Cu and a
loaded organic of 4.24 g/L Cu as predicted by the first iteration
McCabe-Thiele extraction diagram (Figure 3). The stripped organic of
1.80 g/L Cu is close to the 1.77 g/L Cu predicted by the McCabeThiele strip diagram (Figure 5).

20

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
95% efficiency as shown in Figure 6. The resultant McCabe-Thiele
two stage extraction diagram predicts a raffinate of 0.28 g/L Cu, a
value identical to that achieved in the circuit run.

5.0

LO
4.0

Feed = 2.50 g/L Cu

Generating an isotherm helps to develop a feel for the system.

The isotherm will usually reflect any unusual metallurgical
behavior characteristics of the system.
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
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
extraction.

Figure 6: McCabe-Thiele Extraction Isotherm Circuit Data

Organic g/L Copper

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

3.0

SO

2.0

1.0

0.5
Raff. = 0.28

1.5

2.0

2.5

Aqueous g/L Copper

Table 3: Circuit Profile Data with 8.7% v/v LIX 984N

in Escaid 110
Sample

The feed chosen for the above example is typical of the leach solution
generated by many copper leach operations and represents one of
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
in a similar fashion as described in the above example. The extraction
and strip isotherms as well as the circuit staging can, however; be
significantly more complex. With complex metal extraction systems,
the initial circuit may have to be modified several times before the
best recovery scheme is worked out.

1.0

Organic

Aqueous

g/L Cu

g/L Fe

g/L Cu

g/L Fe

Extraction
Stage 1

4.08

0.002

1.31

Extraction
Stage 2

2.88

0.0038

0.28

Strip Stage

1.80

N.D.

51.2

0.026

LE

30.7

0.010

Aqueous Leach

2.50

1.30

3.0

21

4. C
 opper Extraction
from Ammoniacal Solution

It is more selective.
Metals such as iron and manganese are not soluble in the leach
liquor.
It can be used to treat ores containing high levels of acid
consuming gang and is less corrosive than acid leach systems.
It is also well suited for recovery of copper from secondary
sources such as scrap copper wire, consumer electronics such
as printed circuit boards, copper drosses, and smelter flue
dusts1,4,5,6.
Due to the volatile nature of ammonia, leaching is typically carried out
in closed vats to minimize ammonia losses1,3. Recent developments
in use of ammonia for heap leaching suggest that it may become
practical as well7.
General Mills Mining Chemicals division (now a part of BASF Mining
Solutions) demonstrated that copper could be extracted from
ammoniacal leach solutions using LIX 63 and introduced it to the
industry in 19634. LIX 63, an alpha hydroxy oxime, was quickly
supplanted by LIX 65N, a hydroxy benzophenone oxime, which
in turn has been replaced by LIX 84-I, a acetophenone oxime
(Ketoxime). The variation in extractive behavior for LIX 84-I with
copper, nickel and zinc as a function of total ammonia concentration
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
84-I (RH) is shown below (Formula 1).

Increasing the ammonia concentration in the aqueous shifts the

equilibrium to the right. Ammonia competes with the reagent
for the metal ion. As illustrated by the ammonia isotherms, extraction
decreases as the ammonia concentration increases. This suggests
that under some circumstances one might be able to strip the metal
from the loaded reagent with high concentrations of ammonia.
The ammonia isotherms in Figure 1 show that copper(II) is more
strongly extracted from an ammoniacal solution than is nickel (II)
suggesting that it should be possible to selectively extract copper
away from the nickel. The feasibility of such a separation was
demonstrated using LIX 65N8. An alternative separation scheme is
suggested by considering the LIX 84-I ammonia isotherms and pH
isotherms. While copper and nickel are relatively strongly extracted
from ammonia by LIX 84-I, the corresponding pH isotherms show
that nickel is readily stripped at a pH of 2.53.0 where copper is
strongly extracted. Co-extraction of nickel and copper with the same
organic stream followed by a pH controlled wash to remove small
amounts of co-extracted ammonia and then selectively stripping the
nickel and copper loaded organic using pH control to give a copper
free, nickel-rich solution and a copper rich solution containing a small
amount of nickel9,10.

Figure 1: Metal Extraction by LIX 84-I as a Function of Total

Ammonia Concentration
100

80
Metal Extraction (%)

The use of ammonia as a leaching agent for copper has been

practiced on a commercial scale since the early 1900s. In 1916,
Kennecott Copper Company and Hecla Mining Company began to
recover copper from gravity plant tailings using an ammoniacal leach.
The copper was recovered as a copper oxide precipitate after
stripping the ammonia from the solution with steam. Ammonia has
been used to leach copper from native copper ores, copper oxide
ores and copper sulfide ores including chalcopyrite1,2,3. The use of
ammonia for the leaching of copper from ores has a number of
advantages:

Ni

Cu

60

40
Zn
20

50

100

150

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)

200

250

22

While the study of pH isotherms, selectivity data and ammonia

isotherms allows the conceptualization of a metal separation
flowsheet, it does not provide one with the specific details on how to
most effectively carry out the separation in the most efficient, costwise manner. Laboratory work is still required to determine the
precise extraction and stripping conditions, circuit staging
requirements, etc.

amounts of entrained aqueous. This will result in transfer of ammonia

and chloride to the strip circuit leading to the buildup of ammonium
sulfate and chloride in the strip solution. Both of these chemical
species are undesirable. The excess ammonium sulfate must be
disposed of and high chloride levels can lead to chlorine gas
formation in the electrowinning tankhouse. The stripped organic can
also transfer sulfuric acid to extraction by entrainment leading to
undesirable buildup of ammonium sulfate in the regenerated etchant.
Typically, the aqueous phase in the wash stages would be a dilute
acid stream. By coupling the two wash stages as illustrated, a weak
acid solution can be generated by scrubbing the stripped organic in
W2 to remove the entrained acid and the resultant weakly acidic W2
aqueous can then be fed to W1 where it contacts the loaded organic.
Scrubbing with dilute acid removes the ammonia from the loaded
organic. The resultant W1 aqueous can then return to W2. This
arrangement results in an efficient use of fresh water for washing and
reduces reagent consumption11,12.

The manufacture of printed circuit boards (PCB) involves selectively

etching copper from the board leaving the desired circuit. Ammoniacal
etchants based on either ammonium chloride or ammonium sulfate
are typically used. As the concentration of copper in the etchant
increases, the efficiency of the etching process decreases. Typically,
at about 140 g/L of copper, the etchant is considered to be spent.
The spent etchant can then be regenerated for reuse by extraction of
the copper. This can be carried out on-site or the spent etchant can
be sent off to a central treatment facility. The recovery of copper and
regeneration of the spent etchant by solvent extraction with LIX 84-I
has been practiced commercially for a number of years and BASF
has had previous experience with a number of these operations
globally. A typical layout for a PCB spent etchant copper solvent
extraction plant is shown in Figure 2.

Extraction reagents based on ketoxime such as LIX 84-I and LIX

84-IT are favored for the recovery of copper from ammoniacal
solutions. Copper is strongly extracted by ketoxime from an
ammoniacal solution and is readily stripped with acid resulting in very
high net transfer. The high extractive strength of aldoxime based
formulations is not required to achieve high recoveries and they are
not as readily stripped with acid so net transfers are lower. LIX 84-IT
is based on ketoxime modified with a small amount of an ester
modifier. Addition of a small amount of modifier reduces ammonia
co-extraction13.

Two wash stages are employed to minimize or prevent transfer of

impurities between extraction and stripping. Due to the high
concentrations of ammonia and ammonium ion in the aqueous feed
solution, co-extraction of ammonia by LIX 84-I will occur. In addition
to the co-extracted ammonia, the loaded organic will contain small

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

Raffinate

Loaded Organic
W1 Aqueous

E2

Spent Etchant

W1

S1

E3

E1

S2

W2

Spent
Electrolyte

Strong
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/
cyclone/scrubbing

Ore pretreatment

H2SO4
Sulfur, steam

Tails

S
L
Hydroxide
precipitation pH 5.0

Air
CaO or MgO
Reject or
recycle to leach

CCD

Precipitation and
removal of iron

S
L
MgO is the preferred alkali as it
permits use of an ammonium
carbonate leach. CaO requires
an ammonium sulfate leach.

Hydroxide
precipitation pH 9.0

MgO or CaO

Rejection of
Mn2+, SO42+, Cr2+

Fe(SO4)2 disproportionates to
Fe2O3 and H2SO4, Ni, Cu, Co and
Zn leach as sulfates. Cr is Cr2+.

Autoclave acid leaching

S
L
Base metal hydroxide
filter cake intermediate

Belt filter

To ammonia
leach and SX-EW

24

With the increased interest in the recovery of nickel from laterite ores and
drawing on its experience in extraction of nickel from ammoniacal
solutions, BASF conceptualized a flowsheet for the recovery of nickel
from laterite ores. This flowsheet was further developed and implemented
by Cawse Nickel Operations9. The basic elements of the front half of the
Cawse process (Figure 1) are:

High Pressure Acid Leaching (HPAL) of the laterite ore.

Solid-Liquid separation.
pH adjustment to remove iron.
Further adjustment of pH to precipitate the base metals
(Ni, Cu, Co, Zn) as crystalline hydroxides.

The refinery portion (Figure 2) of the process includes:

Re-leach of the Mixed Metal Hydroxide Precipitate (MHP) with
ammonia under oxidizing conditions.
Solvent extraction of the nickel with a ketoxime,
LIX 84-INS.
Recovery of nickel cathode.
Recovery of cobalt from nickel raffinate by precipitation of cobalt
sulfide which can be further refined into high purity cobalt metal.

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

Base metal hydroxide

filter cake intermediate
Air/O2
NH3/CO2

To acid leach

Ammonia leaching

S
L
Steam stripping
and oxidation

Steam/air

Reject or return
to acid leach

Steam stripping to remove

free ammonia and to help
oxidize Mn and Co

S
L

Clarification to remove MnO

and other suspended solids

Peroxide to oxidize
all Co2+ to Co3+

Raffinate to Co
recovery H2S PPT

Nickel SX extraction
with LIX 84-INS
Loaded organic wash
Zn and NH3 removal

Nickel electrowinning

Nickel stripping

Stripped organic wash

Organic bleed
to Co and Cu strip
and reoximation

25

The Cawse flowsheet possesses a number of advantages relative to

other proposed flowsheets for treatment of laterite ores9. They
include:

A schematic of the Cawse SX plant is shown in Figure 39. The

chemistry of extraction and stripping is summarized in the following
equations (Formula 1).

Process has been industrially proven having produced

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.
The MHP can be stockpiled allowing a steady feed to the nickel
refinery portion of the plant when the HPAL is not operating.
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.
Use of MgO for the hydroxide precipitation minimizes gypsum
formation downstream from the re-leach of the MHP.
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.
Ammonia is recycled resulting in low ammonia consumption per
ton of nickel produced.
Overall metal recovery is very high due to recycling of
intermediates
Process employs only one SX circuit and one extractant type
removing the potential for cross contamination of the circuit
organics.

Figure 3: Schematic of Cawse SX plant

PLS

Raffinate
E1

E2

E3

Wash Aq
SOW

Dil. acid wash Aq.

LOW 2

LOW 1

S1

S2

S3

S4

Nickel Electrowinning

Formula 1

Extraction

Stripping

2 RH(Organic) + Ni(NH3)4+2 (Aqueous)

R2Ni(Organic) + H2SO4 (Aqueous)

R2Ni(Organic) + 2 NH3(Aqueous) + 2 NH4+(Aqueous)

Ni+2(Aqueous) + SO4-2(Aqueous) + 2 RH(Organic)

26

Successful operation of an ammoniacal nickel SX circuit must take

into consideration a number of factors:
As nickel is extracted, the concentration of ammonia and
ammonium ion in the aqueous phase increases, effectively
limiting nickel transfer into the organic phase.
Copper, zinc, cobalt and manganese are typically present in the
MHP ammoniacal re-leach liquor and will co-extract with the
nickel. Cobalt(+2) and manganese(+2) will be converted to higher
oxidation states on the organic making them difficult to strip and
resulting in a buildup in concentration over time poisoning the
organic.
Due to the nature of the organic and ammoniacal solutions, the
interfacial tension is quite low relative to the interfacial tensions
observed when extracting copper from acidic sulfate solutions.
Nickel electrowinning limits the pH of the incoming rich
electrolyte to 3.04.0.
Ammonia and ammonium ion can be transferred to strip by both
entrainment and chemical loading
Potential for formation of metal amine sulfate salts which may
precipitate in lines or alter chemistries in some fashion.
Nickel stripping kinetics are slow.
Choice of MHP re-leach solution impacts extraction kinetics.

Use conservative settler design, settler flux of 34 m3/

m2/hr in extraction and 35 m3/m2/hr in stripping, with aqueous
continuous mixing in all stages.
Use S1 to consume excess acid in aqueous and control pH of
rich electrolyte at 3.04.0.
Use wash stages to remove ammonia/ammonium ion from the
loaded organic and entrained acid from the stripped organic.
Use 57 minute mixer retention times in stripping and operate
at 5060C.
Increase extraction mixer retention times slightly when using
ammonia/ammonium sulfate leach conditions.
Analytical methodology for measurement of ammonia transfer on
loaded organic, determination of cobalt(+2) concentration in
leach liquor, and determination of the concentration of sodium
lauryl sulfate in electrolyte.
The treatment of ammoniacal leach solutions containing higher
copper concentrations than those normally seen in laterite processing
such as those generated by autoclave leaching of nickel sulfide
concentrates has been proposed9. Use of pH controlled selective
stripping of nickel and copper have shown in the laboratory that a
high purity nickel strip solution containing up to 150160 g/L of
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
re-oximation to re-generate oxime hydrolyzed under reductive
strip conditions.

For further information concerning the extraction of nickel from

ammoniacal solutions contact your nearest BASF Mining Solutions
representative.

27

6. B
 ASF Alamine and
Aliquat Reagents

BASF offers a series of tertiary amines (Alamine reagents) and a

quaternary amine (Aliquat 336) (Table 1) for metal extraction. The R
groups are alkyl hydrocarbon chains which may be branched or
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
processing by solvent extraction. BASF currently offers three
Alamine reagents for metal solvent extraction applications but has
the capability to produce other tertiary amines if the need should
arise. Aliquat 336 is derived from quaternization of Alamine 336
with methyl chloride.

Tertiary amines have the

general formula:

Alamine 308

R = Iso octyl (Highly Branched C8 Chain)

Alamine 336

R = Mixed C8 and C10 (Straight Chain)

Alamine 304

R = C12 (Straight Chain)

R
N

Alamine Reagents

Aliquat 336 has the

general formula:

R
R

Table 1: Alamine and Aliquat Extractants

Aliquat Reagent
N+

CH3

CI

The tertiary amines and quaternary amine are examples of the ion
pair class of extractants. Protonation of the tertiary amine results in
formation of an organic ammonium cation which then forms a
hydrocarbon soluble ion pair with an anion as illustrated in the
following equations (Formula 1).

Aliquat 336

R = Mixed C8 and C10 (Straight Chain)

The extent to which the protonated amine will exchange one anion
for another is dependent on the relative affinity of the two anions for
the organic ammonium cation and the relative stability of the two
anions in the aqueous phase (Formula 2). Typically, extraction favors
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

Stripping with a base typically results in the best stripping and in the
fewest number of strip stages. In some cases, changes in pH will
result in changes in the nature of the extracted anionic species
making stripping more favorable. For example, polymolybdates
which are strongly extracted on the acid side are converted to
molybdate at pHs greater than 8.0, which is much less strongly
extracted than the polymolybdate.
The chemistry of extraction and stripping with Aliquat 336 differs
from that of the tertiary amines due to the fact that the quaternary
amine functionality is always positively charged. While the same
considerations of anion size and relative charge determine the relative
ease of extraction of different anions, extraction of anions is not pH
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
basic leach solution. The biggest disadvantage to using a quaternary
amine type extractant is that it will not deprotonate so it is necessary
to use crowding with high concentrations of another anion as a
stripping strategy.
Alamine 308 is a tri-isooctyl amine. Its primary application is:
Separation of cobalt from nickel in acidic chloride systems1,2
Recovery of zinc from spent electrolyte solution3
Alamine 336 is a tri(n-C8, C10 alkyl) amine.
Principle applications are:
Recovery of uranium from acidic sulfate leach solutions
Recovery of molybdenum from acidic sulfate leach liquors
Recovery of vanadium(+5) from acidic leach liquors
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

Alamine 304 is tridodecyl amine. Its major applications are:

Recovery of molybdenum from acidic sulfate leach liquors
Extraction of organic acids such as citric acid from fermentation
broths8
Aliquat 336 is tri(n-C8, C10 alkyl) methyl ammonium chloride.
Its uses include:
Recovery of molybdenum from acidic sulfate leach liquors
Recovery of vanadium(+5) from acidic leach liquors
Rare earth separations9
Removal of arsenic from copper refinery electrolytes10
In general, any metal capable of forming an anionic complex in an
aqueous solution is a candidate for extraction by tertiary or quaternary
amines. Figure 1 summarizes some extraction data for Alamine 336
and/or similar amines for a wide variety of metal aqueous systems11.
Oak Ridge National Laboratory has carried out an extensive series of
studies with regard to the effect of chloride concentration and pH on
extraction of various elements as their chloride complexes by amines
or quaternary amines12. Figure 1 summarizes the extraction isotherms
for a number of metals as a function of chloride concentration in the
aqueous at pH 2 and 40C.

Figure 1: Extraction Isotherms for Alamine 336 as a Function

of Choride Concentration (pH = 2, 40C).
100

Mo
Zn

Cu

80

Fe2+

Fe3+
Extraction %

have a high charge density. The selectivity of extraction will also be

influenced to some extent by the relative amounts of the two anions
in the aqueous solution. While the choice of stripping agent depends
on the overall recovery process, there are two approaches that can
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
phase by contacting the organic with a concentrated aqueous
solution of another anion such as chloride. Alternatively and most
typical, the amine is deprotonated by contacting it with an aqueous
solution of a base such as sodium carbonate as illustrated in For
mula3.

Co

60

40

Sn

20
Mn
0

100

Ni, Cr
200

[CL], g/L.

300

29

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

Li

Be

Na

Mg

Al

Si

Cl

Ca

Ga

Ge

As

Se

Br

Rb

CS

Fr

Sc

Fe

Co

Cu

Zn

VI

III

II

II

II

bk

bh

Zr

Nb

Mo

Tc

Ru

Rh

Ag

Cd

In

Sn

Sb

Te

III

IV

VI

VII

IV

hj

vc

bcdg

abcdlm

bh

La*

Hf

Ta

Re

Os

Hg

TI

Pb

Bi

Po

At

III

IV

III

IV

bc

cg

Ce

Pr

Nd

Pm

Sm

Eu

Tm

Yb

Lu

III

III

III

III

III

III

Th

Pa

Np

Pu

Am

Cm

Bk

Cf

Es

No

103

IV

VI

VI

VI

III

III

III

III

III

abcdh

abcd

ab ab

hj

hj

hj

hj

hj

Sr

Ba

Ra

Ti

Cr

IV

b
Y

Mn

Ir

Ni

Pd

Pt

Au

Ac

* Elements 5871

Elements 90103

ab ab ab abf

Gd

Tb

Dy

Ho

Er

III
h
Fm

Md

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
reagents such as the LIX oximes is somewhat straight forward due
to the constraints imposed by the chelation chemistry, amine systems
tend to be more complicated due to:
The large number of aqueous anionic systems where an amine
extractant might be applicable.
Protonated amines and quaternary amines must be paired with
an anion to maintain charge neutrality in the organic phase which
often results in poor selectivity depending on the relative
amounts of amine or quaternary amine relative to the targeted
species.
The large number of potential stripping agents as compared to
copper loaded oximes where stripping with sulfuric acid is the
standard.
The pH, the metal oxidation state and the effects of
concentration of the anionic complexing agent all have an impact
on the chemical behavior of the system.
Development of amine systems can be more of an art form rather
than a science. Any investigation of a potential separation process
should start with a laboratory program whose goal is to develop the
best conditions for extraction, stripping and final product recovery
consistent with the overall metallurgical flowsheet.
The development of a separation process for cobalt, iron and nickel
from an acid chloride solution illustrate the importance of the factors
cited above. Figure 1 shows that nickel(+2) is only slightly extracted
at greater than 200 g/L chloride ion while cobalt(+2) and iron(+3) are

For additional information regarding BASF amines and quaternary

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

extracted at chloride ion concentrations of 150

200 g/L.
Furthermore, iron(+3) is still strongly extracted at 50 g/L chloride ion.
Given these points, one can expect to develop an excellent separation
of these metals by first dissolving the mixture into a concentrated
hydrochloric acid solution, oxidizing the iron to the +3 state, coextracting the cobalt(+2) and iron(+3) with an amine while leaving the
nickel(+2) in the original aqueous solution. The cobalt can then be
selectively stripped off the loaded organic by water. This flowsheet
has been studied in a BASF laboratory. Several slightly different
flowsheets for this separation have also been reported13,14. The best
choice of flowsheet is dependent upon the relative amounts of
cobalt, nickel and iron present.
Often, the complex of the protonated amine or quaternary amine
cation with the extracted anion may have only limited solubility in a
typical hydrocarbon diluent resulting in the formation of a third phase
and/or phase separation problems. A third phase is a viscous layer
that typically collects at the interface. It is primarily composed of the
precipitated complex. Due to the ionic nature of the complex, the
third phase is highly polar which makes it a very good solvent for
polar materials such as the free amine or quaternary amine. The free
extractant (amine or quaternary amine) will distribute from the
hydrocarbon diluent into the third phase resulting in a rapid loss of
loading capacity and net transfer. Addition of a solvation modifier
(phase modifier) such as a long chain alcohol, e.g., isodecanol,
isotridecanol; to the organic phase is normally employed to prevent
third phase formation and
/
or phase separation problems.
Replacement of at least a portion of the hydrocarbon diluent with a
high aromatic diluent may also be employed.

31

7. Extraction of Uranium

In 1957, the Mining Solutions unit of BASF (which in part originated

from the General Mills Mining Chemicals Division) introduced
Alamine 336, tri(octyl, decyl) amine, to the mining industry for the
recovery of uranium by solvent extraction from acidic sulfate leach
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
industry in the late 70s, approximately 80% of the production in the
USA used the Alamine 336 solvent extraction flowsheet. It was this
ongoing involvement in the uranium industry that eventually led to the
conceptualization and development of the phenolic oximes for the
recovery of copper from acidic leach liquors. The hydrometallurgical
processing of uranium has been extensively reviewed2,3,4,5.
The general chemistry for the processing of uranium through leaching
with dilute sulfuric acid, solvent extraction and precipitation to yield
high grade U3O8 is summarized in Figure 1. Sulfuric acid leaching of
uranium ores is carried out under oxidizing conditions at a redox
potential of 400500 mV relative to a saturated calomel electrode.
While ferric ion is the primary oxidant, oxidants such as manganese
dioxide, sodium perchlorate or hydrogen peroxide are employed to
convert ferrous ion to ferric ion. Under these conditions, uranium is
converted to the +6 valence state and is solubilized as the anionic
uranyl di-sulfate or tri-sulfate complexes. After clarification to remove
residual solids, the leach solution is contacted with an organic phase
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 preprotonate the amine and load the organic with sulfate or bisulfate.
This ensures that the amine will be protonated in extraction, the pH
of the aqueous phase will remain approximately constant since no
acid extraction will occur, and will help to maximize selectivity for
uranium. In extraction, the sulfate/bisulfate anion is exchanged for
an anionic uranyl sulfate complex. Uranium extraction is an anion
exchange process. Depending on a variety of factors, there is the
potential for competitive extraction by other anions present in the
leach liquor. To achieve the desired uranium purity, a number of
scrubbing stages as illustrated in Figure 2 may be employed in the
solvent extraction circuit to remove these unwanted anions from the
organic phase and prevent their transfer to stripping.
Stripping of the loaded organic can be carried out with ammonia,
strong sulfuric acid solutions, sodium chloride or nitrate solutions.
The use of ammonia/ammonium sulfate is a preferred option6,7,8,9.
Stripping is carried out by pH controlled addition of ammonia gas or
ammonium hydroxide solution to each strip stage10,11. Careful control

Figure 1: General Chemistry of Uranium Processing

H2SO4
LEACHING

UO2 + Fe3+ UO22+ + 2Fe2+

UO2+ + 3H2SO4 UO2(SO4)34- + 6H+

Solvent
Extraction
(SX)

Pre-protonation
2 R3N(Organic): + H2SO4(Aqueous)
(R3NH+)2S04-2 (Organic)
Extraction
UO2(SO4)34- + 2 (R3NH+)2SO4-2
(R3NH+)4UO2(SO4)3-4(Organic) + 2 S04-2(Aqueous)
Stripping
(R3NH+)4UO2(SO4)3-4(Organic) + 4 NH4OH(Aqueous)
4 R3N(Organic) + (NH4)2UO2(S04)2(Aqueous) +
(NH4)2S04(Aqueous) + 4 H2O

Yellowcake
Production

Precipitation
2 (NH4)2UO2(SO4)2 + 6 NH4OH
(NH4)2U2O7 + 4 (NH4)2SO4 + 3 H2O
Calcination (Heat > 580C)
(NH4)2U2O7 + heat 2U3O8

of ammonia addition is required. The presence of excess ammonia

will result in the precipitation of ammonium diuranate in the mixers
resulting in crud formation and operational problems. After stripping,
additional ammonia is added to the pregnant strip solution to
precipitate the uranium as ammonium diuranate (ADU). After filtration
and drying, the ADU is calcined to produce high purity (99% or
greater) U3O8.
The process described above involving direct solvent extraction of
the uranium from the dilute acid leach solution is often described as
the Amex process (Figure 3) or the Purlex process. An alternative
flowsheet involves pre-concentration of uranium by use of an ion
exchange resin followed by extraction of the uranium from the resin
eluate solution with an amine. This is referred to as the Eluex process
(Figure 4) (Bufflex process in South Africa). The Eluex process takes
advantage of the use of relatively non-selective ion exchange resins
to treat very dilute solutions to generate a much more concentrated
solution of uranium and then use of the more selective amine solvent
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
Extraction

PLS

Raffinate

E1

Organic
scrubbing

Uranium
Stripping

E2

to PLS
or leach
Loaded
organic

E3

H2O

E4

H2SO4

NH3/(NH4)2SO4

Sc1

Sc2

Sc3

Sc4

S4 pH 4.8

S3 pH 4.0

S2 pH 3.8

S1 pH 3.3

H2O

NH3

ADU
precipitation

L
S

Barren strip liquor

HX
3040C

Liquor

to calciner

Na2CO3/NaOH

regeneration
pH ~11.0

Each uranium leach, ion exchange and

/
or solvent extraction
operation is somewhat unique due to differences in the pregnant
leach solution stemming from the ore and gangue mineralogy,
site water quality, and site specific water balance issues. These
differences can give rise to a variety of operational challenges 13,14,15,16:
Crud Formation
Typical solvent extraction plant design specifications target less
than 20 ppm of solids in the incoming pregnant leach liquor.
Incoming solids can interact with the organic phase in the mixer
to form a solid stabilized emulsion, crud. Depending on the
level, 100s to 1000s of ppm, and nature of the solids, some
crud will be formed. In cases where crud formation is mild, it
may be responsible for transfer of impurities to final product. In
severe cases, it may result in the need to shut down the plant
and clean out the accumulated crud and solids. The presence
of dissolved species such as silica may also contribute to crud
formation. The soluble silica can be converted to insoluble silica
precipitates due to changes in the chemical nature of the

H2SO4

protonation
pH ~1.0

Barren
organic

aqueous solution at the organic-aqueous interface triggering

polymerization of the soluble silica to higher molecular weight
silica species. In addition to reducing the incoming
solids/soluble silica levels, operating the plant using organic
continuous mixing will help to minimize crud formation. In
extreme cases where high levels of solids or soluble silica is
present in the incoming feed, the plant operators may elect to
by-pass or shut down the solvent extraction process until the
pregnant leach solution returns to normal.
BASF offers a broad product range of floculants and
coagulants as well as technical expertice to assist plant
operators in solving pregnant leach liquor clarification issues
as well as reduce soluble silica levels.
Poor phase disengagement
Poor phase disengagement can arise from a number of
sources. Many uranium ore deposits contain a range of
organic substances such as humic acids. Under the oxidative
conditions of the leach, these materials can be converted to

33

carboxylic acids and organic sulfates which are surfactant-like

in nature, distribute into the organic phase and build up in
concentration in the organic phase over time resulting in
longer phase disengagement times. Carboxylic acids have
also been generated by bio-oxidation of the alcohol solvation
modifier and the hydrocarbon diluent. Carboxylic acid
contamination of the organic may also result in a reduction of
uranium from extraction to strip either by reacting with the
amine to reduce extraction capacity or by transferring uranium
from stripping back to extraction. The overall level of these
organic contaminants can be reduced by scrubbing a bleed
stream of the stripped organic phase with a strongly alkaline
aqueous carbonate solution (i.e., pH ~1112).
Chemical transfer of impurities from extraction to strip.
Under the typical pH of the leach solution, molybdenum will be
present as a polymolybdate anion which is also readily
extracted by tertiary amines such as Alamine 336. Under the
conditions of the ammonia strip, the molybdenum will also
strip and will report to the final uranium product. Depending
on the pH of the leach solution, its redox potential, and the
presence of other anions such as phosphate, silicate,
arsenate, etc., molybdenum can be present in a number of
reduced polymolybdate or heteropolymolybdate (i.e.,
containing Mo5+) species which tend to form complexes with
the amine extractant that are poorly soluble in the organic
phase and tend to form sticky third phases or goo which
collect in the settlers at the interface and in the bottoms of the
settlers reducing settling volume. These precipitates may be
orange, yellow, green, blue, or gray in color. The color being
dependent on the oxidation state of the molybdenum and
heteroatoms present . If the formation of these insoluble
molybdenum third phases is a problem, BASF recommends
the use of Alamine 304-1. The use of diluents having a high
aromatic content, higher concentrations of alcohol solvation
modifiers, and operating at a redox potential high enough to
insure that molybdenum is all present in the +6 oxidation state
will also help to prevent third phase formation. Where sufficient
molybdenum is present, one can selectively strip the uranium
using an acidified chloride solution and then strip the
molybdenum off the organic using a sodium carbonate solution.
If vanadium is present, one can selectively recover it by
controlling the redox potential of the aqueous. Vanadium(+4) is
not extracted by tertiary amines from sulfate solutions while
the vanadium(+5) forms a polyvanadate which is readily
extracted. At redox potentials below about 600 mV (against
standard calomel electrode), vanadium is present only in the
+4 oxidation state and the uranium can be extracted away

from the vanadium. Once the uranium is recovered, one can

adjust the redox potential of the raffinate to about 720 mV at
which point all of the vanadium will be present in the +5
oxidation state and can be extracted as the polyvanadate.
However, the polyvanadate species are strong oxidants and
will cause degradation of the amine.
Zirconates will also be co-extracted along with uranium by
tertiary amines. Careful control of the scrub stage pH between
2.53.0 as well as use of a bit of uranium to crowd the
zirconates off the organic will minimize its transfer to strip.
Other contaminants common to uranium circuits can also be
controlled using appropriate strategies. A thorough
understanding of the components in the leach solution is
critical to operating a uranium recovery plant.
Amine degradation
Nitrate is problematic for a couple of reasons. It is preferentially
extracted over the uranyl sulfate species by tertiary amines
and thus suppresses uranium extraction. Under certain
conditions, the presence of nitrates in the leach solution can
lead to a high redox potential (550700 mV against standard
calomel electrode). Under these conditions, the tertiary amine
undergoes very rapid attack by the nitrate and is converted to
the corresponding di-alkyl nitrosamine resulting in loss of
loading capacity and increased phase disengagement
problems. This problem has been most frequently observed in
Eluex circuits where the uranium is first concentrated by use of
an ion-exchange column. The uranium is then further purified
and concentrated by solvent extraction with a tertiary amine.
The solution has been to control the redox potential to below
510mV by addition of iron wire to the aqueous weirs in
extraction17,18.
Tertiary amines are stable to most process conditions such as
acidity and alkalinity at typical temperatures. At temperatures
over about 90C, protonated amines will slowly degrade by a
Hoffman elimination type mechanism.
Contact with strong oxidants such as vanadium(+5), hydrogen
peroxide, etc., will result in oxidative degradation of amines.
Acid consuming ores are leached with alkaline carbonate solutions to
generate the uranyl tricarbonate complex. While the uranyl
tricarbonate complex can be extracted with Aliquat 336, this
approach has not been pursued commercially to any large extent14,19.
Recovery of uranium from copper solvent extraction raffinates by
solvent extraction with Alamine 336 has also been practiced at BHP
Billitons Olympic Dam Operations and at Anamax Twin Buttes20,21.

34

Figure 3: Amex Process

Figure 4: Eluex Process

Ore
Oxidant

Sulfuric Acid
Leaching

Ammonium
Sulfate

Solids
to tailings

SX
Uranium
Rich Solution

Water
Sulfuric
Acid

S/L Separation
Solids
to tailings

CIX

Ammonium
Sulfate

Barren
Solution

Oxidant

Leaching

Water

S/L Separation

Ammonia

Ore

Sulfuric Acid

Barren
Solution

Uranium
Solution
SX

Uranium
Rich Solution

Precipitation

Barren
Acid

Ammonia
Precipitation

Filtration
Tailings
Yellowcake

Filtration
Yellowcake

Tailings

35

8. E
 xtraction of
Molybdenum and Vanadium

Molybdenum
The primary sources of molybdenum are concentrates derived as
by-products from flotation of copper sulfide ores or directly from
molybdenum ores. These concentrates are typically roasted to
produce a crude molybdenum oxide and a flue dust, which also has
a high molybdenum content. Both can be leached with sulfuric acid
to produce leach solutions from which molybdenum can be recovered
via solvent extraction to produce a high purity molybdenum oxide
product. Since rhenium is often associated with molybdenum, the
option to recover rhenium using solvent extraction exists as well.
Molybdenum sulfide concentrates can also be effectively leached
using high pressure oxidative leach techniques to produce a feed
solution amenable to processing by solvent extraction. Molybdenum
can also be successfully leached from spent hydrocarbon cracking
catalysts and recovered using solvent extraction.

Solvent extraction can also provide routes to recover molybdenum

from non-traditional sources such as acidic heap and dump copper
leach solutions1.
The solvent extraction of molybdenum can be a challenging
undertaking due to molybdenums complicated and unique chemistry.
An understanding of the aqueous solution chemistry and solvent
extraction chemistry of molybdenum is necessary to successfully
operate a molybdenum solvent extraction plant. BASF through its
predecessor companies has been supplying solvent extraction
technology for the recovery of molybdenum since the late 1950s and
the chemical expertise to understand the unique problems faced by
plant operators when dealing with molybdenum2.

Molybdenum Chemistry
Molybdenum can be present as a wide variety of species in an
aqueous solution3. The oxidation potential of the solution, the nature
of the other anions and metals that are present as well as their
concentration, the pH of the solution and the concentration of
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.
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
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
simple molybdate ion predominates. The picture can be further
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.

Figure 1: Distribution of molybdenum(+6) species as

function of pH
Isopolymolybdates Mo7O246, Mo8O264

MoO42

Cationic MoO2+2

2.0

4.0

6.0

8.0
pH

10.0

12.0

14.0

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)

Stripping

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

[(R3NH+)4Mo8O26-4](Org) + 12 OH-(Aq)

Due to the fact that polymolybdates are strongly extracted from acidic
sulfate leach liquors by tertiary amines allowing one to operate at very
high percentages of molybdenum maximum loading, recoveries are
typically very high in 2 to 3 counter current stages of extraction. Stripping
is accomplished by contacting the loaded organic with ammonia. Very
high concentrations of molybdenum, up to 100 g/L, can be achieved
in the strip liquor in 1 to 2 stages of stripping using a concentrated
ammonia solution and maintaining the pH in stripping between 9.0 to
9.5. The results of a mini plant circuit run in a BASF laboratory is shown
in Figure 2.
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
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
97.3% recovery of molybdenum was achieved in E1 and 99.1%
recovery overall indicating that no more than 2 stages of extraction are
required in this case. Stripping was highly efficient with 99.4% stripping
achieved in S1.

8 MoO4-2 + 4 R3N(Org)+ 8 H2O(Aq)

Figure 2: Mini plant circuit

Spent Wash
0.06 g/L
Wash
Water

Rafnate
0.05 g/L

Feed
5.56 g/L

0.15 g/L

W1
pH 1.5

0.07 g/L

E1
6.21 g/L

E2
0.69 g/L

E3
0.54 g/L

Washed SO
0.03 g/L

LO
Surge

6.28 g/L

S1

0.04 g/L

S2

0.03 g/L

p H 9 .7

W2
p H 9 .3 5

64.0 g/L

Rich Strip Liquor

78.2 g/L

Spent Wash
1.3 g/L
NH 3 Strip Soln
65 g/L

Wash Water

37

Molybdenum Solvent Extraction

Technical Challenges
One of the more prevalent problems that molybdenum solvent
extraction plant operators face is the formation of third phases4,5.
These third phases tend to be very thick oils that collect in the organic
phase, at the organic/aqueous interface, and in some instances
even on the sides and bottom of the settler. Depending on their
chemical composition, they may range from a yellow/green to a dark
blue/green in color. If a small proportion of the molybdenum is
present in the +5 oxidation state, the molybdenum amine complex
tends to have limited solubility in the organic phase, especially if the
diluent is predominantly aliphatic in character. The resultant third
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.

As noted earlier, heteropolymolybdic acids will form species such as

in the case of phosphorus, PMo12O40-3, in solution. The amine
complexes of these heteropolymolydates tend to vary in color and
have limited solubility in the organic phase. A yellow green crystalline
material has been isolated from a uranium plant and characterized as
(R3NH)3[PMo12O40]3(R3NHCl). Figure 4 shows a sample of a yellow
green goo obtained from a molybdenum solvent extraction plant.
This material had collected on the bottom of the settlers.

Figure 4:

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
such as:
Water leach of salt roasted carnotite ore.
Sulfuric acid leach of carnotite ore.
Water leach of salt roasted ferro-phosphorous slag.
By product streams from uranium recovery processes.

Figure 5: Distribution of vanadium(V) as a function of pH

Isopolyvanadates H2V10O284 , HV20O285, H2V2O72

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
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.

Cationic VO2+1

Vanadium Extraction

2.0

4.0

6.0

8.0

10.0

12.0

14.0

pH

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

Stripping

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

(R3NH+)4H2V10O28-4(Org) + 5 NH4OH(Aq)

(R3NH+)4H2V10O28-4(Org)

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

addition of additional ammonium hydroxide to promote the
precipitation of ammonium metavanadate.
To achieve efficient extraction of vanadium with Alamine 336, the
pH has to be controlled between about pH 2.5 to 3.511. Above about
pH 3.5, there is insufficient acid available to insure that the amine is
adequately protonated to form the ammonium cation. Below pH
~2.5, extraction begins to decrease because vanadium is primarily
present as the vanadyl cation. As the concentration of the vanadium
decreases in the aqueous, the balance between the anionic species
and the cationic species shifts to favor the presence of the anionic
species resulting in vanadium recoveries of 9798%. Heating the
solution shifts the equilibrium towards the anionic form. Increasing
the temperature in extraction to 50C increases vanadium recovery
to about 99%. The use of heat to decrease the vanadium in the
raffinate and increase recovery appears to have a constant effect
irregardless of the intial vanadium concentration in the incoming
pregnant leach solution. In general, the extraction of vanadium with
Aliquat 336 is less sensitive to pH and does not require fine pH
control. In minilab circuit trials, the use of the Aliquat 336 appears to
provide better physical performance. When dealing with chloride
liquors, Aliquat 336 is more selective for the polyvanadate12.
Stripping is also carried out with pH control between 6.0 and 7.8. If
excess ammonium hydroxide is present, one can begin to trigger the
precipitation of sodium metavanadate in the strip stages resulting in
emulsions and crud formation.

Vanadium Solvent Extraction Technical

Challenges
The formation of third phases similar to those observed with
molybdenum has been reported when using Aliquat 336 as
extractant13. These third phases may be due to the formation of
V(+4)
:
V(+5) mixed valence decavanadate complexes due to
oxidative attack on the organic phase.
Vanadium(+5) species are relatively strong oxidants. Once loaded on
the organic phase, they will carry out an oxidative attack on the
amine extractant. Over time, the tertiary amine will be degraded to
secondary amines and a variety of other oxidation products.
Fortunately, the degraded organic is also a good extractant for
vanadium(+5). In cases where solvent extraction circuits using
Alamine 336 to recover another metal such as uranium are in
operation at the same site, BASF recommends that organic from the
uranium circuit be used as make up for the vanadium circuit and
fresh reagent should be added to the uranium circuit to the greatest
degree practical.

Separation of Vanadium from Uranium

Vanadium is frequently found associated with uranium. Both the
uranium and vanadium are leached with sulfuric acid. Both can be
selectively extracted by controlling the redox potential of the
aqueous14. Uranium leaching is typically carried out at redox potential
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

include:
Germanium recovery1
Copper recovery from typical tankhouse electrolytes2
As part of synergistic blends with other reagents for recovery of
cobalt and nickel3,4,5
Separation of molybdenum from uranium in dilute sulfuric acid
solution6
LIX 84-I: A ketoxime based reagent which contains no added
modifier and is readily stripped of copper with 150 g/L sulfuric acid.
It is more hydrolytically stable than the corresponding aldoximes.
Uses include:
Copper recovery from dilute sulfuric acid solution
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

LIX 7820: A mixture of a weak organic acid with a quaternary

amine developed for extraction of anions from solutions having a pH
less than ~10 and stripping efficiently at pHs greater than ~1115.
Proposed uses include:
Extraction of gold from cyanide leach liquors15
Extraction of gold from thiosulfate leach liquors16
Cyanide recovery17
While the above covers a broad range of potential applications, it
should not be considered as limiting. BASF continues to work on the
development of new extractant chemistries as well as on new
applications for existing LIX reagents. If you have an interest in a
particular application, you should contact your local BASF Mining
Solutions representative to explore possible solutions to your
application.

41

10. Appendices
10.1 Isocalc* Computer Modeling Software

The BASF Isocalc (Total Metallurgy) computer simulation program

was developed as a tool to provide plant operators with fast and
accurate simulations of virtually any copper solvent extraction
processes involving sulfuric acid leaching followed by copper
extraction with a phenolic oxime type extractant. The functions of
Isocalc include:
From the description of a common (or complex) copper leach
solution and the stripping conditions, extraction and stripping
isotherms are calculated based on a comprehensive chemical
model. McCabe-Thiele diagrams can then be constructed for
many solvent extraction plant configurations.
Laboratory generated extraction and/or strip isotherm data can
be manually entered instead of relying on the chemical models
provided. This is useful for reagent compositions that do not
perform exactly the same as new or fresh LIX Reagents. This is
often the case with aged plant organics. McCabe-Thiele
diagrams can also be developed for these extraction and
stripping isotherms.
From a chemical model or a lab-generated extraction isotherm
developed for an operating plant, plant operating data or profiles
can be inserted into the program and stage efficiencies will be
accurately calculated.
Results from each isotherm/McCabe-Thiele diagram can be
saved as project files and later retrieved for use again in another
simulation.
Accurate comparisons of different plant configurations and
operating conditions can be realized.
The Isocalc program includes a combination of chemical modeling
of the extraction and stripping processes and mathematical
manipulation of the data points. A stripped organic value from
either chemical modeling or a manually input stripped organic value
must be used as a starting point for each extraction isotherm. Once
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.

The effect of changing any one or more variables in the configuration

can be quickly and accurately determined through to final copper
recovery.
The chemical model for the equilibrium extraction curves is based on
the equilibrium constants for several important chemical reactions in
the process. By using these chemical criteria for the model, it is
possible to take into account most of the variables commonly found
in a copper solvent extraction process.
A second generation of the Isocalc solvent extraction modeling
program is currently in development. The new BASF Isocalc EHM
(Enhanced Hydrometallurgy Model) program retains all the
functionality of the first generation software coupled with an novel,
user-friendly processing platform. It offers the user a flexible mass
balance package tailored for the LIX stable of reagents. Isocalc
EHM offers expanded functionality including many additional
features, some of which are:
Greater flexibility in specifying acid and copper tenor ranges for
spent and advance electrolytes.
Capability of handling broader range of circuit configurations and
flows.
Additional general modeling functionality.
It has complete mass flow functionality allowing for complete
minerals processing and hydrometallurgy flowsheet modeling.
The user interface input has been simplified by having all
inputs on one page at start up with the capability to rerun the
model with any number of stream attribute changes.
User-selected Isocalc EHM models and outputs can be
exported into a comprehensive Xcel spreadsheet report.
For additional information about Isocalc EHM contact your local
BASF Mining Solutions technical representative.

* 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
extraction (CuSX) organic for solution health, including phasedisengagement-time (PDT), Cu/Fe selectivity and extraction/stripping
kinetics.
Background
The standard quality control test for LIX reagents is designed to be
a relatively simple and easy way to ensure that these LIX reagents
meet rigid specifications for those properties critical to the
performance of these reagents as copper extractants. Reagent
specifications are tied to the specific conditions of the BASF quality
control test and for this reason it is very important to strictly adhere
to the test equipment, reagents, conditions and procedures
described in this method.
Equipment
The test vessel is a 1-L PYREX glass beaker fitted with a set
of 4 Type 316 stainless steel baffles 4.7 inch (11.95 cm) tall by
0.4 inch (0.90 cm) wide with 20 gauge thickness set 0.125 inch
(0.318 cm) away from the beaker walls), clean and free of soap
or detergent residue.
The polypropylene impeller is 1.75 inches (4.45 cm) in diameter
with 6 slots, 0.125 inches deep and 0.125 inches (0.32 cm)
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.
The mixer speed is adjusted to 1,750 25 rpm. While BASF
uses Stirrer Type RZRI available from Caframo (Wiarton, Ontario,
Canada N0H 2T0), any good constant speed stirrer capable of
maintaining 1,750 25 rpm is acceptable.
The test vessel, baffles, and impeller are available to BASF
customers free of charge from BASF.
When sampling the emulsion it is important that no additional
mixing occur. A large bore sampling tube should be used. A 10
ml volumetric pipette with the tip cut off or a 10 ml serological
pipette with the sample drawn through the large end are
satisfactory devices.
Reagents
Organic from neat formulated reagent
Prepare a 500 ml solution of exactly 10 v/v % of neat LIX reagent in
the diluent, Shellsol D70 or its approved equivalent. If v/v dilution is
not convenient, w/v dilutions can be calculated and made using the
density of the LIX reagent lot being tested.

Organic from neat concentrated reagent except LIX 860-I

Prepare a 500 ml solution of exactly 7.143 % v/v of neat LIX reagent
in the diluent, Shellsol D70 or its approved equivalent. If v/v dilution is
not convenient, w/v dilutions can be calculated and made using the
density of the LIX reagent lot being tested.
Organic from neat concentrated reagent LIX 860-I
Prepare a 500 ml solution of exactly 8.00 % v/v of neat LIX reagent
in the diluent, Shellsol D70 or its approved equivalent. If % v/v dilution
is not convenient, w/v dilutions can be calculated and made using
the density of the LIX reagent lot being tested.
Organic from used plant material
Prepare a 500 ml solution of plant organic with a maximum copper
loading of 5.6 g/L Cu.
Standard extraction aqueous phase
The extraction aqueous phase contains 6 0.1 g/L Cu+2, 3 0.1 g/L
Fe+3 (both as sulfates) at a pH of 2.0 0.1.
Standard strip aqueous phase
The strip aqueous phase contains 35 0.7 g/L Cu (as the sulfate)
and 160 2 g/L H2SO4.
All solutions are prepared from reagent grade chemicals dissolved in
D. I. water. All solution temperatures are equilibrated to 23 1 C
before use.
Before and after each test all equipment should be rinsed several
times with DI water followed by methanol or acetone and completely
dried before each use. Failure to adequately rinse and dry the
equipment can result in erroneous results.
Procedure
Extraction Kinetics, extraction isotherm point, extraction PDT
and extraction Cu/Fe selectivity
Vigorously contact 400 ml of the organic phase with 400 ml of strip
aqueous phase for two minutes in a separatory funnel. After the
phases have separated, filter the organic phase through Whatman
1PS or equivalent filter paper. Add 350 ml of filtered organic into the
test vessel and adjust the impeller so that it is centered in the test
vessel and the top of the polypropylene hub of the impeller is at the
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

seconds using the wide end of the pipette, smoothly remove
1015ml of sample emulsion from the top 2 cm of the test vessel
and transfer the sample into a small beaker or separatory funnel.
After the phases have separated, filter the organic sample through
Whatman 1PS or equivalent filter paper, label as the E30 sample and
save for analysis. If ketoxime, such as LIX 84-I is being tested a 60
second kinetic sample (E60) is taken in the same manner as E30.
Continue mixing for a total of 300 seconds at which time the stirrer is
stopped. Immediately start a stopwatch and determine the time
required for complete separation of the phases. Phase separation is
considered complete when only a monolayer of bubbles remains at
the interface. Sample the organic phase, filter the organic sample
through Whatman 1PS or equivalent filter paper, label as the E300
sample and save for analysis. Refer to the copper aqueous and
organic procedures for analysis.

after the addition of the organic. Starting at 29 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
organic phase through Whatman 1PS paper or equivalent and label
as the S30 sample. Continue stirring for a total of 300 seconds, stop
the stirrer and allow the phases to separate measuring the phase
separation time as previously described. Sample the organic phase,
filter the organic sample through Whatman 1PS or equivalent filter
paper, label as the S300 sample and save for analysis. Refer to the
copper aqueous and organic procedures for analysis.
Maximum copper loading
Take an aliquot of the diluted LIX reagent and an equal volume of
standard extraction aqueous and contact them vigorously for 2
minutes in a separatory funnel. Allow the phases to separate and
discard the aqueous phase. Add fresh standard extraction aqueous
and repeat the contact. Continue until a total of 4 contacts have been
made. After the last contact, filter the organic sample through
Whatman 1PS or equivalent filter paper, label as the Max Load
sample and save for analysis.

Strip kinetics, strip isotherm point and strip PDT

The organic and aqueous phases from the extraction test above
are transferred to a separatory funnel and the phases allowed
to completely separate. The aqueous phase is withdrawn and
discarded. Loaded organic (325 ml) is carefully transferred to a
graduated cylinder making sure no aqueous transfers with the
organic. The standard strip aqueous (325 ml) is added to a clean test
vessel. Adjust the impeller height as previously described, start the
stirrer and adjust the speed to 1,750 25 rpm. Over a period of 5
seconds add the loaded organic. Start the stopwatch immediately

Organic samples E30, E60, E300, S30 and S300 and the Max Load sample
are assayed by Atomic Absorption Spectroscopy (AAS) for Cu. The
E300 sample is also assayed by AAS for Fe. All results are expressed
in units of g/L. AAS procedures used by BASF to determine copper
and iron in organics are available upon request.

Calculations
1. Extraction isotherm point

Cu = E300

2. Strip isotherm point

Cu = S300

3. Extraction kinetics

% =

4. QC Extraction Cu/Fe selectivity

E30
E300

x 100 or

E60
E300

x 100

E300 (Cu)
E300 (Fe)
E300 (Cu) S30 (Cu)

5. Strip kinetics

% =

6. Net transfer

Cu = E300 S300

E300 (Cu) S300 (Cu)

x 100

44

BASF quality control test

of LIX nickel oxime reagents
Quality control test of neat reagents and in process nickel solvent
extraction (NiSX) organic for solution health, including phasedisengagement-time (PDT), Ni/Zn selectivity and extraction/stripping
kinetics.
Background
The standard quality control test for LIX reagents is designed to be
a relatively simple and easy way to ensure that these LIX reagents
meet rigid specifications for those properties critical to the
performance of these reagents as copper extractants. Reagent
specifications are tied to the specific conditions of the BASF quality
control test and for this reason it is very important to strictly adhere
to the test equipment, reagents, conditions and procedures
described in this method.
Equipment
The test vessel is a jacketed 1 liter beaker equipped with
stainless steel baffles, clean and free of soap or detergent
residue.
The polypropylene impeller is 1.75 inches (4.45 cm) in diameter
with 6 slots, 0.125 inches (0.32 cm) deep and 0.125 inches
wide, the top of the hub is 1 cm above the top of the impeller,
and the shaft is 316 L stainless steel, 23 cm long.
The mixer speed is adjusted to 1,650 25 rpm. While BASF
uses Stirrer Type RZRI available from Caframo (Wiarton, Ontario,
Canada N0H 2T0), any good constant speed stirrer capable of
maintaining 1,650 25 rpm is acceptable.
The test vessel is maintained at 40 0.5C by a recirculating
water bath.
When sampling the emulsion it is important that no additional
mixing occur. A large bore sampling tube should be used. A 10
ml volumetric pipette with the tip cut off or a 10 ml serological
pipette with the sample drawn through the large end are
satisfactory devices.
Reagents
Organic from neat formulated reagent
Prepare a 500 ml solution of exactly 30 v/v % of neat LIX reagent in
the diluent Orfom SX-12 or its approved equivalent. If v/v dilution is
not convenient, w/v dilutions can be calculated and made using the
density of the LIX reagent lot being tested.

Standard extraction aqueous phase

The extraction aqueous phase contains 15 0.1 g/L Ni+2, 1 0.1 g/L
Zn+2 (both as sulfates), 32.5 g/L NH3 and 25 g/L (NH4)2SO4.
Standard strip aqueous phase
The strip aqueous phase contains 60 0.7 g/L Ni (as the sulfate) and
30 1 g/L H2SO4.
1.0 M NaOH
Weigh 20.0 g NaOH into a 500 ml flask and dilute to volume with
deionized water which has been boiled to remove carbon dioxide.
Mix well. Standardize. Protect from CO2 absorption during storage to
prevent concentration changes.
KHP Buffer Solution
Into a 1 liter volumetric flask weigh 51.05 g potassium hydrogen
phthalate, KHP. Add about 400 ml of deionized water and mix until
the KHP is dissolved. Add the volume of standardized 1.0 M NaOH
calculated from the following equation: ml NaOH = 113/M NaOH.
Dilute to volume with deionized water and mix well. The pH of the
buffer should be 5.0 0.1.
50 g/L Potassium Oxalate (K2C2O4)
Weigh 55.4 g K2C2O4 x H2O into a 1 liter flask and dilute to volume
with deionized water. Mix well.
Before and after each test all equipment should be rinsed several
times with DI water followed by methanol or acetone and completely
dried before each use. Failure to adequately rinse and dry the
equipment can result in erroneous results.
Procedure
Extraction Kinetics, extraction isotherm point, extraction phase
separation and extraction Ni/Zn selectivity
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
impeller so that it is centered in the test vessel and the top of the
polypropylene hub of the impeller is at the surface level of the organic
phase. Start the stirrer and adjust the impeller speed to 1,650
25 rpm and then over 5 seconds smoothly add 400 ml of the
standard extraction aqueous phase. Start the stopwatch immediately
at the end of the aqueous addition.

45

Take a 30 second kinetic sample (E30) as follows: Starting at 29

seconds, smoothly remove 1015 ml of sample emulsion from the
top 2 cm of the test vessel and transfer the sample into a small
beaker or separatory funnel. After the phases have separated, filter
the organic sample through Whatman 1PS or equivalent filter paper,
label as the E30 sample and save for analysis. Continue mixing for a
total of 300 seconds at which time the stirrer is stopped. Immediately
start a stopwatch and determine the time required for complete
separation of the phases. Phase separation is considered complete
when only a monolayer of bubbles remains at the interface. Sample
the organic phase, filter the organic sample through Whatman 1PS
or equivalent filter paper, label as the E300 sample and save for
analysis.
Strip Kinetics, Strip Isotherm Point, and Strip Phase Separation
The organic and aqueous phases from the extraction test above are
transferred to a separatory funnel and the phases allowed to
completely separate. The aqueous phase is withdrawn and dis
carded. Loaded organic is filtered through Whatman 1PS paper or
equivalent filter paper. A 25 ml sample is withdrawn and set aside for
the NH3 loading procedure. The remaining loaded organic is
equilibrated to 40 0.5C, and transferred to a graduated cylinder.
The strip aqueous (325 ml) is added to a clean test vessel. Adjust the
impeller height as previously described, start the stirrer and adjust
the speed to 1,650 25 rpm. Over a period of 5 seconds add 325ml
of the loaded organic. Start the stopwatch immediately after the
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

organic phase through Whatman 1PS paper or equivalent and label

as the S10 sample. Continue stirring for a total of 20 minutes, stop the
stirrer and allow the phases to separate measuring the phase
separation time as previously described. Withdraw a 75 ml sample of
the organic phase, filter through Whatman 1PS or equivalent filter
paper, label a 10 ml aliquot as the S20 sample and save the remainder
of the filtered stripped organic for interfacial tension analysis.
NH3 Loading
Into a 60 ml separatory funnel accurately pipette 20.0 0.1 ml of
filtered loaded organic. Pipette accurately, 10.0 0.1 ml of the KHP
buffer solution. Shake the separatory funnel containing the organic
and aqueous for 5 minutes. Allow the phases to separate and remove
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
oxalate solution and mix well. Determine the acid content by titration
with standardized 0.1 M NaOH. Calculate the M of H+ using the
equation in the calculation section. Into a titration vessel accurately
pipette an aliquot of the aqueous phase from the separatory funnel.
Usually 2.00 0.02 ml is an appropriate volume. Add 20 ml of the
50g/L potassium oxalate solution and mix well. Determine the acid
content by titration with standardized 0.1 M NaOH. Calculate the M
of H+ using the equation in the calculation section. Determine the
concentration in M of Ni+2 and Zn+2, in the aqueous phase from the
separatory funnel that have been stripped from the organic. C
alculate
the acid consumed by the metal stripped from the organic using the
equations shown below.

46

Calculations
Maximum Nickel Loading
Take an aliquot of the diluted reagent and an equal volume of
standard extraction aqueous and contact them vigorously for 2
minutes in a separatory funnel. Allow the phases to separate and
discard the aqueous phase. Add fresh standard extraction aqueous
and repeat the contact. Continue until a total of 4 contacts have
been made. After the last contact, filter the organic sample through
Whatman 1PS or equivalent filter paper, label as the Max Load
sample and save for analysis.
Organic samples E30, E300, S10 and S20 and the Max Load sample
are assayed by Atomic Absorption Spectroscopy (AAS) for Ni. The
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
and zinc in organics are available upon request.

1. Extraction isotherm point Ni E300 Ni g/L

2. Strip isotherm point

Ni = S20 Ni g/L

3. Extraction kinetics

% = (E30/E300) x 100

4. QC Extraction Ni/Zn

selectivity

= E300 (Ni g/L)/E300 (Zn g/L)

(E300 Ni S10 Ni)

5. Strip kinetics

% =

6. Net transfer

Ni = E300 Ni S20 Ni

(E300 Ni S20 Ni)

x 100

Copper in aqueous solvent extraction solutions

Instrument settings
Slit width
0.7 mm
Wavelength
327.4 nm with no background correction
Burner height The center of the light beam should be about
1 cm above the top of the burner.
Flame Air-acetylene, oxidizing, fuel lean, blue, air flow
7.0 L/min, fuel flow 1.1 L/min
Lamp current 12 ma (refer to lamp manufacturers recom
mended setting)
Integration time
3.0 seconds
Replicates 4
Reagents
Aqueous diluent: 10 g/L H2SO4 in deionized H2O
Deionized H2O
1,000 mg/L Cu Aqueous standard available from Fisher
Scientific,
PN#- PLCU2-2Y
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

Analysis
Ignite the flame and aspirate deionized H2O for 5 minutes to
allow the instrument and burner head to warm up.
Aspirate the aqueous diluent for at least 5 minutes to allow the
system to stabilize.
Zero the instrument using the aqueous diluent as the blank.
Aspirate the highest working standard and adjust the angle
of the burner so that the absorbance of the highest standard
will be ~ 0.4.
Set up a standard curve using the working Cu aqueous
standards. Use the aqueous diluent as the blank and the
30.00mg/L standard as the reslope standard.
Dilute the samples with the aqueous diluent to get the
concentration within the calibration standards.
Aspirate each sample, read and record the concentration.
Check the blank and standards as necessary to ensure that
the calibration has remained constant.
After completing the analyses aspirate deionized H2O for 5
minutes to flush all salt from the spray chamber and burner.
Shut down the instrument.

47

Copper in organic solvent extraction solutions

Background
Copper can be determined directly by atomic absorption spectro
scopy in organic solvent extraction solutions. The instrument must
be equipped to handle organic solutions and the standards and
samples must be diluted in an appropriate diluent.
The manufacturer of the instrument should be consulted for
instructions on setting up the instrument for the direct analysis of
organics. Usually the o-ring seals in the nebulizer/spray chamber
must be changed to materials that are compatible with organic
solutions. Once this change is made it is not necessary to change the
o-rings back to the original material to analyze aqueous solutions. All
water must be removed from the spray chamber before aspirating
organic. A convenient way to accomplish this is to ignite the flame
and aspirate deionized H2O for 5 minutes to allow the instrument and
burner head to warm up. Then aspirate methanol or other similar
water miscible organic for 5 minutes to flush all water from the spray
chamber and burner. Then aspirate the organic diluent for 5 minutes
to allow the system to stabilize. The organic should be removed from
the spray chamber before analyzing aqueous solutions or shutting
down the instrument. Aspirate methanol for 5 minutes to flush all
organic from the spray chamber and burner. Then aspirate deionized
H2O for 5 minutes to flush all methanol from the spray chamber and
burner. The instrument is now ready for the analysis of aqueous
solutions or can be shut down.
For organic sample preparation, filter each sample through PS1
paper to remove aqueous entrainment.
An organic matrix is necessary for the dilution of samples and
standards. BASF recommends a matrix of 5 % v/v of a LIX reagent
in a petroleum hydrocarbon approved for use as solvent extraction
diluent. The diluent must be free of all copper. The use of diluent
without a solvent extraction reagent gives low results with some
samples. The use of higher concentrations of solvent extraction
reagents in the diluent causes the burners in some instruments to
rapidly clog. If all samples are diluted at least 1:10 in the diluent
matrix used to prepare the standards no matrix effects are observed.
For samples containing copper at such low concentrations that a
1:10 dilution is not possible the matrix of the standards should be
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

volumetric flasks requires the calibration of the pipettes with the

diluent to achieve acceptable accuracy. The relatively high coefficient
of expansion of organic solutions requires all standards and samples
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 concentration of copper in the samples is in the g/L range. The
air-acetylene flame should be as lean as possible, in other words an
oxygen rich flame. The aspirated organic sample will act as a fuel and
will give a neutral or fuel rich flame. The absorbance and linearity of
the standard curve of copper are not very sensitive to the flame
conditions and height of the burner. For most instruments the angle
of the burner head should be adjusted so the absorbance of the
highest standard is between 0.4 and 0.6.
Instrument settings
Slit width
0.7 mm
Wavelength
327.4 nm with no background correction
Burner height The center of the light beam should be about
1 cm above the top of the burner
Flame Air-acetylene, oxidizing, fuel lean, blue, air flow
7.0 l/min, fuel flow 1.1 l/min
Lamp current 12 mA (refer to lamp manufacturers recom
mended setting)
Integration time 3.0
seconds Replicates 4
Reagents
Organic diluent: 5 (v/v)% LIX 984N in Conoco 170 exempt
solvent
Methanol
Deionized H2O
1,000 mg/L Cu organic standard (available from BASF Mining,
2430 N. Huachuca Dr., Tucson, AZ 85745, USA. Telephone
+1 520-622-8891, Fax +1 520-624-0912)
Working standards: 60.00 mg/L Cu, 30.00 mg/L Cu, and
10.00 mg/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
organic standard and the organic diluent

48

Analysis
Ignite the flame and aspirate deionized H2O for 5 minutes to
allow the instrument and burner head to warm up.
Aspirate methanol for 5 minutes to flush all water from the spray
chamber and burner.
Aspirate the organic diluent for at least 5 minutes to allow the
system to stabilize.
Zero the instrument using the organic diluent as the blank.
Aspirate the highest working standard and adjust the angle of
the burner so that the absorbance of the highest standard will
be ~ 0.4.
Set up a standard curve using the working Cu organic standards.
Use the organic diluent as the blank and the 30.00 mg/L
standard as the reslope standard.
Dilute the samples with the organic diluent to get the
concentration within the calibration standards.

Note: If a dilution of < 1:10 is used for a sample a matrix effect study
should be performed to ensure accuracy of the results. If necessary
the samples should be reanalyzed using conditions and standards
which allow for 1:10 dilutions, using a standard additions technique,
or using standards which have been matrix matched to the samples.
Aspirate each sample, read and record the concentration.
Check the blank and standards as necessary to ensure that
the calibration has remained constant.
After completing the analyses aspirate methanol for 5 minutes to
flush all organic from the spray chamber and burner. Aspirate
deionized H2O for 5 minutes to flush all methanol from the spray
chamber and burner.
Shut down the instrument.

Clay treatment of LIX reagents

Tests the effectiveness of clay treatment on improving the health of
copper solvent extraction (CuSX) circuit organic. Refer to BASF
quality control test of LIX reagents (Standard QC Test).
Background
During the operation of an CuSX circuit the organic phase can
become contaminated with organic substances which can adversely
affect the phase separation time, kinetics, and the Cu/Fe selectivity.
Clay treatment of the organic phase can sometimes be used to
remove the contaminant from the organic phase.
To determine if clay treatment will improve the performance of the
organic, the phase separation time, kinetics, and the Cu/Fe selectivity
are measured before and after clay treatment. Clay treatment is
normally tested initially at the concentration of 1 % w/w. If the clay
treatment is effective at 1 % w/w then lower concentrations can be
tested to determine the minimum concentration necessary for
effective treatment.

Equipment and solutions

Clays that have proven to be effective are acid leached montmorillinite
clays. Lupromin F-20X from BASF has been successfully used for
many years by a number of operators.
An efficient mixing chamber and mixer are needed. The equipment
used in BASFs Quality Control Procedure works well but other
equipment can be used if this is not available. The BASF Quality
Control extraction and stripping solutions are also used in the test. If
these are not available PLS and barren electrolyte solutions known to
be free of contaminants can be used.
When sampling the emulsion it is important that no additional mixing
occurs. A large bore sampling tube should be used. A 10 ml
volumetric pipette with the tip cut off or a 10 ml serological pipette
with the sample drawn through the large end are satisfactory devices.

49

Before and after each test all equipment should be rinsed several
times with water followed by methanol or acetone and completely
dried before reuse.
Procedure
Clay treatment procedure
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 impeller disc is 1 cm below the surface level of the organic phase.
If a BASF QC impeller is used the top of the polypropylene hub of the
impeller should be at the surface level of the organic phase. Begin
stirring, set the impeller speed to 1,750 25 rpm and over 5 seconds
add the clay. Continue stirring for 60 seconds. Then stop the stirrer
and immediately filter the treated organic to remove the clay. Longer
mixing times are usually not necessary. Very long mixing times, > 5
minutes, usually result in the absorption of some of the LIX reagents
onto the clay and may also allow some of the contaminants to be
released from the clay back into the organic phase.
Extraction and strip test procedure
Place 350 ml of stripped organic phase into the test vessel and
adjust the impeller position as described previously. Begin stirring,
set impeller speed to 1,750 25 rpm and then over 5 seconds add
350 ml of the extraction aqueous phase. A stopwatch is started at
the end of the 5 seconds aqueous addition. At 29 seconds smoothly
remove about 1015 ml of sample emulsion from the stirring test
vessel and allow the sample to drain into a small beaker or separatory
funnel. After the phases have separated, filter the organic sample
through Whatman PS1 phase separation filter paper, label as the E30
sample and save for analysis. If LIX 84-I is used take an E60 sample
as opposed to an E30.

Continue mixing for a total of 300 seconds at which time the stirrer is
stopped and the stopwatch is quickly reset and started. Determine
the time required for complete separation of the phases. Phase
separation is considered complete when only a monolayer of bubbles
remains at the interface. Sample the organic phase, filter the organic
sample through Whatman 1PS or equivalent filter paper, label as the
E300 sample and save for analysis.
The organic and aqueous phases from the extraction test above are
separated in a separatory funnel (discard the aqueous phase) and
then 325 ml of the loaded organic is carefully transferred to a
graduated cylinder. Make sure no aqueous transfers with the organic,
filter if necessary. Next add 325 ml of strip aqueous to a clean test
vessel. Adjust the impeller position as previously described and begin
stirring at 1,750 25 rpm. Over 5 seconds add the loaded organic
and then start the stopwatch. Start the stopwatch immediately after
the addition of the organic. Starting at 29 seconds, smoothly remove
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 organic
phase through Whatman PS1 paper or equivalent and label as the
S30 sample. Continue stirring for a total of 300 seconds, stop the
stirrer and allow the phases to separate measuring the phase
separation time as previously described. Sample the organic phase,
filter the organic sample through Whatman PS1 or equivalent filter
paper, label as the S300 sample and save for analysis.
Organic samples E30 or E60 and E300 from extraction, S30 and S300 from
stripping are assayed by Atomic Absorption Spectroscopy (AAS) for
Cu; samples E300 from extraction and S300 from stripping are also
assayed by AAS for Fe. AAS procedures used by BASF Corporation
to determine copper and iron loaded on organic are available upon
request.

Calculations

1. Extraction kinetics

2. QR Extraction
Cu/Fe selectivity
3. Strip kinetics

% =

E30 g/L Cu
E300 g/L Cu

x 100 or

E60 g/L Cu
E300 g/L Cu

E300 g/L Cu S300 g/L Cu

E300 g/L Fe S300 g/L Fe

% =

E300 g/L Cu S30 g/L Cu

E300 g/L Cu S300 g/L Cu

x 100

x 100

50

Direct colorimetric determination

of uranium on amine
This is a simple, rapid and accurate method for the direct colorimetric
determination of uranium on amine (Alamine 336) extractants. This
procedure is linear from 0800 ppm uranium, the color development
is almost instantaneous and the color is stable for 12 hours.
Preparation of organic standard and standard curve
1) 1 g/L uranium aqueous atomic absorption standard
2) 6 % v/v Alamine 336 + 4 % v/v decyl alcohol + 90 % v/v kerosene
Transfer 100 ml of aqueous uranium standard and 100 ml Alamine
solution to a mixer box. Equilibrate the solutions for 3 minutes at pH
1.5 using H2SO4 to adjust the emulsion pH. Stop the mixer and allow
the phases to separate. Discard the aqueous layer and filter the
organic phase through 1-PS filter paper.
This procedure yields a 1 g/L organic uranium standard. From the
1 g/L organic standard, make a series of standards ranging from
10800 ppm uranium and assay for uranium following the general
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

Transfer 13 ml of the amine sample containing 0800 ppm of

uranium and less than 21 mg sulphate to a 50 ml volumetric flask.
Dilute to the 50 ml mark with chromogenic solution and mix well.
Color development is almost instantaneous and is stable for
12 hours.
Read absorbance at 410 nm using chromogenic solution as the
blank. Note: Use matched cells.
Calculations
The optical density of the unknown samples should fall in the range
generated by the standard solutions. If the uranium concentration of
the unknown solutions is greater than 800 ppm, proper dilutions
should be made prior to the general procedure. For samples in the
correct concentration range, ppm uranium is read directly from the
standard curve. This procedure is linear between 0

800 ppm
uranium. The standard curve should pass through the origin.

51

10.3 S
 X Extractants and
Process Auxilliaries

LIX Reagents
BASF offers a broad range of LIX reagents based on three phe
nolic oximes: C9 aldoxime (5-nonylsalicylaldoxime), C12 aldoxime
(5-dodecyl
salicylaldoxime) and ketoxime (2-hydroxy-5-nonyl
aceto
phenone oxime). Combining these reagents in various proportions
with one another allows BASF to formulate a series of reagents
having varying extractive strengths for copper. These extractants are
referred to as non-modified blends. BASF also offers blends of the
aldoximes with varying proportions of thermodynamic modifiers
(modified aldoximes) as well as blends of aldoximes with ketoxime
and thermodynamic modifiers (modified mixtures). Increasing the
level of the thermodynamic modifier results in decreasing the
extractive strength of the modified aldoxime or the modified mixtures

blend. BASF has the capability of formulating an extractant tailored

to best meet the needs of the individual operation. For applications
where hydrolytic degradation of the C9 aldoxime may be an issue
due to higher temperatures, the use of the more stable C12 aldoxime
may be recommended.
For help in choosing the best reagent formulation for your application,
contact your local BASF Mining Solutions technical representative.
Representative examples of the more common formulations based
on C9 aldoxime are listed in Table 1.

Table 1:
Relative
Reagent
Strength

Non-Modified Blends

Modified Aldoximes

LIX 84-I
Based

LIX 8180
Based

Ester Modified

Alcohol
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 946N

LIX 684N-LV
LIX 9790N
LIX 8180

LIX 84-I

LIX 674N-LV

52

Alamine and Aliquat Reagents

Many of these reagents are also available as concentrates which can
result in reduced transportation costs. These are designated with a C
added to the name. Reagents containing C9 aldoxime are designated
by using an N after the number
Specialized formulations have also been developed for certain
applications. These are listed in Table 2.

BASF offers three tertiary amines and a quaternary amine

(Table 3).

Table 3:
Reagent

Alkyl
Groups

Application

Table 2:
Tertiary Amines
Reagent

Application
Alamine
308

Tri-iso
C8

Extraction of cobalt away from

acidic nickel solutions

Alamine
336

Tri-n
C8C10

Extraction of uranium,
molybdenum, vanadium,
tungsten

Alamine
304-1

Tri-n
C12

Extraction of molybdenum,
citric acid

Ketoxime Based
LIX 84-INS

Extraction of nickel from ammonia

LIX 84-IT

Reduced ammonia transfer when extracting

copper or nickel from ammoniacal feeds
Alpha-Hydroxy Oxime

LIX 63

Component of synergistic mixture systems for

separation of cobalt and nickel; Extraction of
germanium and gallium
Quaternary Amine/Weak Acid

LIX 7820

Extraction of anionic species coupled

by stripping with strong caustic;
Gold extraction from cyanide

Quaternary Amine
Aliquat
336

Tri-n (C8
C10), Methyl

Extraction of anionic metal

complexes on alkaline side

53

10.4 Mixer Settlers

Efficient solvent extraction requires the dispersion of one immiscible

phase as droplets in another immiscible phase. In our case, the
phases are typically a solution of a metal extractant in a high flash
point petroleum distillate (organic phase) and an aqueous phase. The
stage efficiency is dependent on the rate of mass transfer of the
material of interest from one phase to the other phase. The rate of
mass transfer is highly dependent on the rate of diffusion of the
various species to the interface and the rate of any chemical reactions
that occur at the interface. The amount of interfacial area available for
mass transfer is dependent on the size of the droplets of the
dispersed phase. Decreasing the droplet size increases the interfacial
area resulting in an increase in mass transfer. The droplet size is
determined by a variety of factors including the viscosities of the
phases, the power input into the mixer, and design of the mixer.
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.

Typical design criteria for a conventional mixer-settler unit for copper

SX plants using current oxime reagent technology to treat typical
acidic heap or dump leach solutions are as follows:
Mixer
O/A in mix box = 0.91.2 (Recycles used if needed)
Mixer residence time = 2 mins (3 mins if solutions are cold)
Mixer tip speed = 250300 meter/min
Turbine diameter = 0.50.6 diameter of mixer
Settler
Specific flow rate (total flow) = 4.06.5 m3/m2/hr;
3.03.5 m3/m2/hr if cold
Organic space velocity = 36 cm/sec
Organic depth = 2030 cm

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

conventional dual mixer-settler unit.

Organic
Advance
Aqueous Recycle

Organic
SETTLER

Aqueous

Fixed Organic Weir

Organic Discharge
Aqueous Up Comer
Aqueous Recycle
Advance

Adjustable
Aqueous
Weir

Aqueous
Advance

Fixed Aqueous
Advanced Weir

54

When dealing with ammoniacal solutions of nickel10, the use of the

following design criteria is suggested:
Mixer
O/A in mix box = 0.91.1 (Recycles used if needed)
Mixer residence time = 3 mins in extraction;
57 mins in stripping
Mixer tip speed = 250300 meter/min
Turbine diameter = 0.50.6 diameter of mixer
Settler
Specific flow rate (total flow) = 34 m3/m2/hr in extraction;
35 m3/m2/hr in stripping
Organic space velocity = 34 cm/sec
Organic depth = 2030 cm

When extracting uranium from dilute sulfuric acid solutions with

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 residence time = 12 mins in extraction; 23 mins in
wash; 24 mins in stripping; 23 mins in regeneration
Mixer tip speed = 250300 meter/min
Turbine diameter = 0.50.6 diameter of mixer
Settler
Specific flow rate = 34 m3/m2/hr
Organic space velocity = 24 cm/sec
Organic depth = 3040 cm

Figure 2: Dual Mixer Settler Unit

No. 1
Pump Mixer

No. 2 Axial
Flow Mixer

Adjustable
Aq Weir

Picket
Fence

Fixed Org Weir

Organic
Dispersion
Aqueous
Settler
Organic In

Org
Out

False Bottom
Aqueous Recycle

Aqueous In

Aq
Out

55

10.5 D
 iluents for
Metal Solvent Extraction Applications

The diluents used in metal solvent extraction applications have

evolved over the years and are no longer simple kerosene fractions.
Diluent suppliers have developed ranges of diluents specifically
for use in metal solvent extraction applications. These diluents
typically contain a mixture of paraffinic, aromatic and naphthenic
hydrocarbons. The relative proportions of these different hydrocarbon
classes can be altered to give improved performance for particular
applications. The diluents are also hydrotreated during the
manufacturing process to ensure that the olefinic content of the
diluent is very low. Olefinic double bonds tend to be reactive sites in
hydrocarbons that can undergo a variety of chemical attacks;
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

The selection of the proper diluent for use with a specific extractant
in a given extraction process is important due to potential effects on
both the chemical and physical properties of the system. Of equal
importance is maintenance of an on-going program to monitor the
quality of diluent make-up as it is received at the solvent extraction
plant. For help in developing a good laboratory program to select the
appropriate diluent and monitor the quality of the supplied material,
contact your local BASF Mining Solutions technical representative.
For additional information regarding diluents and their applications,
see the references on Chapter 10.5.

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

12

197

Pour Point (C)

(ASTM D97-09)

54

54

10

14

Fire Point (F)

(ASTM D92)

ND

179

254

ND

Flash Point (F)

(Pennsky-Marten CC)

150

210

190

132

Boiling Point (C)

350370 @ 1 atm1

260280 @ 23 mm Hg
185 @ 0.3 mm Hg

220228 @
0.03 mm Hg

Decomposes
(Slow onset at
80C @ 1 atm)

Surface Tension
(dyne/cm @ 25C)

27

29.3

57

29.5

Heat Capacity (cal/g/K)

0.406

0.450

0.523

0.550

Conductivity (pS/m)

5.3

5.2

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)

10

Pour Point (C)

(ASTM D97-09)

56

47

52

42

Fire Point (F)

(ASTM D92)

116

116

112

110

Flash Point (C)

(Pennsky-Marten CC)

>77

>77

>77

>77

Boiling Point (C)

Decomposes

Decomposes

Decomposes

Decomposes

Surface Tension
(dyne/cm @ 25C)

29.8

30

28.9

77

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)

(ASTM D97-09)

20

20

18

25

Fire Point (F)

(ASTM D92)

112

122

128

118

Flash Point (C)

(Pennsky-Marten CC)

>77

>77

>77

>77

Boiling Point (C)

Decomposes

Decomposes

Decomposes

Decomposes

Surface Tension
(dyne/cm @ 25C)

31

32

31

31

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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22

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12

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V
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13

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14

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15

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16

17

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29

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30

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31

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32

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E
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M
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M
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 ordosky, G.A.; Champion, W.H.; Dolegowski, J.R. Olafson, S.M. and W.S.Jensen The Use
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 rice, M.J. and Reid, J.G., Separation and Recovery of Nickel and Cobalt in Ammoniacal
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U.S. Patent 5,470,552

ackenzie, M., Virnig, M. and Feather, A., The Recovery of Nickel from
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10

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M
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Chapter 3.3
1

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Extraction Plants, Tsinghua Science and Technology, Vol 11(2), April, 2006, pp 160164.

61
11

 ackenzie, J.M., and Virnig, M.J., Solvent Extraction Technology for the Extraction of Nickel
M
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2004, eds, Imrie, W.P. and Lane, D.M., The Minerals, Metals and Materials Society, Warrendale,
PA., 2004, pp 457475.

12

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V
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13

Feather, A., Ramus, C. and Kordosky. G., Cognis LIX 84-INS Delivers High Concentration
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14

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10

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11

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12

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13

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M
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14

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C
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15

Ivanova,I., Fraser, K.S., Thomas, K.G., and Mackenzie, M., Uranium Hydrometallurgy
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16

 ender, J., Virnig, M., Nisbett, A., Crane, P., Mackezie, M., and Dudley, K., Uranium Solvent
B
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17

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18

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19

 eeley, F.G., Hurst, F.J. and Crouse, D.J., Solvent Extraction of Uranium from Carbonate
S
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20

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21

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 autista, R.G., The Solvent Extraction of Cobalt, Nickel and Their Associated Metals,
B
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British Patent 1,366,380

U.S. Patent 4,882,131

 ischer, D.D., Bauer, D.J., and Lindstrom, R.E., Recovery and Separation of Molybdenum
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U.S. Patent 4,965,054

 ee, J., Acar, S., and Virnig, M., Gold-Thiocyanate Solvent Extraction with Tertiary Amine
L
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U.S. Patent 5,426,220; U.S. Patent 4,994,609

U.S. Patent 3,323,857

10

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12

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C
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 ordosky, G.A., Some Aspects of Molybdenum Solvent Extraction, SME Annual Meeting,
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13

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 ewis, C,.J. and House, J.E., Recovery of Molybdenum by Liquid-Liquid Extraction from
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14

 ue, A., Skjutare, L., Bjorling, G., Reinhardt, H., and Rydberg, J., Separation of Iron, Cobalt
A
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 kac, P. and Paulenova, A., Speciation of Molybdenum(VI) in Aqueous and Organic Phases of
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 ialino, E., Mignot, C., Michel, P. and Vial, J., Extraction and Selective Stripping of Uranium
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 oyer, B.A. and McDowell, W.J., Characterization of Molybdenum Interfacial Crud in

M
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Society of AIME, New York, 1983, pp 503516.

 cDonald, J.P., Mattison, P.L. and Mackenzie, J.M.W., Problems in the Hydrometallurgical
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 hurchward, P.E. and Rosenblum, J.B., Sources and Recovery Methods for Rhenium,
C
USBM Report of Investigation, RI-6246, USBM, 1963.

 ischer, D.D., Bauer, D.J. and Lindstrom, R.E., Recovery and Separation of Molybdenum and
F
Rhenium from a Process Solution, USBM Report of Investigation RI-8088, USBM, 1975.

 acInnis, M.B., Quatrini, L.R. and Kim, T.K., An Improved Solvent Extraction Process for the
M
Separation of Rhenium From Molybdenum, 106th AIME Annual Meeting, March 610, 1977,
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10

 aylor, M.J.C., Green, B.R., Wyethe, J.P., Padayachee, D.P. and Mdlalose, K.E., Recovery of
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Chapter 8

Chapter 7
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M
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M
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Commercial Processes for Uranium from Ore, Handbook of Solvent Extraction, eds. Lo,
T.C., Baird, M.H.I. and Hanson,C., John Wiley & Sons, New York, 1983,
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Ivanova, I., Fraser, K., Thomas, K. and Mackenzie, M., Uranium Hydrometallurgy an
Overview, ALTA 2009 Nickel-Cobalt, Copper and Uranium Conference, Perth, Australia, May
2530, 2009.

 rane, P., Dudley, K. and Virnig, M., Uranium Solvent Extraction Using Tertiary Amines-Past,
C
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12

 gers, D.W., Drobnick, J.L. and Lewis, C.J., The Recovery of Vanadium from Acidic Solutions
A
by Liquid Ion Exchange, Annual Meeting of AIME, February 1822, 1962, New York, 1962.

13

 al, Y., Bal, K-E., Cote, G. and Lallam, A., Characterization of the Solid Third Phases that
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Vanadium(V)., Hydrometallurgy, 75, 2004, pp 123134.

14

 ordosky, G., Virnig, M., Crane, P., Dudley, K. and Feather, A., Uranium Solvent Extraction
K
from Acid Sulfate Leach Solutions Using Tertiary Amines, Preprint No 078-017, SME Annual
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 yman, B., Ekman, E., Kuusisto, R., Pekkala, P. and Lyyra, J., The OutoCompact SX
N
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Vol VI Hydrometallurgy of Copper (Book 2), eds., Riveros, P.A., Dixon, D., Dreisinger, D.B.
and Menacho, J., Canadian Institute of Mining, Metallurgy, and Petroleum, Montreal, Quebec,
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 iralico, M., Gigas, B. and Preston, M., Optimized Mixer Settler Designs for Tomorrows
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of Copper (Book 2), eds., Riveros, P.A., Dixon, D., Dreisinger, D.B. and Menacho, J., Canadian
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 iller, G., Design of Mixer-Settlers to Maximize Performance, ALTA 2006 Copper

M
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 ancas, M.F., Interface Level Control in Settlers, Copper 2007Cobre 2007, Vol IV The
V
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D., Dreisinger, D.B. and Collins, M.J., Canadian Institute of Mining, Metallurgy, and Petroleum,
Montreal, Quebec, Canada, 2007, pp 7179.

 aylor, A. and Jansen, M.L., Solvent Extraction Mixer-Settler Design, ALTA 2007 Copper
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Australia, 2007.

 illiam, Y., Simic, K., Rajasingam, R., Chovar, M. and Schwarz, M.P., Characterisation of
W
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Conference, ISEC 2011, October 37, 2011, eds., Valenzuela L., F. and Moyer, B.A.,
Gecamin, Santiago, Chile, 2011, pp123.

10

 irnig, M.J., Mackenzie, J.M.W., Wolfe, G.A. and Boley, B.D., Nickel Laterite Processing:
V
Recovery of Nickel from Ammoniacal Leach Liquors, Proceedings of 1999 SME Annual
Meeting: Mining in a New Era; Denver, CO, USA, March 13, 1999, pp 129.1129.11

11

Ivanova, I., Fraser, K.S., Thomas, K.G. and Mackenzie, M., Uranium Hydrometallurgy
Circuits-An Overview, ALTA 2009 Nickel-Cobalt, Copper & Uranium Conference, May
2530, 2009, Perth, Australia, ALTA Metallurgical Services, 2009.

12

 ackenzie, M. and Miller, G., Uranium Solvent Extraction Plant Designs Where does
M
Copper come into it? ALTA 2012 Nickel/Cobalt/Copper, Uranium and Gold Conference,
May 25June 2, 2012, Perth, Australia, ALTA Metallurgical Services, 2012.

Chapter 9
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U.S. Patent 3,883,634; U.S. Patent 4,432,952 and U.S. Patent 4,915,919.

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Quebec, Canada, April 2125, 1974.

U.S. Patent 4,018,865

 sseo-Asare,K., Leaver, H.S., Davis, P.K., and Lafferty, J.M., Extraction of Nickel and Cobalt
O
from Acidic Solutions Using LIX63-DNNS Mixtures, American Institute of Mining, Metallurgy
and Exploration, Annual Meeting, Denver, Colorado, February 26March 2, 1978.

 heng, C.Y., Zhang, W., and Pranolo, Y., Separation of Cobalt and Zinc from Manganese,
C
Magnesium and Calcium Using Synergistic Solvent Extraction Consisting of Versatic 10 and
LIX 63, Proceedings of ISEC 2008, International Solvent Extraction Conference, Vol 1, ed.
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2008, pp 163168.

U.S. Patent 5,229,086

 irnig, M, Eyzaguirre, M., Jo, M., and Calderon, J., Effect of Nitrate on Copper SX Circuits:
V
A Case Study, Proceedings of CopperCobre 2003 Internation Conference, Vol. IV (2),
Hydrometallurgy of Copper, eds., Riveros, P.A., Dixon, D.G., Dreisinger, D.B., and Menacho,
J.M., Canadian Institute of Mining, Metallurgy, and Petroleum, Montreal, Canada, 2003,
pp 795810.

 udderth, R.B., Copper Solvent Extraction from Ammoniacal Solutions: The Past, The
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Present and The Future, Proceedings Randol Copper Hydromet Roundtable 2000, Randol
International Ltd, 2000, pp. 203214.

 udley, K., Shaw, R., Vance, S. and Kibble, S., Regeneration of Ammoniacal Printed Circuit
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Board Spent Etchant Liquors Using LIX 84-I, Proceedings of ALTA 2005 Copper Conference,
May 1820, 2005, Perth, Australia, ALTA Metallurgical Services, 2005.

10

 chwab, W. and Kehl, R., Copper Recycling From Spent Ammoniacal Etching Solutions and
S
their Regeneration using Solvent Extraction, IMPC Conference, Aachen, Germany, 1997.

11

U. S. Patent 4,331,634

12

 ackenzie, M., Virnig, M. and Feather, A., The Recovery of Nickel from High-Pressure Acid
M
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Engineering, Vol 19, Issue 12, September, 2006, pp12201233.

13

U.S. Patent 6,210,647

14

U.S. Patent 4,563,256

15

Mattison, P.L. and Virnig, M.J., LIX-7800 Series: A New Reagent Family for Reversibly
Extracting Anions from Alkaline Solutions, Proceedings of International Solvent Extraction
Conference 1999, Vol 1, eds, Cox, M., Hidalgo, J., and Valiente, M., Society of Chemical
Industry, 2001, pp 375380.

16

U.S. Patent 5,939,034

17

 avis, M.R., MacKenzie, M.W., Sole, K.C. and Virnig, M.J., Recovery of Cu and CN- by SX
D
from Solutions Produced in Leaching of Cu/Au Ores, Proceedings of Gold and Silver Forum
99, May 1114, 1999, Randol International, 1999, pp 175187.

Chapter 10.5
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 andbook of Solvent Extraction, eds., Lo, T.C., Baird, M.H.I., and Hanson, C., John Wiley and
H
Sons, New York, 1983, pp 638647.

 itcey, G.M., and Ashbrook, A.W., Solvent Extraction, Principles and Applications to Process
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 ishop, M.D., Gray, L.A., Young, T.L. and Greene, M.G., Technical Developments Leading to
B
Modern Solvent Extraction Diluents, Pre-Print 9649, SME Annual Meeting, March 1114,
1996, Phoeniz, AZ, 1996.

 ishop, M.D., Solvent Extraction Diluents, What are they and How do they affect SX Plant
B
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Vancouver, B.C., Randol International Ltd, 1998, pp 121126.

 ishop, M.D., Gray, L.A., Greene, M.G., Bauer,K., Young, T.L., May, J., Evans, K.E. and
B
Amerson-Treat, I., Investigation of Evaporative Losses in Solvent Extraction Circuits,
Proceedings of the Copper 99Cobre 99, Vol IV, Hydrometallurgy of Copper, eds., Young,
S.K., Dreisinger, D.B., Hackl, R.P. and Dixon, D.G., TMS, 1999, pp 277290.

 irnig, M.J., Olafson, S.M., Kordosky, G.A. and Wolfe, G.A., Crud Formation: Field Studies
V
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 ollao I., N., Jennemann, G.E., Sublette, K., Bishop, M.D., Young, S.K. and Morrison, A.G.,
C
Biological Degradation of Solvent Extraction Circuit Plant Organic, Hydrometallurgy 2003
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Alfantazi, A.M., Anderson, C.G., Dreisinger, D.B., Harris, B., and James, A., TMS, 2003,
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 alzada, M.A., Kowalik, R. and Guyomar, P.Y., Comparison of Low Aromatic and Traditional
C
Hydrocarbon Extraction Diluents in Copper Production, ISEC 2011, 19th Internation solvent
Extraction Conference, October 37, 2011, Santiago Chile, eds., Valenzuela L, F., and Moyer,
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 aig, P.A., Duthie, A.M. and Valladares, S.M., Copper Solvent Extraction Diluent Choice
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solvent Extraction Conference, October 37, 2011, Santiago Chile, eds., Valenzuela L, F., and
Moyer, B.A., Gecamin, 2011, Paper #31.

Chapter 10.4
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 itcey, Gordon M., Solvent Extraction, Principles and Applications in Process Metallurgy,
R
Revised Edition 2006, Vol 1, Gordon M Ritcey and Assoc., Ottawa, Canada, 2006,
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 andbook of Solvent Extraction, eds., Lo, T.c., Baird, M.H.I. and Hanson, C., John Wiley and
H
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 ancas, M.F., Solvent Extraction Settlers, A Comparison of Various Designs, Copper

V
2003Cobre 2003, Vol VI Hydrometallurgy of Copper (Book 2), eds., Riveros, P.A., Dixon,
D., Dreisinger, D.B. and Menacho, J., Canadian Institute of Mining, Metallurgy, and Petroleum,
Montreal, Quebec, Canada, 2003, pp 707717.

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North America

Australia

BASF Corporation
2430 N. Huachuca Drive
Tucson, Arizona 85745
US
Phone: +1 520 622 8891
Fax: +1 520 624 0912

BASF Australia Ltd.

Level 12, 28 Freshwater Place
VIC 3006, Southbank
Australia
Phone: +613 8855 6600
Fax: +613 8855 6511

BASF CHILE S.A.

Av. Carrascal N 3851
Quinta Normal
Santiago
Chile
Phone: +56 2 2640 7000
Fax: +56 2 775 3095

For further information:

miningsolutions@basf.com
www.mining-solutions.basf.com

The descriptions, designs, data and information contained herein are presented in good faith, and are based on BASFs
current knowledge and experience. They are provided for guidance only, and do not constitute the agreed contractual
quality of the product or a part of BASFs terms and conditions of sale. Because many factors may affect processing or
application/use of the product, BASF recommends that the reader carry out its own investigations and tests to determine
the suitability of a product for its particular purpose prior to use. It is the responsibility of the recipient of product to ensure
that any proprietary rights and existing laws and legislation are observed. No warranties of any kind, either express or
implied, including, but not limited to, warranties of merchantability or fitness for a particular purpose, are made regarding
products described or designs, data or information set forth herein, or that the products, descriptions, designs, data or
information may be used without infringing the intellectual property rights of others. Any descriptions, designs, data and
information given in this publication may change without prior information. The descriptions, designs, data, and information
furnished by BASF hereunder are given gratis and BASF assumes no obligation or liability for the descriptions, designs,
data or information given or results obtained, all such being given and accepted at the readers risk. (02/2014)
= registered trademark of BASF SE

EVG1368e

South America