Professional Documents
Culture Documents
Mining Solutions
Content
1. Introduction
2. Solvent Extraction
3.1
3.2
13
3.3
15
21
23
27
7. Extraction of Uranium
31
35
40
10. Appendices
41
41
42
51
53
55
56
11. Footnotes
59
1. Introduction
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.
2. Solvent Extraction
Formula 1
Extract
2RH(Organic) + Cu+2(Aqueous)
R2Cu(Organic) + 2H+(Aqueous)
Strip
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
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
Final Metal
Recovery
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.
H
O
O N
O
N
H
O
O N
O
N
H
R
CH3
O
Cu
CH3
N
Aldoxime
Ketoxime
C9H19
C9 Aldoxime,
5-Nonylsalicylaldoxime
Ketoxime, 5-Nonyl-2hydroxyacetophenone
Oxime
C12H25
O
O
H
R
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
80
Mo
Extraction %
Metal
Cu(II)
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
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
3.5
3
Cu Conc (g/L)
2.5
2
Stripped Organic
1.5
1
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.
LIX 84-I1)
100
LIX 937N
70
30
LIX 984N
50
50
LIX 973N
30
70
LIX 860N-I2)
100
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.
3.5
3
Cu Conc (g/L)
2.5
2
Stripped Organic
1.5
1
0.5
0
LIX
654N-LV
LIX
664N-LV
LIX
674N-LV
LIX
684N-LV
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)
12
13
3.2 D
evelopment of a Cu SX
Process Flow Sheet
Cu (g/L)
pH
<1 to 6
1.3 to 2.2
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
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
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
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
Equation1
[2.50 g/L Cu x (0.90)]/0.26 g/L Cu per % v/v = 8.7% v/v LIX 984N
16
5.0
60
4.0
50
3.0
2.0
1.0
0.5
1.0
1.5
2.0
2.5
40
30
20
3.0
0.5
1.0
1.5
2.0
2.5
3.0
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
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.
3.0
2.0
1.0
SO
0.5
Raff. = 0.22
1.0
1.5
2.0
2.5
3.0
18
LO
4.0
3.0
2.0
1.0
SO
0.5
1.0
1.5
2.0
2.5
3.0
Raff. = 0.15
60
RE
50
40
SE
30
SO = 1.77
0.5
1.0
1.5
2.0
2.5
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
19
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.
20
5.0
LO
4.0
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
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).
80
Metal Extraction (%)
Ni
Cu
60
40
Zn
20
50
100
150
Formula 1
M(NH3)4+2(Aqueous) + 2 RH (Organic)
200
250
22
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.
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+.
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:
To acid leach
Ammonia leaching
S
L
Steam stripping
and oxidation
Steam/air
Reject or return
to acid leach
S
L
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
Organic bleed
to Co and Cu strip
and reoximation
25
PLS
Raffinate
E1
E2
E3
Wash Aq
SOW
LOW 1
S1
S2
S3
S4
Nickel Electrowinning
Formula 1
Extraction
Stripping
26
27
6. B
ASF Alamine and
Aliquat Reagents
Alamine 308
Alamine 336
Alamine 304
R
N
Alamine Reagents
R
R
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
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
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
Mo
Zn
Cu
80
Fe2+
Fe3+
Extraction %
Co
60
40
Sn
20
Mn
0
100
Ni, Cr
200
[CL], g/L.
300
29
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
kH2CrO4
mHI
cH2SO4
fCH3COOH
(a) Taken from Standard Methods of Chemical Analysis, Volume II A, Sixth Edition, page 190. Van Nostrand Reinhold Company, 1963.
30
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
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
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
HX
3040C
Liquor
to calciner
Na2CO3/NaOH
regeneration
pH ~11.0
H2SO4
protonation
pH ~1.0
Barren
organic
33
34
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.
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.
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.
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
Spent Wash
1.3 g/L
NH 3 Strip Soln
65 g/L
Wash Water
37
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.
Vanadium Chemistry
Cationic VO2+1
Vanadium Extraction
2.0
4.0
6.0
8.0
10.0
12.0
14.0
pH
Extraction
Stripping
(R3NH+)4H2V10O28-4(Org) + 5 NH4OH(Aq)
(R3NH+)4H2V10O28-4(Org)
Extraction
4 R3NCH3+Cl-((Org) + H2V10O28-4(Aq)
(R3NCH3+)4H2V10O28-4(Org) + 4 Cl-(Aq)
Stripping
39
40
9. L
IX Reagents
Additional Applications
41
10. Appendices
10.1 Isocalc* Computer Modeling Software
42
43
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
Cu = S300
3. Extraction kinetics
% =
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
x 100
44
45
M H+ in aqueous = A x B/C
where A = ml 0.1 M NaOH
B = M NaOH
C = ml aliquot titrated
M H+ consumed by stripping metal = 2 x D
where D = total M of metals stripped into the buffer
g/L NH3 in organic = (E F G) x 17.03/H
where E = M H+ in KHP buffer
F = M H+ in aqueous
G = M H+ consumed by stripping metal
H = O/A in shake out
46
Calculations
Maximum Nickel Loading
Take an aliquot of the diluted reagent and an equal volume of
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.
Ni = S20 Ni g/L
3. Extraction kinetics
% = (E30/E300) x 100
5. Strip kinetics
% =
6. Net transfer
Ni = E300 Ni S20 Ni
x 100
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
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.
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
% =
x 100
x 100
50
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
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
Table 3:
Reagent
Alkyl
Groups
Application
Table 2:
Tertiary Amines
Reagent
Application
Alamine
308
Tri-iso
C8
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
LIX 84-IT
LIX 63
LIX 7820
Quaternary Amine
Aliquat
336
Tri-n (C8
C10), Methyl
53
Organic
Advance
Aqueous Recycle
Organic
SETTLER
Aqueous
Organic Discharge
Aqueous Up Comer
Aqueous Recycle
Advance
Adjustable
Aqueous
Weir
Aqueous
Advance
Fixed Aqueous
Advanced Weir
54
No. 1
Pump Mixer
No. 2 Axial
Flow Mixer
Adjustable
Aq Weir
Picket
Fence
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 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
Alamine 336
Alamine 304
Aliquat 336
S.G. (g/cc)
0.81
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
54
54
10
14
ND
179
254
ND
150
210
190
132
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
0.406
0.450
0.523
0.550
Conductivity (pS/m)
5.3
5.2
High
57
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
56
47
52
42
116
116
112
110
>77
>77
>77
>77
Decomposes
Decomposes
Decomposes
Decomposes
Surface Tension
(dyne/cm @ 25C)
29.8
30
28.9
77
0.478
0.406
0.430
0.454
Conductivity (pS/m)
214
109
52
47
58
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
20
20
18
25
112
122
128
118
>77
>77
>77
>77
Decomposes
Decomposes
Decomposes
Decomposes
Surface Tension
(dyne/cm @ 25C)
31
32
31
31
0.406
0.478
0.502
0.430
Conductivity (pS/m)
44
33
21
13
59
11. Footnotes
Chapter 1
ender, J.T. and Virnig, M., Stripping Equilibrium Modification Based on the Chemical
B
Structure of Equilibrium Modifiers, ISEC 2008, Solvent Extraction: Fundamentals to Industrial
Applications, Proceeding of ISEC 2008, Vol I, ed, Moyer, B.A., Canadian Institute of Mining,
Metallurgy and Petroleum, Montreal, Quebec, Canada, 2008, pp 101106.
irnig, M., Eyzaguirre, D., Jo, M. and Calderon, J., Effects of Nitrate on Copper SX Circuits:
V
A Case Study, Copper 2003Cobre 2003, Hydrometallurgy of Copper, Vol II, Modeling,
Impurity Control and Solvent Extraction, eds, Riveros, P.A., Dixon, D.G., Dreisinger, D.B. and
Menacho, J.H., Canadian Institute of Mining, Metallurgy, and Petroleum, Montreal, Quebec,
Canada, 2003, pp 795810.
irnig, M.J., Olafson, S.M., Kordosky, G.A. and Wolfe, G.A., Crud Formation: Field Studies
V
and Fundamental Studies, Fourth International Conference Copper 99Cobre 99, Vol IV:
Hydrometallurgy of Copper, eds, Young, S.K., Dreisinger, D.B., Hackl, R.P. and Dixon, D.G.,
The Metallurgical Society of AIME, Warrendale, PA, 1999, pp 291304.
ordosky, G. and Virnig, M., Equilibrium Modifiers in Copper Solvent Extraction Reagents
K
Friend or Foe?, Hydrometallurgy, 2003 Fifth International Conference in Honor of Professor
Ian Ritchie, Vol I: Leaching and Solution Purification, eds, Young, C.A., Alfantazi, A.M.,
Anderson, C.G., Dreisinger, D.B., Harris, B. and James, A., The Minerals, Metals and Materials
Society, Warrendale, PA, 2003, pp 905916.
isbett, A., Bender, J. and Kordosky, G., The Effect of Modifier Properties on the Performance
N
of Copper Solvent Extraction Reagents, HydroCopper 2011, Proceedings of the 6th
International Seminar on Copper Hydrometallurgy, 68 July 2011, Vina Del Mar, Chile, eds,
Casas, J.M., Lightfoot, C. and Tapia, G., Gecamin, Santiago, Chile, 2011.
orrison, G., and Freiser, H., Solvent Extraction in Analytical Chemistry, John Wiley and Sons,
M
Inc., New York, 1957.
oss, A.M., Solvent Extraction Newcomer to the Colorado Plateau, AIME Annual Meeting,
R
New Orleans, Louisiana, February 12, 1957.
ouse, J.E., The development of the LIX reagents, AIME Transactions Volume 286, 1989,
H
Part B Minerals and Metallurgical Processing, February 1989.
ower, K.L, Operation of the First Commercial Copper Liquid Ion Exchange and
P
Electrowinning Plant, AIME Annual Meeting, New York, New York, February, 1970.
laschuk, B., and Joy, S., A Brief History of the Freeport McMoRan Bagdad Solvent
B
Extraction Plant, Preprint 10128. SME Annual Meeting, Phoenix, Arizona, February 28
March 3, 2010.
udderth, R.B., Copper Solvent Extraction from Ammoniacal Solutions: The Past, The
S
Present, and The Future, Randol Copper Hydromet Roundtable 2000, Tucson, AZ,
September 58, 2000, pp 203214.
10
gers, D.W. and Dement, E.R., The evaluation of new LIX reagents for the extraction of
A
copper and suggestions for the design of commercial mixer-settler plants, AIME Annual
Meeting, San Francisco, CA, February 1972, TMS Paper A7287.
Chapter 3.2
11
attison, P.L., Kordosky, G.A., and Champion, W.H., Enhancement of solvent extraction by
M
clay treatment of contaminated circuit organics, Hydrometallurgy Research, Development
and Plant Practice, ed Osseo-Asare,K., and Miller, J.D., Proceedings of the 3rd Intenational
Symposium on Hydrometallurgy, 1983, pp 617628.
upta, C.K. and Mukherjee, T.K., Hydrometallurgy in Extraction Processes, Volume 1., CRC
G
Press, Ann Arbor, MI, 1990, pp 3546.
12
13
14
lrich, B., Andrade, H. and Gardner, T., Lessons learnt from heap leaching operations in
U
South America An update, Journal of South African Institute of Mining and Metallurgy,
January/February 2003, pp 2328.
15
16
ackenzie, J.M.W., and Virnig, M.J., Recovery of nickel from ammoniacal solutions using
M
LIX 84-I, Proceedings of Nickel/Cobalt Pressure Leaching & Hydrometallurgy Forum, ALTA
Conference, Perth, Western Australia, May 1314, 1996.
eacey, J., Guo, X.J. and Robles, E., Copper Hydrometallurgy Current Status, Preliminary
P
Economics, Future Direction and Positioning Versus Smelting, Copper 2003Cobre 2003,
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18
19
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Collins, M.J., Canadian Institute of Mining, Metallurgy and Petroleum, Montreal, Canada,
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10
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1
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M
Hydrochloric Acid by Oxime Extractants Effect of the Composition of the Extractants, ISEC
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60
11
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C
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ordosky, G., Copper SX Circuit Design and Operation Current Advances and Future
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WO 2009/009825
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ordosky, G., Using the Flexibility of Copper Solvent Extraction Reagents and Plant Staging
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10
19
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11
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20
12
21
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13
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22
23
24
25
26
27
12
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V
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13
ordosky, G., Virnig, M. and Boley, B., Equilibrium Copper Strip Points as a Function of
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14
oyer, H.R., Copper Sulphate Via Solvent Extraction and Crystalization, AIME Annual
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15
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16
17
udley, K. and Shaw, R., Regeneration of Ammoniacal Printed Circuit Board Spent Etchant
D
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28
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29
ordosky, G.A., Development of Solvent Extraction Processes for Metal Recovery Finding
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30
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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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1
ordosky, G., Virnig, M. and Boley, B., Equilibrium Copper Strip Points as a Function of
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12
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13
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14
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14
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15
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16
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17
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18
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19
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20
all, S. and Reed, M., Cross Contamination of ODC Solvent Extraction Circuits, SME Annual
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21
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14
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10
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M
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M
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rane, P., Dudley, K. and Virnig, M., Uranium Solvent Extraction Using Tertiary Amines-Past,
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12
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13
al, Y., Bal, K-E., Cote, G. and Lallam, A., Characterization of the Solid Third Phases that
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14
ordosky, G., Virnig, M., Crane, P., Dudley, K. and Feather, A., Uranium Solvent Extraction
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and Menacho, J., Canadian Institute of Mining, Metallurgy, and Petroleum, Montreal, Quebec,
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10
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V
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11
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12
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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,
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10
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12
ackenzie, M., Virnig, M. and Feather, A., The Recovery of Nickel from High-Pressure Acid
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