Commercial Application of Extracting Reagents

for Metal Recovery

Part – II. Basic and Neutral Extractants
Muhammad Tariq Saeed*, Z. H. Rizvi** Javaid Ahmad** and M. Y. Shaheen*

Abstract

The developments in reagents’ availability and their application in commercially successful

metal recovery operations have been described in this review. Basic and neutral or solvating
extractants are presented in this part of the paper.

Introduction organic moiety causes the extraction of a large,

In part–I of this paper1, the developments in anionic metal complex into the organic phase, with
reagents’ availability and extraction of acid and concomitant expulsion of a small common anion to
chelating extractants in commercially successfully the aqueous phase. Henkel Corporation markets
metal recovery operations were described. The two classes or compounds which fall into the
present paper deals with the developments and general classification. Alamine and Aliquat are the
application of basic and neutral or solvating registered trade names of Henkel Corporation for
extractants. them.

Basic Extractants Alamine Series

For metals existing in solution in anionic The Alamine Series of reagents contain a
form, an anion exchange process is more effective, basic nitrogen capable of forming amine salts with
so basic extractants are used. The only basic a variety of inorganic and organic acids. The
extractants studied for the extraction kinetics are amines which find the widest use in metals
high molecular weight amines. The extraction recovery processing by solvent extraction are the
takes place through the formation of an ion-pair tertiary amines of the general formula R3N where
and for this reason these extractants have also R can represent a verity of hydrocarbon chains.
been called liquid anion exchanger. Metal ions can The equations below represent the extraction
be extracted both as negatively charged complexes chemistry of the Alamine series reagents:
and natural complexes. The neutral or negatively
[ R3 N ]org + [ HA ]aq [ R3 H+A- ]org (1)
charged metal species are formed in the aqueous
phase with water soluble anions. This type of [ R3 H+A- ]org + [ B- ]aq [ R3 H+B- ]org
extractants is based on the principle of ion
+ [ A- ]aq (2)
association; whereby a large positively charged

*PCSIR Laboratories Complex, Shahrah-i-Jalal-ud-Din Roomi, Lahore – 54600, Pakistan.

** Institute of Chemical Engineering & Technology, University of the Punjab, Lahore
2 Journal of Pakistan Institute of Chemical Engineers Vol. XXXVII

Equation (1) is simply amine salt formation practiced at Falconbridge Nikkelwerk at

while equation(2) represent true ion exchange. The Kristiansand, Norway9,10, finally divided copper-
extent to which [ B- ] will exchange for [ A- ] is a nickel converter matte is treated with strong HCl
function of the relative affinity of the two anions and nickel is selectively dissolved, leaving copper
for the organic cation and the relative stability of and platinum metals in the insoluble sulphide
the anions in the aqueous medium. Since tertiary
residue. The oxidized iron is extracted with 4%
amines can form salt with a wide variety of acids,
TBP (tri-n-butyl phosphate) in aromatic
the choice of reagents for a liquid ion exchange
hydrocarbon diluent. From the loaded TBP, iron is
process is not strictly limited, i.e. bisulphate,
chloride, etc. of any of the Alamine reagents can be stripped with water and solvent is recycled. From
used. Amine type extractants can be stripped with the iron free solution, both copper and cobalt are
a wide variety of inorganic salt solution such as extracted as anionic chloro-complexes, with 11 vol.
NaCl, Na2CO3 and (NH4)2SO4. The choice of % solution of tri-iso-octyl amine in an aromatic
stripping agent depends on the overall recovery diluent. The metals from the extract can be
process but in general basic stripping agents which stripped with water and from the raffinate nickel
deprotonate the amines give the best stripping in is recovered as NiCl2.4H2O by passing HCl gas
the fewest stages. The equation below shows the through it. The extraction of element 104
stripping action of Na2CO3 on an amine salt. Rutherfordium (Rf) and its group 4 homologs11
2 [ R3 N H+ B- ]org + [ 2 Na+ + CO32- ]aq into tri-iso-octylamine in xylene from various
concentrations of HF has been studied.
2 [ R3 N ]org + [ H2O- ]aq + CO2 + 2 [ Na+ ]aq
+ 2 [ B- ]aq (3) (iii) Alamine 336 (tri-(C8-C10) amine)
The greatest commercial acceptance for This finds application in:
Alamine type reagents has been in uranium
recovery process however, any metal capable of (i) Vanadium extraction12
forming anionic complexes in aqueous solutions is (ii) Cobalt-nickel separations from HCl13
a candidate for extraction by an amine type
extractant. (iii) Chromium extraction14,15

Some of the known uses of Alamine (iv) Iron extraction from aluminium chloride
extractants commercially available from Henkel solution16,17
Corporation are given below:- (v) Uranium recovery from sulphuric acid
leach liquors18 or sulphuric acid resin
(i) Alamine 300 (tri-n-octylamine) eluate solutions19,20
This is used in cobalt extraction from (vi) Platinum group metals separations21
chloride leach solutions2,3, extraction of zirconium
from sulphate solution4, separation of zirconium – (vii) Tungsten recovery and separation of
hafnium from sulphate solutions5,6, extraction of zirconium and hafnium from sulphate
iron from chloride solution7 and copper extraction solution22,23. Extraction isotherms24 for
from chloride solution8. various metals from chloride solutions by
Alamine 336 is shown in Figure 1.
(ii) Alamine 308 (tri-iso-octylamine)
(viii) Extraction of copper and cadmium from
This finds application from cobalt / nickel acidic chloride solutions25
separation from hydrochloric acid liquors9,10 and
copper/nickel extraction from hydrochloric acid (ix) Separation of molybdenum, vanadium and
solutions10. In Falconbridge Matte Leach process nickel26
2009 Muhammad Tariq Saeed, Z. H. Rizvi Javaid Ahmad and M. Y. Shaheen 3

therefore, stripping is usually more difficult than

with the parent amine type reagents.

Aliquat 336 (tri-(C8-C10) methyl ammonium

Chloride)
Vanadium extraction12, separation of
platinum group metals21,27, rare earth
extractions28, rhenium recovery29, arsenic
extraction from refinery electrolytes , extraction
30

of chromium31, tungsten and copper are carried out

with this reagent. Mixtures of Aliquat 336 and
TOPO (tri-n-octyl phosphine oxide) result in
synergistic extraction of zirconium and hafnium32
from acidic thiocyanate media. Extraction of
copper and cadmium from acidic chloride
solutions25, zinc and cobalt recovery and
separation33, purification of nickel sulphate
Fig. 1 Alamine® 336 extraction isotherms from solutions from micro quantities of Co(II), Zn(II)
chloride solution at 40OC and pH=2 (24). and Cu(II)34 and gold extraction35 have been
achieved by solvent extraction using this reagent.
(v) Alamine 310 (tri-isodecylamine)
This is used in uranium and vanadium Aliquat 336 Nitrate
extraction from acidic sulphate leach liquors and The nitrated salt of Aliquat 336 is a specific
platinum group metals separations21. product for rare earth separations. Extraction
mechanism of bismuth (III)36 from nitrate aqueous
(vi) Alamine 304 (trilaurylamine)
solution with trioctyl methyl ammonium nitrate in
This is used for uranium and molybdenum xylene has been studied.
extraction from acidic leach liquors, the advantage
Further possible uses of these types of
being that the molybdenum amine complex is
reagents (Alamine and Aliquat series) may lie in
highly soluble.
the areas of :-

Aliquat Series (a) Inorganic acid purification37

The Aliquat series of reagents is based on (b) Niobium, titanium, tantalum and
methyl chloride quarternization of a respective zirconium separations38
Alamine reagent. Because a quarternized amine is (c) Separation of cobalt, copper and zinc from
always positively charged, anion extraction with nickel39
Aliquat reagents is not pH dependent as it is with
(d) Reclaiming metals from spent catalysts40
the tertiary amines. As a result, some basic metals
leach solutions may be successfully treated by In addition to these two classes of extractant
Aliquat type reagents without pH adjustment. The (Alamine and Aliquat series), the other important
biggest disadvantage of using an Aliquat reagent extractants of this type are :-
is that these reagents will not deprotonate,
4 Journal of Pakistan Institute of Chemical Engineers Vol. XXXVII

Primene JM-T (Primary amines, R-NH2) H2SO4 leach liquors in the Amex process.
The Amex process is widely used than the
This can be obtained from Rohm and Haas Depex process because of the greater
and is used for the extraction of iron from sulphate selectivity of tri-alkyl amine for uranium in
solution and separation of hafnium and zirconium H2SO4 solution than that of DEHPA (di (2-
from sulphate solutions41. ethylhexyl phosphoric acid).

Amberlite LA-1 and Amberlite LA-2 iii) Adogen 381 (Tertiary amine)
[Secondary amine. R2NH (n-laurylalkyl
This has various uses, e.g. extraction of
methylamine)]
uranium and cobalt42.
These are the products developed by Rohm
and Haas and are used for the extraction of
iv) Adogen 464 (Quaternary amine)
uranium from sulphate solutions and extraction of
iron and cobalt from chloride solutions42. It is proposed for the extraction of uranium,
vanadium, chromium and tungsten.
Hostarex-A327 (Tertiary amine, N3N, R=C8 –
C10) TOA (Tri-cctylamine)
This is the product developed by Farbwerke Sumitomo Metal Mining Company of Japan
Hoechst AG., Germany and is used for the utilized a different approach for the recovery of
extraction of uranium, vanadium, molybdenum cobalt and nickel from a sulphide concentrate at
and tungsten from sulphate solution. It is also their Niihama refinery3. The concentrate, assaying
used for the extraction of cobalt and copper from 25% Ni and 15% Co, with iron, manganese, copper
chloride solution and separation of zirconium from and silica as impurities, is pressure leached
hafnium. The purification of nickel sulphate autogenously with air. After removing impurities,
solutions from micro-quantities of Co(II), Zn(II) cobalt and nickel are extracted together from the
and Cu(II)34 by Hostarex-F3541 has been studied resultant solution, using Versatic-10 and stripped
for optimal conditions. out from the loaded solvent using HCl. From the
chloride solution, cobalt is selectively extracted
Adogens with tri-octylamine. Both nickel and cobalt are
Sherex Chemicals Co. introduced the finally recovered as metals electrolytically from
following reagents: the chloride solutions.

i) Adogen 283: (Secondary amine, di,tri- Baroncelli et al43 have used TOA to extract
gold from chloroanions of, for example copper, iron,
decyl amine)
tin and zinc, in aqua regia solution. The selectivity
This is proposed for the extraction of is attributed to the presence of TOA. Coextracted
vanadium and tungsten.
metals are scrubbed with dilute HNO3 and gold is
recovered by an HCL-thiourea solution.
ii) Adogen 364 (Tertiary amine, tri-iso-octyl
amine) Figure 2 illustrates the effect of HCl
concentration on cobalt extraction, with a
This may be used for the extraction of
maximum cobalt extraction observed at
platinum group metals from chloride
approximately 9 M. Above this concentration, the
solution. Commercial mixtures of tri-octyl to
HCl2– ion competes with CoCl42- for the extractant,
tri-decyl amines (e.g.Adegen 364 or Alamine
replacement of HCl by a metal chloride solution,
336) are used to recover uranium from
2009 Muhammad Tariq Saeed, Z. H. Rizvi Javaid Ahmad and M. Y. Shaheen 5

such as LiCl, eliminates this maximum. The figure resulting organo-metal complex which is insoluble
also shows that extraction depends on the in the aqueous phase and soluble in the organic
concentration and type of extractant44, thus, phase. Solvating extractants have an atom capable
extraction is greater for tertiary > secondary > of donating electron density to a metal in the
primary amines. This anion exchange process45 is formation of an adduct and are classified according
used commercially in Norway (Falconbridge to that ability:-
Nikkelwerk) and Japan (Sumitomo) for cobalt- R3PO > (RO)3PO > R2CO > ROH > R2O
nickel separation.
Trialkylphosphine oxides > trialkylphosphonates
In general, the use of organic phase > ketones > alcohols > ethers.
modifiers, normally polar organics such as long
chain alcohols, is required with amines in order to Extractions with solvating extractants are
keep the amine metal complexes soluble, to limited due to:
prevent third phase formation and/or to have a) The metal’s ability to form neutral complexes
acceptable phase separation. with anions.
b) The co-extraction of acid at high acid
concentrations.
c) The solubility of the organo-metal complex in
the organic diluent.

Important extractants of this type are tri-n-

butyl phosphate (TBP), tri-n-octylphosphine oxide
(TOPO), di-butyl butylphosphonate (DBBP), di-n-
octylsulphide (DOS), Methyl isobutyl ketone
(MIBK).

TBP (tri-n-butyl phosphate)

This has been marketed by Union Carbide,
U.S., Albright & Wilson, U.K. and Daihachi
Chemicals Co., Japan. TBP is one of the first
phosphorous-based extractants and today has
many commercial applications. It is used in
uranium refineries at various locations in the
USA, Canada, UK and France, A mining company
Fig. 2 Extraction of metal chlorocomplexes as a
in South Africa uses TBP to recover uranium from
function of chloride concentration (44).
tailings from a copper operation 46. TBP has also
been used in nuclear fuel reprocessing plants in
Neutral or Solvating Extractants
the USA, UK, France and Germany47. The solvent
A fourth category of extractants is known as extraction process that uses TBP solutions to
netural or solvating type extractants. Extractants recover plutonium and uranium from irradiated
of this type are basic in nature and facilitate nuclear fuels is called Purex (Plutonium and
extraction by coordinating with the metal uranium extraction). The Purex process provides
complexes and simultaneously replacing waters of recovery of more than 99% of both U and Pu and
hydration and formation of a neutral complex also provides excellent decontamination of both
through ion association, thereby causing the elements from fission products. Many variations of
6 Journal of Pakistan Institute of Chemical Engineers Vol. XXXVII

the Purex process have been extensively developed the case when the aqueous phase contained
and demonstrated on a plant scale. This process is NH4NO3. Extraction of Cd and Zn halo-complexes
now used world wide to reprocess spent reactor has been carried out by TBP58 to determine
fuel. separation factor.

TBP is used in the separation of rate earth The Belgian firm of Metallurgie Hoboken
elements in plants in USA and France. TBP was Overpelt59 (MHO) holds a patent for leaching the
also used in plants in USA and Canada to recover ocean nodules with hydrochloric acid. The leach
high purity zirconium from mixtures with solution is amenable from metal recovery only by a
hafnium, for use in nuclear applications. Neither solvent extraction technology. In the proposed
plant is currently operating. However, it is used in scheme, iron, zinc, molybdenum and vanadium are
a nickel refinery in Norway to remove iron, prior to separated by extraction using TBP and LIX 63
the separation of copper and cobalt and while copper, cobalt and manganese are recovered
precipitation of nickel48,49. At one time nuclear- by chemical precipitation. However, there appears
grade thorium was produced with TBP in the USA to be no reason why the latter, particularly copper,
and France, now neither facility is operating 46. nickel and cobalt, cannot also be recovered by
TBP is used as a synergist or phase modifier in solvent extraction. This process has the advantage
various solvent extraction processes including of a closed loop operation resulting in the
those for uranium, yttrium and indium. TBP is elimination of pollution problems.
also used for the extraction of zirconium and for
Solvent extraction of Mn(II) and Co(II) from
separating it from hafnium in the Port Hope
thiocyanate solutions60 by TBP, Rutherfordium
refinery of Eldorade Nuclear Limited, Ottawa 44,50
(Rf) and its group 4 homologs and other
and in India51.
tetravalent cations from various concentrations of
TBP is used commercially in the recovery of HBr and HCI61 by TBP, Europium, Eu(III), from
molybdenum and tungsten52, extraction of arsenic aqueous nitrate, perchlorate and thiocyanate
from electrolyte copper refinery in Australia 53, solutions62 by TBP, TOPO and dioctylsulfoxide,
recovery of nitric acid and hydrogen fluoride from and silver63 by the commercial extractants TBP
waste acid from steel pickling in Sweden and and Cyanex 471X has been studied
Japan54, recovery of platinum in Canada,
The use of the TBP, Cyanex 923 and many
separation of iridium from rhodium in West
other extractants are reviewed for the recovery of
Germany, recovery of iridium in South Africa 46
arsenic, antimony and bismuth from copper
and removal of chromium from chrome plating
electrolytes64. The chemistry and processes are
wastes in France55. From the mixture of high
presented and discussed. The mechanisms
temperature chlorination of fly ash by Hichlor
involved in the extraction of rare earths using
process, titanium can be recovered from the
different types of extractants like TBP, DEHPA, 2-
aqueous phase using the TBP in kerosene17.
ethylhexyl 2-ethylhexyl phosphoric acid and
Recently, there has been interest in the use of
quaternary ammonium salts are discussed in a
solvating extractants such as TBP and DBBP, for
review65 with 69 references. The flowsheets
the extraction of gold56 from alkaline cyanide
designed for the separation of various rare earths
solution. Extraction of trivalent ions of La, Pr, Nd
are also given.
and Sm (Lanthanum, Praesodymium, Neodymium
and Samarium) from aqueous nitrate solution by Extraction of zinc (II) from spent pickling HCl
either one component (TBP or DEHPA) or a mixed solutions66 obtained in zinc hot dip galvanizing
organic phase (TBP-DEHPA) has been carried plants has been studied. TBP and its mixtures
out57. The synergistic effect was discovered only in with DEHPA, HOEF 2562, Aliquat 336, Alamine
336 and many other Alamine 304, Alamine 308,
2009 Muhammad Tariq Saeed, Z. H. Rizvi Javaid Ahmad and M. Y. Shaheen 7

Alamine 310, and Cyanex 301 were used as many years. Albright and Wilson supplies
extractants. The acidic extractants (DEHPA and DEHPA/TOPO blends to customers who prefer to
Cyanex 301) did not extract both zinc (II) and iron avoid this step. TOPO has good performance in
(III) from 10% HCl. A precipitation occurred or other solvent extraction applications for many
stable emulsions were formed when Alamines 304, other metals but its high price has limited its wide
and 310 were used. Each of other reagents spread use.
coextracted both zinc (II) and iron (III). The latter
A pilot plant process using Cyanex 921
had to be reduced to iron (II) prior to extraction.
extractant to recover and separate niobium and
TBP and HOEF 2562 showed the best extraction
tantalum has been demonstrated77,78. Both metals
performance. TBP was used for separation carried
out in laboratory mixer settlers. The dynamics of wee extracted from a hydrofluoric sulphuric acid
extraction and stripping was studied and leach liquor and then selectively stripped from the
successfully modelled. loaded organic. The advantages of Cyanex 921
extractant in comparison to the commercially used
Cyanex 921 (tri-n-octylposphine oxide) MIBK extractant were shown to be higher
stability, lower aqueous solubility, rapid phase
This has been developed by American
disengagement and particularly the production of
Cyanamid Company and is known as TOPO. The
extraction characteristics of TOPO with a wide high purity niobium oxide which meets the
variety of metals have been investigated 67. The stringent specifications required for nuclear,
most important commercial application of TOPO optical and electronic applications.
in solvent extraction is its synergistic combination Rhenium has been recovered using Cyanex
with di (2-ethylhexyl) phosphoric acid (DEHPA) for 921 from petroleum reforming catalysts source
the extraction of uranium from wet process materials79. The process involves leaching the
phosphoric acid68-76. spent catalyst with sulphuric acid extracting
The TOPO-DEHPA process, originally rhenium and then stripping with ammonium
developed at the Oak Ridge National Laboratory 68, sulphate. Excellent selectivity against typical
is the most widely accepted one for industrial scale impurity metals such as aluminium, calcium,
exploitation. The solvent consists of a mixture of di magnesium and iron is achieved.
(2-ethylhexyl) phosphoric acid (DEHPA) and The removal of arsenic impurities from copper
TOPO dissolved in kerosene. This solvent electrolytes80 by solvent extraction with Cyanex
combination is effective for extracting hexavalent 921 has been carried out. The process describes
uranium from phosphoric acid. The extraction the selective extraction of arsenic followed by
coefficient with the mixture is higher than with stripping with an acidic sodium sulphate solution
either reagent alone. Commercialization of the and recovery of arsenic from the strip liquor by
process developed at Oak Ridge has been done by precipitation with H2S. Cyanex 921 is shown to be
Wyoming Minerals, Fla., by the Freeport Uranium stronger extractant for arsenic than tributyl
Recovery Co. La., and by the International phosphate which is now used in two commercial
Minerals & Chemical Corp. (IMC), Fla. The arsenic solvent extraction plants.
process for the recovery of uranium using a
synergistic mixture of Cyanex 921 extractant and A novel solvent extraction process using
DEHPA is operating successfully in a number of Cyanex 921 extractant to recover lithium from one
commercial plants in the U.S.A. Canada and of its sources (neutral brines) has been described 81.
Belgium. TOPO is a solid which must be melted Extraction of lanthanum (III) and Yttrium (III) 82
prior to blending the solvent and is being used for from aqueous HCl containing KSCN by TBP or
TOPO in benzene has been studied. It is found
8 Journal of Pakistan Institute of Chemical Engineers Vol. XXXVII

that extraction efficiency of TOPO is higher than DBBP (di butyl butylphosphonate)
that of TBP. The partition of Eu(III) between
DBBP is an under-used extractant with
benzene containing solvating extractants (TBP,
properties lying somewhere between TBP and
TOPO, dioctyl sulphoxide) and aqueous nitrate,
TOPO. Recently, interest in DBBP has increased
perchlorate and thiocyanate solution 62 has been
due to new commercial and developmental
investigated.
applications. DBBP has been used with DEHPA in
the recovery of uranium from wet process
Cyanex 923
phosphoric acid. It was used in the USA to recover
This extractant is a mixture of four trialkyl americium-241 from plutonium in waste streams
phosphine oxides where alkyl groups are hexyl and recovery system, but is no longer used in this
octyl groups. It exhibits extraction properties application86.
similar to those of TOPO. The major advantage of
Recently, there has been interest in the use of
Cyanex 923 extractant over similar extraction
DBBP in new processes in the recovery of
reagents, e.g. TOPO (trioctylphosphine oxide), is
titanium, gold and silver but these have not yet
that it is a liquid and is completely miscible with
been commercilized87. This has been marketed by
all commonly used hydrocarbon diluents. It is
Albright and Wilson as Albrite DBBP.
particularly useful for the removal of arsenic from
copper electrolytes and the recovery of carboxylic
DOS (di-n-octylsulphide)
acids, phenols and ethanol from effluent streams.
Cyanex 923 extractant is a potential substitute for It is used for the extraction of palladium from
TOPO in the process for the recovery of uranium chloride solutions88. Two commercial flowsheets
from wet process phosphoric acid. The advantage have been developed using either di-n-
of using Cyanex 923 extractant in place of TOPO octylsulphide or a hydroxyoxime as selective
in niobium-tantalum separation is due to its liquid extractants to remove the palladium, followed by
state and higher solubility in organic solvents. TBP and an amine to recover platinum. The
extraction of palladium by the sulphide is slow
Recently Cyanex 923 extractant has been used for
with 2 – 3 hours to achieve the equilibrium, which
the extraction of hafnium83 from acidic chloride
inhibits flowsheet design. However, it has been
solution. The solvent used for the extractant is
shown that tertiary amines can act as a kinetic
kerosene. The use of TBP, Cyanex 923 and many accelerator, reducing equilibrium times to
other extractants64 are reviewed for the recovery of minutes. High loading of the sulphides is possible
arsenic, antimony and bismuth from copper and stripping is easy with aqueous ammonia.
electrolytes. Recovery of cobalt84 using solvent
extraction has been carried out with Cyanex 923. MIBK (Methyl iso-butyl ketone)
It is used for the separation of zirconium and
Cyanex 925 (Bis (2,4,4-trimethylpentyl)
hafnium from a chloride solution 89,90 by American
octylphosphine oxide)
Metal Climax, Teledyne, Wah Chang and Ugine,
Cyanex 925 is a highly hindered phosphine who are the major zirconium producers in the
oxide which exhibits a greater degree of selectivity World. It is also used for the separation of
than conventional straight chain phosphine oxides. niobium/tantalum. Selective extraction of gold
Potential applications of this extractant include from chloride solutions91 is being carried out by
the recovery of tin from chloride solutions, removal Matthey Rustenberg Refiners, United Kingdom for
of arsenic from copper electrolytes and the their Royston refinery. Figure 3 shows the
separation of niobium and tantalum85. extraction of elements from a chloride medium by
MIBK92. Kinetics of extraction of copper and
2009 Muhammad Tariq Saeed, Z. H. Rizvi Javaid Ahmad and M. Y. Shaheen 9

cadmium15 from an acidic aqueous chloride coextracted elements can be easily scrubbed with
medium into a coexisting organic phase containing dilute HCl. Because of the high distribution
MIBK and high molecular amines have been coefficient recovery of gold is best achieved by
studied for stirred and unstirred systems. chemical reduction. Thus, oxalic acid at 90 oC
produces easily filtered gold grain. However, the
slow kinetics necessitates a batch process.

INCO has utilized solvent extraction methods

for recovering gold from solutions. The process is
based on the extraction of gold in oxidized form
with dibutylcarbitol from 3 to 4 M HCI solution.
Barnes and Edwards88 have described in detail the
flow sheet developed by INCO for their Acton
Precious Metals Refinery. Extraction of elements
from chloride medium by dibutylcarbitol 96 is
shown in Figure 4.

Fig. 3 Extraction of elements from a chloride

medium by MIBK ((2).

DHSO (di-n-heptyl sulphoxide)

A suggested flow sheet for the extraction of
platinum group metals (Pd, Pt, Ir, Rh) using
DHSO as extractant in trichloroethylene has been
described by Lewis et al93. Solvent extraction study
of Nd (III) , Eu(III) and Tn(III) has been carried
out by dimethyl sulphoxide (DMSO)94.

Dibutylcarbitol (diethyleneglycol dibutyl

ether)
Gold exists in the leach solution as AuCl 4- and
all the processes rely on the extraction of this ion Fig. 4 Extraction of elements from a chloride
or the parent acid by ion pair or solvating medium by dibutylcarbitol (96).
extractants respectively. The early studies by
Cyanex 471X (tri-isobutyl phosphine
Morris and Khan95 led to the adoption of
dibutylcarbitol (Butex) by INCO in a gold refinery
sulphide, TIBPS)
several years before the complete solvent Cyanex 471X is particularly useful extractant
extraction refining flowsheet was produced. The for the selective recovery of sliver using a DEHPA
extractant has a high selectivity for gold and phase modifier and separation of palladium and
10 Journal of Pakistan Institute of Chemical Engineers Vol. XXXVII

platinum using a nonylphenol phase modifier. It 4 Malek, Z., Schrotterova, D., Jedinakova, V.,
will also extract mercury and gold. Solvent Mrnka, M. and Celleda, J.; Proc. Int. Solv.
extraction of silver63 by commercial extractants Extr. Conf: 74, Vol. 1, 477 (1974).
TBP, Cyanex 471X, Cyanex 301 and Cyanex 302 5. Takahashi, O.; ‘Process for the Separation of
has been carried out. Zirconium and Hafnium’ U.S. Patent 3,
It is of interest to note that virtually all the 658,466, April 25 (1972).
equilibrium and phase modifiers commonly used 6 Takahashi, M., Miyazai, H. and Katoh, Y.;
come from this class of extractants. This is no Proc 6th ASTM Int. Conference on Zirconium
surprise since both equilibrium and phase in the Nuclear Industry, Vancouver,
modifiers require a group having the ability to Canada, June 20 –July 1 (1982)
donate electron density and in some cases 7 Harada, M., Yamazaki, F., Shiomi, N.,
hydrogen bond. Adachi, M. and Eguchi, W.; J. Chem Eng.
Japan, 17(5), 521 (1984)
Conclusions
8. Kyuchaukov, G. and Mihaylov, Y.:
The potential of solvent extraction is well Hydrometallurgy, 27(3) 361 (1991).
documented by the wide variety of metal 9. Magner, J.E.: Proc. AIME Annual Meeting,
containing solutions which are amenable to New York, February 15-18 (1960).
recovery, purification and concentration by liquid
10. Thornhill, P.G., Wigstol, E and Van Weert,
ion exchange. Although the above-mentioned list of
G.: J. of Metals, 23(7), 13 (1971).
extracting reagents is very impressive but still it
should not be considered as limiting. The 11 Kacher, C.D. et al; Radiochim Acta,75(3),
development and successful marketing of the 135-139 (1996).
existing reagents has resulted in the commercially 12. Agers, D.W., Drobnick, J.L. and Lewis, C.J.;
successfully metal recovery operations around the Proc. AIME Annual Meeting, New York,
World. The researchers are constantly working on February 18-22 (1962).
the development of new reagents and new 13. Baggott. E.R., Fletcher, A.W. and Kirkwood,
applications for the existing extractants. A day T.A.W.; Ninth Commonwealth Mining and
will come when the hydrometallurgist could have Metallurgical Congress, London (1969).
an unlimited selection of commercially available
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