Separation & Purification Reviews

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Solvent Extraction and Its Applications on Ore

Processing and Recovery of Metals: Classical
Approach

Y.A. El-Nadi

To cite this article: Y.A. El-Nadi (2017) Solvent Extraction and Its Applications on Ore Processing
and Recovery of Metals: Classical Approach, Separation & Purification Reviews, 46:3, 195-215,
DOI: 10.1080/15422119.2016.1240085

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Published online: 31 Oct 2016.

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Separation & Purification Reviews, 46: 195–215, 2017
Copyright © Taylor & Francis Group, LLC
ISSN: 1542-2119 print / 1542-2127 online
DOI: 10.1080/15422119.2016.1240085

Solvent Extraction and Its Applications on Ore

Processing and Recovery of Metals:
Classical Approach
Y.A. El-Nadi
Hot Laboratories Center, Atomic Energy Authority, Abo Zaabal, Kalyobeia, Egypt

Solvent extraction is widely employed in a variety of industries for both the upgrading and
purification of a range of elements and chemicals. The technology is used in applications as diverse
as ore processing, pharmaceuticals, agriculture, industrial chemicals, petrochemicals, food industry,
purification of base metals and refining of precious metals. This review deals with the basics of
solvent extraction technique and discusses in detail its applications in several fields focusing on ore
processing and recovery of important metals from economic and industrial point of view.

Keywords: Solvent extraction, separation, metals, applications, ionic liquids

INTRODUCTION
The term (solvent or liquid–liquid extraction) refers to the dis-
tribution of a solute between two immiscible liquid phases in
contact with each other, i.e., a two-phase distribution of a solute.
It can be described as a technique, resting on a strong scientific
foundation (1).
Solvent extraction techniques have a broad field of appli-
cations in inorganic and organic chemistry and large-scale
industrial separations, in analytical chemistry, in pharmaceu-
tical and biochemical industries, and in waste treatment. In
addition, solvent extraction is a good instrument for study-
ing fundamental understanding of equilibrium and kinetics
of complex formation processes. Extraction methods have
now become a routine procedure in separation technologies.
In metal recovery, it is one of the favored separation techni-
ques because of its simplicity, speed and wide scope. By utiliz-
ing relatively simple equipment and requiring less time to
perform, extraction procedures offer much to chemists and
engineers (2).
Since the early days of the Manhattan Project, when
scientists extracted uranyl nitrate into diethyl ether to purify
Received 23 January 2016, Accepted 1 September 2016.
Address correspondence to Y.A. El-Nadi, Hot Laboratories Center, Atomic
Energy Authority, Kalyobeia 13759, Egypt. E-mail: yael_nadi@yahoo.com
Color versions of one or more of the figures in the article can be found
online at www.tandfonline.com/lspr.
the uranium used in the first reactors, solvent extraction has
been an important separation technique for radiochemists.
Thus, it is a technique used both in the laboratory and on the
industrial scale.
The schematic diagram of the solvent extraction process is
shown in Figure 1. Usually the transfer of metal ions from the
aqueous to the organic phase does not occur completely in one
contact (3). Multiple contacts are necessary. This also holds true
for scrubbing (contacting the loaded organic phase with an
aqueous solution to collect back the impurities extracted by
the solvent) and stripping (contacting the scrubbed organic
phase with an aqueous solution to recover the main extracted
species from the organic phase, back to the aqueous phase) (4).
Principles of Solvent Extraction
Extractants
Because metals generally exist in aqueous solution as
hydrated ions before the metal can be extracted into a non-
polar organic phase, the water molecules must be replaced and
any ionic charge reduced or removed. This can be achieved in
different ways by using three types of extractants: acidic, basic,
and solvating, which extract metals according to the following
equilibrium reactions (5):
Acidic :Mzþ ðaqÞ þ zHAðaq or orgÞ
(1)
, MAzðorgÞ þ zHþ ðaqÞ
196 Y.A. EL-NADI
FIGURE 1 Typical solvent extraction flow sheet.
þ ðnzÞ
Basic : ðn  zÞR4 N ðaq or orgÞ þ MXn ðaqÞ
, ðn  zÞR4 Nþ MXn ðnzÞ ðorgÞ
Solvating : MXzðaqÞ þ mSðorgÞ
, MXz SmðorgÞ þ mH2 O
Acidic Extractants. Acidic extractants include simple
reagents such as carboxylic acids and organophosphorus
acids, as well as chelating acids such as β-diketones, 8-
hydroxyquinoline and hydroxyoximes (6).
For metals in the first transition series the extraction extent
follows the order: V < Cr < Mn < Fe < Co < Ni < Cu > Zn, for
divalent metals. Thus, unless other factors are involved copper
will be extracted at lower pH values than the other elements. In
addition, it is found that M4+ > M3+ > M2+ > M+, so that
thorium(IV) will be extracted before iron(III) in turn before
copper(II) before sodium. In this respect, Fe(III) was success-
fully extracted from sulfuric acid solution containing chro-
mium using D2EHPA (HA) mixed with kerosene according
to the following reaction (7):
   
ðaqÞ þ 3 ðHAÞ2 ðorgÞ , FeðHA2 Þ3 ðorgÞ
Fe3þ
þ 3Hþ ðaqÞ
Basic Extractants. Basic extractants normally consist
of alkylammonium species (8). Quaternary ammonium spe-
cies or uncharged alkylammonium compounds may be used
as extractants. It has been observed that the magnitude of
extraction follows the order R4N+ > R3NH+ > R2NH2+ >
RNH3+ with the size of the alkyl group R generally between
8 and 10 carbon atoms. In commercial practice the trialk-
ylammonium compounds are generally more commonly
used in spite of their inferior extraction properties because
they are cheaper than the quaternary extractants (9).
These extractants require the presence of stable anionic
metal complexes to form the extractable ion pair complexes,
so that only metals that produce such species can be
extracted with these compounds. Thus, in halide solution,
gold(III) > iron(III) > zinc > cobalt > copper >> nickel.
An example of this kind of extractants is observed in the
work performed as a comparative study of vanadium extraction
by Aliquat-336 (N-methyl-NNN-trioctylammonium chloride,
R3CH3N) from acidic sulfuric acid and alkaline sodium hydro-
xide media, respectively, giving the following equilibria (10):
½H2 V10 O28 4 ðaqÞ þ 4½R3 CH3 NClðorgÞ
 
, ðR3 CH3 NÞ4 H2 V10 O28 ðorgÞ þ 4Cl ðaqÞ (5)
½VO3 OH2 ðaqÞ þ ½R3 CH3 NOHðorgÞ
, ½R3 CH3 NVO3 ðorgÞ þ 2OH ðaqÞ (6)
(2) Solvating Extractants. Solvating extractants operate
by replacing the solvating water molecules around the aqueous
metal complex, making the resulting species more lipophilic.
The types of organic compounds used include those based on
(3) carbon, i.e., alcohols, ethers, esters and ketones with com-
pounds such as dibutylcarbitol, nonyl phenol and methyl iso-
butyl ketone (MIBK). Amides, RCONR2, have also been
proposed for specialized applications such as the extraction
of lanthanides, actinides (11–14) and precious metals (15–17).
However, the most commonly used oxygen-donating solvat-
ing extractants are based on the organophosphorus com-
pounds: alkylphosphates, (RO)3PO; alkylphosphonates,
(RO)2RPO; alkylphosphinates, (RO)R2PO; and alkyl phos-
phine oxides, R3PO (18, 19). Some commercial solvating
extractants include Cyanex 921, Cyanex 923 and Cyanex
925. However, sulfur donor extractants are less common,
although dialkylsulfides have been used in precious metal
extraction, and a trialkylphosphine sulfide, R3PS (Cyanex
471X), is available commercially. Such sulfur-donating extrac-
tants will need to be considered when extracting and separating
soft metals, such as second- and third-row transition metals
(e.g., cadmium, mercury and palladium).
Actually, Cyanex reagents are considered as potential
(4) extractants for different elements of nuclear importance as
U(VI), U(IV), Th(IV), etc. from different aqueous media
(20). These reagents have the advantage of not extracting
nitric acid, which is extracted by tri-n-butylphosphate (TBP)
usually used in the extraction processes of the spent nuclear
fuel. Cyanex reagents are also effective extractants for
lanthanides and rare earth elements as well as platinum
group metals as Pd(II). Moreover, the extraction equilibrium
using these reagents is usually reached after few minutes
and the separation factors between different elements in the
Cyanex systems are usually higher than that of other related
systems (20).

Synergistic Extraction
On occasion, mixtures of two different extractants will
enhance the extraction of a metal above that expected
from the summation of the performance of the two reagents
separately. This gives rise to the synergistic factor (SF),
defined using the metal distribution ratios D in the different
extractant media as follows:
SF ¼ DAB =ðDA þ DB Þ (7)
A large number of examples of synergism can be found in
the literature (21–50), although very few of these have actually
been commercialized. The main reason for the lack of indus-
trial interest is probably the difficulty in maintaining the opti-
mum ratio of extractants in the organic phase to provide
synergism. The most common synergistic system consists of
a mixture of an acidic and a solvating extractant acting on a
metal ion where the preferred coordination number cannot be
satisfied by just the acidic extractant. Table 1 summarizes the
structure of the above referenced synergistic mixtures, the
metal ions extracted, the aqueous media used and the stripping
conditions as well as their applications if present.
It is noteworthy that the extractants used in synergistic
systems are usually composed of a mixture of an acidic
extractant with a neutral one. The acid liberated during the
process of solvent extraction of metals with those acidic
extractants adversely affects the metal extraction. One
extra example is the study of extraction behavior of the
metal ions, La, Nd and Y, using a convenient mixture of
neutral reagents such as trioctylphosphine oxide (TOPO)
and trialkylphosphine oxide (TRPO) extractants (51). In
this system, yttrium was separated in a pure form based on
its trend in the extraction and stripping procedures. Besides,
the method was applied on the hydrous oxide cake resulted
from Egyptian monazite to separate yttrium from lanthanum
and neodymium including in the ore.
Extraction Techniques and Considerations
The maximum degree of separation that can be achieved
between two metals (A and B) in a single equilibrium of the
two phases is governed by:
1. The separation factor (α), which is the ratio of the
distribution ratios (D) of the two metals.
2. The phase ratio (r), which is the ratio of the volume of
the organic phase to the volume of the aqueous phase.
A comparison can be made of the fraction A extracted
(RA) with the fraction of B extracted (RB) utilizing the
following equation:
 
DB þ 1=r
RA =RB ¼ α (8)
DA þ 1=r
SOLVENT EXTRACTION FOR METAL RECOVERY 197
Thus, the ratio, RA/RB, the recovery factor ratio, is an
expression of the degree of separation (52).
A single equilibrium is unlikely to provide an adequate
degree of separation and further contact stages are almost
necessary.
Cross-current Batch Extraction
In a cross-current extraction process, the feed containing
the solutes is contacted with fresh solvent for each extrac-
tion stage. The extracts can be collected separately or com-
bined for further processing, Figure 2.
Counter-current Batch Extraction
In counter-current batch extraction, Figure 3, the aqueous
phase is extracted with successive volumes of solvent such
that the fresh organic phase always extracts from the weak-
est aqueous phase and the most concentrated solvent
extracts from the strongest aqueous phase. This method of
extraction provides the lowest residual concentration of
solute in the final raffinate while at the same time producing
maximum solute loading of the organic phase (52, 53).
In industrial practice batch processing is impracticable. It
is much more effective from the chemical engineering
aspect to carry out the extraction with continuous counter-
current flow of the two phases.
Continuous Counter-current Extraction
Contactors for counter-current extraction, Figure 3, described
in detail (9), may be divided into two types: 1) stage-wise
contactors and 2) truly continuous contactors. The former is
typified by mixer-settler contactor, Figure 4, in which the two
phases are equilibrated and then separated in the settler section
before passing on counter-current to each other (54). Truly
continuous, counter-current operation is obtained when the two
phases pass continuously in opposite directions as in a simple
packed column. A continuous counter-current contactor,
Figure 5, can be designed from the number of equilibrium stages
required to affect a separation (55).
A graphical construction can be used to relate the feed
concentration to the aqueous and organic solute concentra-
tions for a given number of contact stages and for specific
flow rate. The resulting diagram is usually termed an extrac-
tion equilibrium diagram or a McCabe–Thiele diagram,
Figure 6 (51).
A number of published papers in which the mixer-settler
contactor has been extensively used can be found in the litera-
ture. Some of them include the extraction of copper from
ammoniacal waste solution (56), extraction and recovery of
zinc from simulated and real industrial waste resulting from
rayon industry (57), separation of thorium from leached mon-
azite solution using counter-current extraction (58), and recov-
ery of U(IV) from phosphoric acid by octylphenyl acid
phosphate (OPAP) extractant (59).
 TABLE 1 198
Extraction data obtained from synergistic systems (21–50)

Aqueous
Extractant Metal ion medium Stripping agent Application Ref.

CA-12+ Cyanex 272 in heptane Y Chloride Diluted HCl Separation of Y from rare earths (21)
Cyanex 272+ D2EHPA and Cyanex 302+D2EHPA in Co, Ni Diluted sulfate 200 g/L H2SO4 Improvement of Co and Ni by elevating the temperature (22)
Y.A. EL-NADI

kerosene
HRJ-4277+ Cyanex 471x in Shellsol 2046 Cd, Zn Distilled water 20 g/L H2SO4 Batch continuous extraction test (23)
Hhfa and Htta+ Co(III) chelates in toluene lanthanides Distilled water 0.1 M HClO4 Spectrochemical study of the adduct formation (24)
HTTA or HP+PAN in benzene Lanthanides Deionized N/A Increasing a selectivity (25)
water among the lanthanides
TPTZ+HL-10-LH in CHCl3 N/A 0.1 M nitrate N/A Proposal of the interaction complexes stoichiometries (26)
TPTZ+HL-10-LH in CHCl3 La, Eu, Lu 0.1 M nitrate 1 M HNO3 Improvement of the selectivity of (27)
Eu over Lu and Eu over La
TBP+N235 in heptane Zn, Cd Distilled water N/A Separation of Zn from bulk Cd solutions (28)
D2EHPA+ HEH/EHP in kerosene Nd, Sm Diluted sulfate 3 M HCl N/A (29)
D2EHPA+ HEH/EHP in kerosene La, Nd, Sm, Gd Diluted sulfate N/A Calculation of equilibrium and stability constants (30)
D2EHPA+ Cyanex 923 in heptane Ce, F Sulfuric acid N/A Separation of Ce and F from bastnasite (31)
D2EHPA+ HEH/EHP in kerosene Ce Sulfuric acid N/A N/A (32)
CA100+Phen in benzene La, Nd, Sm, Tb, Nitrate N/A Separation of the lanthanoids from yttrium (33)
Y
Versatic 10+ LIX63 or 4PC in Shellsol D70 Ni, Co Tap water H2SO4 Separation of Ni and Co from Mn, Mg and Ca (34)
CA100+N235 in heptane In, Ga Chloride N/A Separation of In and Ga (35)
Cyanex272+ PC-88A in heptane Co, Mn, Li H2SO4 >0.04 M HCl or >0.01 M Recycling of spent cathodic materials of Li-ion batteries (36)
H2SO4
DEO6+ Lanthanides Distilled water N/A N/A (37)
β-diketone in 1,2-dichloroethane
Versatic 10+ LIX 63 in Shellsol D70 Cu, Fe Chloride 53 g/L Cu+ 180 g/L H2SO4 Proposal of flow sheet for copper conventional electrowinning (38)
DNPPA+ neutral oxodonors in n-paraffin U Nitric acid 1 M Na2CO3 Recovery of uranium from nitric acid media (39)
Cyanex 272+ HQ in heptane Sm Chloride N/A Overcome emulsification of HQ (40)
TIOA+TBP in dichloromethane Cd, Co, Ni Acidic iodine 2 M NaOH Separation of Cd from industrial wastewater containing Co and Ni (41)
LIX63+ Versatic 10+ TBP in Shellsol D70 Cu, Ni, Co, Zn Strong chloride 100 g/L H2SO4 Proposal of flow sheet to recover Cu, Co, Zn and Ni from strong (42)
chloride leach
D2EHPA+LIX 860 in toluene Co KNO3 N/A N/A (43)
D2EHPA+ TOPO in Isane IP 185 U H3PO4 N/A Derivation of the uranyl, D2EHPA and TOPO speciation (44)
HA+TOPO or TBuP in nonane Zn (NH4)2SO4 2 M H2SO4 Recovery of zinc from ammoniacal solutions using β-diketone extractant (45)
D2EHPA+ Cyanex 272 in kerosene Y Chloride N/A N/A (46)
D2EHPA+ EHEHPA in n-heptane Nd, Dy, Y HCl N/A Enhancement the separation of Nd (47)
Versatic 10 acid+LIX84-I in kerosene Ni Sulfate 3 M H2SO4 Separation of Ni from Co, Mn and Li contained in Li-ion batteries (48)
Mextral 54-100+ Mextral 84H in kerosene Zn Ammoniacal/ 2 M H2SO4 N/A (49)
(NH4)2SO4
DOP+TBP in kerosene Li MgCl2 6 M HCl N/A (50)

CA100 = sec-nonylphenoxy acetic acid, CA-12 = sec-octylphenoxy acetic acid, Cyanex 272 = bis(2,4,4-trimethylpentyl)phosphinic acid, Cyanex 302 = di-2,4,4,-trimethylpentyl mono-thio-phosphinic acid,
Cyanex 471x = triisobutyl phosphine sulfide, Cyanex 923 = trialkyl phosphine oxide, D2EHPA = bis-2-ethylhexyl phosphoric acid, DEO6 = dodecyl polyether, DOP = dioctyl phthalate, DNPPA = dinonyl phenyl
phosphoric acid, EHEHPA = 2-ethylhexylphosphonic acid mono-2-ethyl hexyl ester, HA = 4-ethyl-1-phenyl-1,3-octadione, HEH/EHP = 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, Hhfa =
hexafluoroacetylacetone, HL-10-LH = heterocyclic β-ketoenol, HP = 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one, HQ = 8-hydroxyquinoline, HRJ-4277 = nonylsalicylic acid, Htta = 2-thenoyltrifluoroacetone,
LIX 63 = 5,8-diethyl-7-hydroxy-6-dodecanone oxime, LIX 84I = 2-hydroxy-5-nonylacetophenone oxime, LIX 860 = 5-dodecylsalicylaldoxime, Mextral 54-100 = 1-benzoyl-2-nonyl ketone, Mextral 84H = 2-
hydroxy-5-nonylacetophenone oxime, N/A = not applicable or not found, N235 = trialkyl amine, Neutral oxodonors = TBP, TEHP, Cyanex 923, PAN = 1-(2-pyridylazo)-2-naphthol, PC-88A = 2-ethylhexyl
phosphinic acid mono-2-ethylhexyl ester, Phen = 1,10-phenanthroline, TBP = tri-butyl-phosphate, TBTZ = 2,4,6-tri(2-pyridyl)-1,3,5-triazine, TBuP = tributyl phosphine, TEHP = tris(2-ethylhexyl) phosphate,
TIOA = triisooctylamine, TOPO = trioctyl phosphine oxide, Versatic 10 = neodecanoic acid.
 SOLVENT EXTRACTION FOR METAL RECOVERY 199

FIGURE 2 Cross-current extraction schemes (53). © Roussel-Robatel Company. Reproduced by permission of Roussel-Robatel Company. Permission to
reuse must be obtained from the rightsholder.

FIGURE 3 Counter-current extraction scheme (53). © Roussel-Robatel Company. Reproduced by permission of Roussel-Robatel Company. Permission to
reuse must be obtained from the rightsholder.

FIGURE 4 Flow diagram of a mixer settler unit [courtesy of Rousselet-Robatel, Annonay, France (55)]. © Roussel-Robatel Company. Reproduced by
permission of Roussel-Robatel Company. Permission to reuse must be obtained from the rightsholder.

APPLICATIONS impetus for the further development of these technologies

Solvent extraction (SX) was employed mainly as an analy-
tical tool for the separation and analysis of elements with
very similar chemical properties. The discovery and isola-
tion of the lanthanide and actinide elements provided
(60). SX is applied nowadays in various industries. This is a
classic method of separation and concentration of metal ions
from aqueous solutions. It is a selective, cost-effective and
uncomplicated chemical process applied in hydrometallur-
gical separation and purification of various metals (61).
200 Y.A. EL-NADI
FIGURE 5 Eight-stage mixer-settler battery with turn-key skid-mounted accessories [Rousselet-Robatel, Annonay, France (55)]. © Roussel-Robatel
Company. Reproduced by permission of Roussel-Robatel Company. Permission to reuse must be obtained from the rightsholder.
FIGURE 6 McCabe–Thiele diagram for extraction of La(III), Nd(III) and Y
(III) from HNO3 solution by a TOPO and TRPO mixture in kerosene at 25 °C
and phase ratio = 1 [adapted from Ref. (51)]. Reprinted from (51) with permis-
sion from Elsevier.
The use of solvent extraction in hydrometallurgy extends to a
wide range of metals from different feeds including low-grade
ore, scrap, waste leachates and dilute aqueous solutions. The
technology was used first in nuclear technology; then, some
high-value metals like precious group metals solvent extraction
technologies became commercially viable and were developed
and used. After the development of selective chelating extrac-
tants, the solvent extraction was able to compete with classical
separation–concentration operations in this field (2).
Ore Processing
Uranium
The process used for recovery of uranium from its ores
depends on the nature of the ore. All the processes include a
leaching step that solubilizes the metal. Solvent extraction is
used most frequently for the recovery and purification of
uranium from the leaching liquors (9).
Most uranium-bearing ores are readily leached in sulfuric
acid and the uranium is recovered by solvent extraction
using amines or dialkylorganophosphorus acids. Phosphate
ores are leached in a mixture of sulfuric and phosphoric
acids or in phosphoric acid alone. Hot nitric acid has also
been used as a lixiviant for uranium ores.
Sulfuric Acid Leach Liquors. Organophosphorus
reagents were among the first used for the commercial
recovery of uranium from solutions obtained from the
leaching of low-grade ores with sulfuric acid. In the
Dapex process (62), diethyl hexyl phosphoric acid
(D2EHPA) is used to selectively extract uranium from
vanadium and iron(III) under conditions of controlled pH
and electrochemical potential (63). TBP or isodecanol is
added to the organic phase to prevent the formation of a
third phase. The extraction of uranium(VI) by D2EHPA
(represented as the dimeric H2A2 structure) occurs via
the reaction:
þ
UO2 2 ðaqÞ þ 2H2 A2ðorgÞ , UO2 ðHA2 Þ2ðorgÞ þ 2Hþ (9)

TABLE 2
Comparison of the Amex and Dapex processes
Point of comparison Amex process
Coextracted ions Mo(VI), Zr(IV)
Stripping Simple, many possibilities
Extractant stability Rather low stability
Diluent Tendency to form third phases with aliphatic hydrocarbons. Long-
chain alcohols as phase modifiers or aromatic diluents are necessary
Extraction kinetics Rapid
Phase disengagement Slow (sensitive to suspended solids)
Uranium is stripped from the loaded organic phase with a
solution of sodium carbonate and recovered as sodium
uranyl tricarbonate, while the extractant is regenerated in
the sodium form.
Today, amines are more widely used for the recovery of
uranium from sulfate leach liquors, and uranium recovery is
one of the most important commercial uses of amines.
Amine systems achieve higher uranium purity than organo-
phosphorus systems (due to the greater selectivity of amines
for uranium) and have lower extractant losses due to their
lower aqueous-phase solubility. Solvent extraction is
applied either directly to the weakly acidic leach liquor
(AMEX process, Vaal River West, South Africa) or to the
strongly acidic eluate from an ion-exchange preconcentra-
tion treatment of the leach liquor (63). A more modern
variation (such as at Southern Cross Resources Uranium
One, South Africa) is to treat the ore by pressure leaching
followed by solvent extraction. The extraction of uranium
(VI) by amines occurs in the order of tertiary > secondary >
primary amines. The extraction of iron(III) occurs in the
reverse order, so tertiary amines represent an obvious choice
of extractant. The tertiary alkyl amine sold as Alamine 336
or Armeen 380 is widely used, usually in conjunction with
an alcohol phase modifier (such as isodecanol) to prevent
the formation of a third phase and inhibit the formation of
emulsions.
Uranium can be stripped from the loaded organic phase using
a variety of reagents, including NaCl, (NH4)2SO4, Na2CO3,
ammoniacal ammonium sulfate or ammonia gas (63). These
stripping systems present few choices based on technical
grounds, so the choice of reagent is usually determined by
economic factors. The advantages and disadvantages of the
Dapex and Amex processes are compared in Table 2. The
Amex process is more widely used than the Dapex process
because of the greater selectivity of trialkylamines than
D2EHPA for uranium in H2SO4 solution.
Phosphoric Acid Leach Liquors. Many phosphate
rock deposits contain quantities of radioactive elements such
as uranium and thorium. Selective leaching of uranium from
raw phosphate ores is difficult because the U(VI) ion is
SOLVENT EXTRACTION FOR METAL RECOVERY 201
Dapex process
Fe(III), Th(IV), V(IV), Ti(IV), Mo(VI), Rare Earths
With Na2CO3 which necessitates addition of TBP to
avoid the separation of NaDEHP in a third phase
More stable than amines
Many diluents can be used
Slow
Rapid
incorporated into the crystal structure of apatite (Ca5(PO4)3
(OH,F,Cl)), rather than adsorbtively associated with it.
Uranium is, therefore, typically recovered from phos-
phate rocks by recovering it from phosphoric acid produced
by sulfuric acid leaching of phosphate ores.
Uranium in phosphoric acid solution is extracted as the
UO22+ species also using D2EHPA mixed with tri-n-octyl-
phosphine oxide (TOPO) that synergistically forms an
organic-phase adduct:
UO2 ðHA2 Þ2ðorgÞ þ TOPOðorgÞ
, UO2 ðHA2 Þ2  TOPOðorgÞ (10)
TBP has also been used as a synergist, but TOPO typi-
cally gives higher synergism and higher selectivity than
TBP. Di(nonylphenyl)phosphoric acid can also be used in
place of D2EHPA (64). Uranium is stripped from the loaded
organic phase with ammonium carbonate, and precipitated
as ammonium uranyl tricarbonate.
Nitric Acid Leach Liquors. High-grade uranium
ores are sometimes leached in hot nitric acid, particularly
when significant amounts of radioactive elements such as
thorium are present in the rock (65). Uranium forms the
uranyl nitrate species that can be extracted by a solvating
mechanism using TBP, forming the species UO2(NO3)2
(TBP)2 (63). TBP extraction of uranium from nitric acid
is also practiced for the purification of uranium and for its
recovery from irradiated nuclear fuel (66).
Thorium
Thorium, which consists mainly of the almost stable
isotope Th-232 (alpha emitter with half-life, t½ = 14.109
years), has been proposed as a secondary source of
nuclear energy (67). Irradiation of Th-232 with neutrons
produces Th-233 (t½ = 22.4 minutes), a beta-emitter that
decays to fissionable U-233. The world reserves of Th-
232 are about three times larger than those of uranium.
However, because the uranium nuclear fuel cycle was
202 Y.A. EL-NADI
TABLE 3
Commercial processes for the recovery of Th from its main ores
Ore
Types of ores (main locations) composition Leaching
Monazite (Brazil, India, Australia, (La,Ce,Th)PO4 Hot concentrated NaOH or
South Africa, United States) H2SO4
Thorianite/Uranothorite ThO2/(U,Th)O2 HNO3 or H2SO4
Thorite/Uranothorite (United States, ThSiO4/(U,Th) Hot H2SO4
Canada) SiO4
developed first and is easier to use for nuclear energy
production, the thorium cycle has not received as much
attention. However, thorium must be considered as a
future nuclear energy source. Fission of thorium produces
less hazardous waste, because the amount of long-lived
transthorium isotopes is about 100 times less than that in
the uranium cycle. Accelerator-driven reactors projects
based on the thorium cycle have been proposed (68).
Table 3 contains, in a simplified way, the composition,
location and treatment of main thorium ores. The purifi-
cation of thorium by TBP extraction takes place after the
dissolution of thorium in nitric acid, generally from a
hydroxide cake. When thorium is dissolved in sulfuric
acid, purification is achieved by extraction with long-
chain alkylamines.
Rare Earth Elements
The rare earths are moderately abundant elements in the
earth’s crust that occur in a large number of minerals. Rare
earths typically occur as carbonates, oxides, phosphates and
silicates in the forming minerals. Even though the rare earth
metals are fifteen in number, about 95% of all the world rare
earth resources occur in just three minerals, bastnasite,
monazite and xenotime. These three therefore are the prin-
cipal ore minerals for rare earth extraction. Among these,
again, bastnasite occurs most frequently, monazite is second
and xenotime is the distant third (4).
The mineral monazite is a phosphate mainly of the cerium
group rare earths and thorium. Monazite is found in many
geological environments. It occurs as an accessory mineral in
acidic igneous rocks, in metamorphic rocks and in certain vein
deposits. Due to its chemical stability it also develops into
detrital mineral in placer deposits and beach sands (69).
The recovery of mixed rare earths and removal of thor-
ium from monazite are accomplished by a variety of meth-
ods (70), after chemically attacking the mineral with sulfuric
acid or sodium hydroxide.
Acid Treatment. The sulfuric acid method had been
used most extensively in the United States (71). With this
method, depending on the acid/ore ratio, temperature and
concentration, either thorium or the rare earths can be
Purification
Dissolution of oxides into HNO3 and then TBP; alkylamines for Th in
sulfate solutions
TBP for nitrates/Alkylamines for sulfates
Alkylamines
selectively solubilized or both thorium and rare earths
totally solubilized. Rare earths and thorium are subsequently
recovered from the solution. The processes available are
shown in Figure 7. The process of rare earth recovery
based on rare earth double sulfate precipitation was largely
developed by Pilkington and Wylie (72) and has found
industrial application. Yttrium and the heavy rare earth
double sulfates are quite soluble and go with thorium.
Even in the stepwise neutralization procedure investigated
at Ames (73), yttrium and the heavy rare earths are precipi-
tated along with thorium as a basic compound. The rare
earths, however, are recoverable from the thorium fraction
during solvent extraction for the purification of thorium and
uranium. Solvent extraction with TBP from an aqueous 8 M
nitric acid solution of thorium and mixed rare earths permits
the recovery of thorium, uranium, cerium and cerium-free
rare earths.
Other commercially significant processes essentially
involve precipitation of thorium pyrophosphate or basic
salts from the leach liquor and subsequent recovery of the
rare earth in solution as double sulfates, fluorides, or hydro-
xides or even selective solubilization of thorium in the ore
treatment stage itself (74). The sulfuric acid process does
not yield pure products and is no longer in commercial use.
Alkali Treatment. The phosphate content of the ore is
recovered as a marketable by-product, trisodium phosphate,
at the beginning of the flow sheet, and this has been a major
attraction for the commercial use of this process. In this
concern, a modified leaching and extraction process of ura-
nium from hydrous oxide cake of Egyptian monazite was
developed (75). In this process, a monazite sample is ground
to mesh size 200–270, then digested by boiling with sodium
hydroxide (50%) for 4 hours at 140 °C and filtered at 80 °C.
The filtrate can be recycled for recovery of sodium phosphate
and excess sodium hydroxide, whereas the precipitate is
washed with water and dried. The dried precipitate, which
consists mainly of thorium and rare earths as well as uranium
hydrous oxides, was leached several times with alkaline
solution composed of sodium carbonate, sodium hydroxide
and hydrogen peroxide to separate uranium selectively.
The solution is filtered and the filtrate containing uranium
is diluted and shaken with 0.1 M Aliquat-336 in kerosene

FIGURE 7 Monazite processing by acid treatment [adapted from Ref. (4)]. © Taylor & Francis. Reproduced by permission of Taylor & Francis. Permission
to reuse must be obtained from the rightsholder.
containing octanol in one-stage solvent extraction to recover
and purify uranium. The resulted uranium which is mainly
tricarbonate complex is precipitated as hydroxide by decreas-
ing pH of the solution with addition of nitric acid (75).
Thorium and rare earths precipitate is dissolved in 4 M
nitric acid with heating. Thorium is extracted from the
above mixture by Aliquat-336 in kerosene, stripped by
shaking with HCl solution and precipitated as hydroxide
by addition of ammonium hydroxide giving thorium (76).
On the other hand, cerium(III) is oxidized to its tetravalent
state by addition of sodium bromate, extracted by Aliquat-
336 in kerosene containing 1-octanol and stripped by shak-
ing the organic phase with diluted HNO3 solution and then
precipitated as hydroxide by addition of ammonia (77). An
integrated schematic diagram displaying the whole process
is shown in Figure 8.
The aqueous solution principally containing La, Nd and
Y is subjected to solvent extraction using a synergistic
TOPO–TRPO mixture in kerosene in 2:1 O/A phase ratio
at 25 °C. The organic phase is stripped by H2SO4 in equi-
molar ratio to separate most of Y and then treated by HCl as
stripping agent to recover La and Nd. The organic layer is
finally washed with water to separate the remaining Y and
then used for another cycle of extraction. Overall recovery
of yttrium from the strip liquors was about 94%, while it
was 79% and 81% for La and Nd, respectively. Yttrium was
SOLVENT EXTRACTION FOR METAL RECOVERY 203
finally recovered from the solution as the oxalate and cal-
cined to oxide. The final product was found to contain
84.5% Y2O3 (51).
Copper
One of the most remarkable success stories in the com-
mercial application of solvent extraction occurred in the
copper industry. The use of solvent extraction for the pri-
mary processing of copper has enjoyed spectacular growth
over the past 35 years. The production of high-purity copper
by a combination of leaching in sulfuric acid, upgrading and
purification of the copper by solvent extraction (SX), and
recovery of the metal by electrowinning (EW) has increased
steadily, now approaching 30% of total copper production
as shown in Figure 9 (78–80).
The first commercial reagents were all based on ketoxime
functionality and were used exclusively for copper extrac-
tion for over a decade after the first full-scale application at
Bluebird Ranchers Mine, Arizona (81). Today, ketoximes
are still successfully used in niche applications for the
recovery of copper from dilute leach liquors and also find
applications in nickel solvent extraction from ammoniacal
solutions and in precious metal refining. Particular applica-
tions of ketoximes in copper production are at El Tesoro and
Lomas Bayas in the Atacama Desert of Chile, where the
204 Y.A. EL-NADI

FIGURE 8 A suggested flow sheet of monazite processing by alkali treatment (51). Reprinted from (51) with permission from Elsevier.

FIGURE 9 Flow sheet for recovery of copper by leaching, SX and EW. RH = organic extractant (60). © Taylor & Francis. Reproduced by permission of
Taylor & Francis. Permission to reuse must be obtained from the rightsholder.

leach liquors of circuits often contain high levels of nitrates
and chlorides. Ketoximes are stable to oxidation under these
conditions (82, 83). Although ketoximes do not generally
allow the extraction of copper at pH values below 1.8, and
have slow extraction kinetics, they exhibit copper selectivity
over iron of about 300:1. Their selectivity as a function of
pH for other cations commonly found in sulfate leach
liquors is shown in Figure 10.
The second-generation aldoxime extractants were devel-
oped to overcome the shortcomings of the ketoximes (84,
85). Aldoxime extractants exhibit very fast extraction
kinetics, high selectivity (Cu:Fe ≈ 2000:1), and high loading
capacity. Because they extract at pH levels below 1—the
stripping of copper is difficult.
Today, modified aldoximes and aldoxime–ketoxime mix-
tures are the most widely used copper extractant systems.
With advances in chemistry and manufacturing processes,
these reagents now have high purity and many of the limita-
tions of earlier reagents have been overcome. They have
faster reaction kinetics, greater selectivity for copper over
other base metals at low pH values, better extraction per-
formance, and more rapid phase disengagement.

FIGURE 10 pH dependence of various cations by LIX 84-I ketoxime extractant (60). © Taylor & Francis. Reproduced by permission of Taylor & Francis.
Permission to reuse must be obtained from the rightsholder.
As a consequence of significant advances in reagent
customization during the past 30 years, large reductions in
capital costs for copper solvent extraction plants have been
possible. Copper production per unit area of plant size has
also increased dramatically, from about 4 ton of copper/y/m2
of settler area in the early plants to 16 t/y/m2. Some of the
most innovative advances in equipment design and circuit
configurations have also been achieved in copper extraction
(86, 87). Earlier plants were designed using only series
configurations of the mixer-settler trains. The trend in recent
years leans toward the use of series parallel configurations,
especially in very large plants, and from series-parallel to
all-parallel (88). This increases overall throughput and
reduces capital costs.
Nickel Laterite Processing
While high-grade nickel sulfides are processed by smelt-
ing, low-grade laterites (0.5–3% Ni), until relatively
recently, could not be economically treated with available
technologies. Since 1998, several new laterite flow sheets
have been commissioned or are under advanced develop-
ment. All of these processes use pressure acid leaching
(PAL) to solubilize the metals of interest, but the down-
stream flow sheets have significant differences. They all
involve solvent extraction as one or more of the unit opera-
tions, either for the removal of cobalt from the nickel-rich
leach liquor or for the purification of nickel liquor.
Bulong Process. The Bulong nickel operation near
Kalgoorlie, Western Australia, was commissioned in 1998
with a design capacity of 9000 ton/y Ni and 720 ton/y Co
(89). This plant closed in 2003, but later reopened as Avalon
Nickel to treat nickel sulfide material. The original flow sheet
remains of interest, since it has many similarities with those
planned for Tati Nickel, Botswana (90), and the Nkomati
project in South Africa (91). Figure 11 shows a simplified
flow sheet of the Bulong downstream purification process.
Following dissolution of the ore at 4500 kPa and 250 °C, the
SOLVENT EXTRACTION FOR METAL RECOVERY 205
leach liquor was then processed directly for the recovery of the
valuable metals. Fe(III), Al and Cr(III) were removed to <1
mg/L by precipitation with limestone. In the first of three
solvent extraction operations, Co, Cu, Zn and Mn were sepa-
rated from Ni by Cyanex 272. Extractions of Co, Mn and Zn
are excellent, with minimum co-extraction of nickel (92).
The raffinate from the cobalt extraction circuit was refined
by nickel extraction to produce a high-grade solution suitable
for the production of nickel cathode. This extraction was
carried out using versatic acid, a long-chain carboxylic acid,
using pH control to limit the co-extraction of Mg and Ca. The
nickel resulting from this process had a purity of >99%, from
which nickel cathode (> 99.5% purity) was produced by
electrowinning.
Goro Process. The Goro process, Figure 12, developed
by Vale-INCO for the treatment of a nickel laterite deposit in
New Caledonia (93, 94) also treats the laterite leach liquor
directly but uses a completely different approach. The lateritic
ore is acid leached under pressure at 270 °C. The clarified
autoclave discharge liquor is partially neutralized to precipitate
Al, Cr(III), Cu, Fe and Si. Trace quantities of residual copper are
reduced to levels of <0.04 mg/l by ion exchange using a chelat-
ing resin because it poisons the extractant used in the subsequent
extraction operation and catalyzes its oxidation (95).
Ni, Co and Zn are quantitatively and selectively extracted
from other metals in solution by Cyanex 301, which is the
disubstituted sulfur analogue of Cyanex 272. Excellent
extraction is achieved under acidic conditions (pH 1–2), so
no pH adjustment is required in the solvent extraction circuit
and the waste streams can be neutralized with inexpensive
limestone. Cobalt and nickel are separated using tertiary
amine extractant (Alamine 308). Nickel is recovered by
pyrohydrolysis as NiO, regenerating HCl for recycle to the
Cyanex 301 strip circuit, while cobalt is recovered as a
carbonate salt. The construction of Goro process was under-
way in 2007 and the project was considered as the first
commercial application of Cyanex 301. The solvent extrac-
tion contacting equipment to be used is pulsed columns
206 Y.A. EL-NADI
FIGURE 11 Bulong flow sheet for purification of nickel and cobalt from laterite leach liquor (60). © Taylor & Francis. Reproduced by permission of Taylor
& Francis. Permission to reuse must be obtained from the rightsholder.
rather than the traditional mixer-settlers used in most base-
metal plants (96).
Zinc
Traditional processing routes for zinc sulfide concen-
trates produce high-tenor purified zinc solutions suitable
for direct electrowinning of the metal. Such schemes are
not cost-effective for lower-grade zinc deposits. Several zinc
projects were developed in which the preferred flow sheets
incorporate SX-EW technology (97, 98). The Skorpion Zinc
operation in Namibia, Figure 13, is an interesting example
of the use of leaching and SX–EW to recover zinc from an
ore previously considered untreatable from both the proces-
sing and economic points of view. This is the first plant to
use direct SX on the mainstream leach liquor in primary
zinc processing and is one of the lowest cost zinc producers.
The Skorpion ore is a low-grade silicate containing
10–40% Zn and about 26% Si. Following an atmospheric
leach in sulfuric acid, Fe, Al and Si are rejected from the
leach liquor by precipitation. Zinc is then purified by
solvent extraction with D2EHPA ahead of electrowinning.
Zinc electrowinning typically requires an extremely pure
electrolyte containing ~100 g/l Zn. Because of the low
zinc content of this feed material, leaching conditions that
produce a high-grade liquor would cause unacceptably
high soluble losses of zinc in the subsequent filtration
step. The Skorpion leach liquor also contains significant
quantities of fluoride and chloride that are detrimental to
zinc electrowinning, Figure 13.
Refining of Precious Metals
The classical refining methods used for precious metals
remained unchanged for several decades. Refining relied heav-
ily on precipitation methods and was extremely tedious and
inefficient because of the substantial and numerous recycles
required, the large number of solid–liquid separations, and the
consequent long residence times of the valuable metals in the
circuit. In the past two decades, significant advances have been
made in the processing of these elements, and solvent extrac-
tion is now widely used as the main separation technique.
Precious metal feed materials are almost always leached in
HCl, with chlorine gas as the oxidizing agent. The dominant
aqueous species formed under these conditions are shown in
Table 4. A variety of oxidation states and coordination structures
exist. These differences are exploited in designing extractant
systems that will be selective for one element over the others
(99). The lower the charge density, the more extractable is the
species. In general, the order of extraction from strong HCl is
AuCl4− > PtCl62− ≈ IrCl62− > PdCl42− > RhCl63− ≈ IrCl63−.
In most processes that use solvent extraction, gold is removed
from solution first, followed by palladium, and then platinum.
The remaining platinum group metals (PGMs) are recovered in a
variety of ways, either up-front or at the end of the overall flow
 SOLVENT EXTRACTION FOR METAL RECOVERY 207

FIGURE 12 Goro process for recovery of nickel from laterites (60). © Taylor & Francis. Reproduced by permission of Taylor & Francis. Permission to reuse
must be obtained from the rightsholder.

sheet. In each case, a pure solution of the respective metal is
obtained, which is then subjected to a reduction to produce the
pure metal powder or sponge. The final products are obtained by
melting to obtain ingots, granules or delivery bars.
Gold
INCO (United Kingdom) first used solvent extraction for the
refining of gold from chloride solution (100, 101). The extrac-
tant, dibutylcarbitol (DBC), is a straight-chain, high-molecular-
mass molecule that contains three oxygen atoms in ether posi-
tions. The extraction mechanism has been shown to involve the
formation of an ion pair between the solvated auric chloride
anion and the oxygen-donor reagent (102). Although several
PGM refiners around the world have used DBC, this reagent
suffers from several disadvantages. Under the high acid condi-
tions of the leach, it is not particularly selective over some of the
metalloid elements often found in solutions of this nature. It is
also very difficult to strip effectively, so recovery of gold from
the loaded organic phase is by direct reduction with oxalic acid
in a batch process. The extractant is also fairly soluble in the
aqueous phase (~3 g/L) and dissolved organic losses are higher
than are generally considered acceptable.
Therefore, the Minataur process for the refining of gold
was developed in South Africa (103). This technology uses
solvent extraction as the main purification step and a variety
of feed materials ranging in gold content from 50% to 99%
can be treated. The identity of the extractant remains pro-
prietary. It is known to be inexpensive and does not present
the disadvantages of DBC mentioned above. Gold loadings
of >100 g/L on the organic phase can be achieved and
stripping efficiency is high (104, 105). The process pro-
duces gold of 99.99% purity. Advantages of the process
are the reduced gold lock-ups and residence times in the
circuit and the ability to produce high-purity gold with
minimal recycles in the flow sheet. This process is presently
operating in South Africa, Algeria and Dubai (106).
Palladium
Most research into the recovery of palladium by SX has
centered on the use of sulfur-based extractants (107).
208 Y.A. EL-NADI

FIGURE 13 Simplified flow sheet of the Skorpion zinc process (60). © Taylor & Francis. Reproduced by permission of Taylor & Francis. Permission to
reuse must be obtained from the rightsholder.

TABLE 4
Precious metal oxidation states and aqueous chloro complexes

Complexes formed

Metal Oxidation state Coordination number Complex geometry Low [Cl−] High [Cl−]

Au +3 4 Square planar AuCl4− AuCl4−

Ag +1 2 Linear AgCl2− AgCl2−
Ru +3 6 Octahedral Ru2OCl8(H2O)24− RuCl63−
+4 6 Octahedral RuCl62−
Rh +3 6 Octahedral Rh(H2O)23+ RhCl63−
Pd +2 4 Square planar PdCl42− PdCl42−
+4 6 Octahedral PdCl62− PdCl62−
Os +4 6 Octahedral OsCl62−
Ir +3 6 Octahedral Ir(H2O)xCl6-x(3−x)− IrCl63−
+4 6 Octahedral IrCl62− IrCl62−
Pt +2 4 Square planar PtCl42− PtCl42−
+4 6 Octahedral PtCl62− PtCl62−

Organic sulfides are selective for palladium over all other
precious metals except gold, so gold is removed from the
HCl leach liquor ahead of palladium. The extraction reac-
tion is:

ðaqÞ þ 2R2 SðorgÞ , PdCl2 ðR2 SÞ2ðorgÞ þ 2Cl ðaqÞ
PdCl4 2
The extraction mechanism involves substitution of the
inner sphere chloro ligands by the dialkyl sulfide. Palladium
extraction with this reagent is extremely slow, taking several
hours to reach equilibrium. The reaction goes to completion,
however, leaving less than 1 mg/L Pd remaining in the
(11) raffinate. The reaction is carried out in batch mode. Strong
ammonia solution is used for stripping. Palladium is

FIGURE 14 Effect of HCl concentration on extraction of platinum group metals by TBP (60). © Taylor & Francis. Reproduced by permission of Taylor & Francis.
Permission to reuse must be obtained from the rightsholder.
recovered by acidification with HCl to precipitate
Pd(NH3)2Cl2, which is calcined to produce the metal.
Various oximes, similar to those used in copper extrac-
tion, have also been widely studied as palladium extrac-
tants. Johnson Matthey (United Kingdom) and Anglo
Platinum (South Africa) recover palladium with a β-
hydroxyoxime. Although the kinetics of this extraction
is extremely slow, the extraction rate can be enhanced
by the addition of amines that act as accelerators. An
advantage of these reagents is that they can be stripped
with strong acid, avoiding the use of ammonia (108).
Stripping is typically achieved using 6 M HCl.
Recovery of the metal is by salt formation, followed by
reduction or calcination.
Platinum Group Metals (PGM)
Platinum is recovered after palladium in most flow
sheets. TBP is the most widely used platinum extractant.
The effect of HCl concentration on the extraction of
PGMs by TBP shows the process has a very
narrow operating window between about 3 and 4 M
HCl. So, it is also necessary to adjust the reduction
potential of the solution to ensure that iridium(IV) is
not coextracted.
Amines are good platinum extractants, and schemes in
which primary through quaternary amines are employed
have been proposed. The extraction occurs via an anion-
SOLVENT EXTRACTION FOR METAL RECOVERY 209
exchange mechanism. The reaction for tertiary amines can
be written as:
2R3 NðorgÞ þ 2HClðaqÞ , 2½R3 NHþ Cl ðorgÞ (12)
2½R3 NHþ Cl ðorgÞ þ PtCl6 2 ðaqÞ
, ½R3 NHþ 2 PtCl6 2 ðorgÞ þ 2Cl ðaqÞ (13)
In these systems, complete stripping can only be
achieved by deprotonation of the extractant using sodium
carbonate solution.
Amines are generally employed in combination with alco-
hols, phenols or carboxylic acids that modify the pH depen-
dence of extraction so that stripping is easier (109). The
relative extraction efficiencies of the amines as a function of
chloride concentration are shown in Figure 14. The use of tri-
n-octylamine to recover platinum from the gold- and palla-
dium-depleted leach liquor was reported where it is necessary
to use 12M HCl for stripping with this reagent (110).
IONIC LIQUIDS AS SOLVENT EXTRACTANTS
Solvent extraction employs water-immiscible organic sol-
vents that can be toxic, flammable or volatile. Given the
rising costs for their eventual disposal and the growing
awareness of the environmental impact associated with
210 Y.A. EL-NADI
their use, it is clear that the replacement of these solvents
with less noxious alternatives is desirable (111). Recently
there has been increasing emphasis on the development of
environmentally benign separation processes. An important
aspect of this effort to devise greener separations is, in fact,
the identification, characterization and application of novel
solvents exhibiting few or none of the drawbacks of their
traditional organic counterparts (112).
Of particular recent interest among alternative solvents
have been ionic liquids (ILs). ILs are highly polar molten
salts possessing large ions with delocalized charges. This
leads to lower Coulomb attraction forces between ions,
which results in low melting temperature of ILs (113).
Ionic liquids exhibit several properties that make them
attractive as a potential basis for improved extraction pro-
cesses, among them are a wide liquid range, good thermal
stability, the ability to solubilize a wide range of solutes, a
near-absence of vapor pressure and an extraordinary degree
of tunability (114).
It has been observed that processes of metal ion separa-
tion from aqueous solutions using ILs as solvents, extrac-
tants and/or ion carriers have grown in significance. ILs
became attractive alternatives to volatile organic solvents
(VOCs) also as a result of good extractability for a variety
of organic compounds and metal ions (115, 116).
The hydrophobic characteristics of some ILs allow for
the extraction of many heavy metal ions, such as zinc,
mercury, lead, cadmium, iron, chromium, copper and nickel,
from aqueous solutions (117). Despite their hydrophobic
character, ILs offer relatively high solubilities for salts and
can consequently be used for the extraction of salts (118).
The solubility of an ILs in water strongly depends on the
type of cation and anion (119). ILs possessing acid anions
can be also used for the leaching of many metals from ores
(120).
In metal recovery and refining, extraction with ILs pro-
vides new prospects to exploit low-value metal ores and to
recycle metal ions (121, 122). A number of studies have
been focused on developing effective extractants for SX;
however, very few reports can be found in the literature
concerning the mixtures of ILs and classic extractants.
Recently, numerous papers have been published on the
application of ILs as extracting reagent solvents and as
individual extractants of metal ions from aqueous solutions
(113).
ILs have also been used as passive diluents for many
extractants in liquid–liquid extraction of various metal ions
from aqueous phase. Imidazolium ILs are solvents with
well-known physicochemical properties (123, 124). For
example, butylmethylimidazolium hexafluorophosphate,
[BMIM][PF6], was used as a diluent of dithizone during
extraction of heavy metals ions, for example, Hg(II), Cd(II),
Pb(II), Ag(I) and Cu(II) ions, from aqueous solutions.
ILs have also been examined in liquid–liquid extraction
of alkali and alkaline metal ions using crown ethers (125) or
calixarenes in extraction of Cs(I) (126). Dioxouranium(VI)
was extracted from nitric acid solutions by TBP/IL mixtures
using three types of 1,3-dialkylimidazolium (127). Sun et al.
(128) reported on the use of Cyanex 923 in 1-octyl-3-
methylimidazolium [C8MIM][PF6] for a selective extrac-
tion–separation of Y(III) from a mixture of heavy lantha-
nides. The extraction efficiency of the Y(III)/Cyanex 923/
[C8MIM][PF6] system was found to decrease rapidly with
increasing aqueous acidity.
It was found that ILs containing disulfide or nitrile
groups exhibit good extraction properties for Ag(I) and Pd
(II) ions. Au(III) ions were also efficiently and selectively
extracted using functionalized ILs containing functional
alkenyl group and nitrile or disulfide groups (115).
The extraction of Eu(III) ions by ILs showed a strong
dependence on the nature of molecular solvents such as
chloroform, n-dodecane and 1-octanol. The effect of diethy-
lenetriamine pentaacetic acid on the extraction efficiency of
Am(III) and Eu(III) ions from water was also described
(129). ILs were also investigated as ion-selective extractants
for Pd(II) ions from 0.1 M HCl solution containing many
metal ions (130). It was noticed that the selectivity of the
extraction of Pd(II) is dependent on the acidity of the aqu-
eous phase and decreases with increasing concentration of
HCl.
Zhang et al. (131) reported the extraction of cerium(IV)
ions, fluoride ions and Ce(IV)–F mixture from sulfuric acid
using bifunctional IL extractants in n-heptane. The investi-
gated systems proved strong separation capabilities, show-
ing the following extraction order: Ce(IV) > Th(IV) > Ce
(III). Rout et al. (132) used ILs to study Nd(III) extraction
and found that the extraction efficiency increases with an
increase in the initial pH of the aqueous solution, reaching a
maximum at pH 2. Using 1-octyl-3-methylimidazolium
[C8MIM] bis(trifluoromethylsulfonyl)imide as IL, Pt(IV)
ion can be removed from gold (133). Extraction of
Pt(SCN)62− was very high at pH 1, exhibiting a distribution
coefficient of 6150.
A novel ionic liquid, 1-hexyl-3-methyl imidazolium
[C6MIM] dodecyl sulfonate, was synthesized and used
for the construction of an aqueous two-phase system
together with PEG6000, which was investigated for Au
(III) extraction later (134). Under the optimum conditions,
the extraction percentage was up to 97.56%. The sug-
gested aqueous two phase system is supposed to be a
promising approach for gold extraction and separation in
acid solutions. In another study, a selective extraction and
recovery of Au(III) from a tertiary metal solution contain-
ing Au(III), Pt(IV) and Pd(II) were investigated using
ionic liquid Aliquat-336 (135). Through sequential extrac-
tion, high purity of each metal solution was separately
obtained from low and high concentrations of multi-
metal solutions.
Zhao et. al. (136) found that isohexyl-BTP in ionic
liquids exhibited remarkably better extraction performance

for lanthanides than that in octanol–dodecane system espe-
cially at lower acidity conditions (<0.1 mol/L).
A solvent extraction of lithium ions from the Mg(II)-
containing salt lake brine into a commonly used ionic liquid
1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)
imide ([BMIM][NTf2]) using TBP as the extractant was
investigated (137). Under the optimal conditions, the single
extraction efficiency of lithium was 92.37%, which indi-
cated that it was an efficient extraction system for the
recovery of lithium ions.
A novel selective ligand, bis-(2-ethylhexyl) carbamoyl meth-
oxy phenoxy-bis-(2-ethylhexyl) acetamide (BenzoDODA), was
studied for Pu(IV) extraction behavior in the presence of
[BMIM][NTf2] ionic liquids (138). The presence of [BMIM]
[NTf2] tended to enhance the extraction of Pu in both HCl and
HNO3 as compared to that of using n-dodecane as diluent. Also,
studies on the nature of species formed by Pu(IV) and
BenzoDODA in both acid media showed formation of a di-
solvate species for IL in contrast to mono-solvate formed in
n-dodecane. In addition, at higher nitric acid concentration (7
M) BenzoDODA was found to be selectively extracting Pu(IV).
Another novel ammonium and phosphonium ionic
liquids (ILs) with thiosalicylate (TS) derivatives as anions
were developed and their extraction efficiencies were eval-
uated toward heavy metals in aqueous solutions (139). Six
ILs were synthesized, characterized and investigated for
their extracting efficiencies for cadmium, copper and zinc.
Phosphonium-based ILs trihexyltetradecylphosphonium 2-
(propylthio)benzoate [P66614][PTB] and 2-(benzylthio)
benzoate [P66614][BTB] showed best extraction efficiency
for copper and cadmium, respectively, and zinc was
extracted to a high degree by [P66614][BTB] exclusively.
SUMMARY
Solvent extraction or liquid–liquid distribution techniques
have a broad field of applications in inorganic and organic
chemistry and large-scale industrial separations. In addition,
it is a good instrument for studying fundamental under-
standing of equilibrium and kinetics of complex formation
processes. Extraction methods have now become a routine
procedure in separation technologies. This review tried to
draw a picture about the important applications of solvent
extraction as processing of ores like monazite, bastnasite,
skorpion, etc. and recovery of valuable metals such as U,
Th, REEs, Pt, Pd and others from different sources. It also
presented a classical approach about the basic principles of
the technique. One of the recent trends in this field concern-
ing with using ionic liquids (ILs) as extractants has also
been included. In this respect, ILs can be considered as
environmental-friendly, low-toxic, green solvents in contrast
to conventional low-boiling organic solvents, which are
usually used in traditional solvent extraction systems.
Therefore, this part has been involved in order to show the
SOLVENT EXTRACTION FOR METAL RECOVERY 211
characteristics of ILs, their structures and their applications
in various separation processes of metal ions, especially that
certain IL–extractant combinations have been shown to
yield metal ion extraction efficiencies far greater than
those obtained with molecular organic solvents.
ORCID
Y.A. El-Nadi http://orcid.org/0000-0003-1889-4981
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