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Present and future applications of ion exchange in hydrometallurgy: An

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Society of Chemical Industry IEx 2016 – Hydrometallurgy Session
PRESENT AND FUTURE APPLICATIONS OF ION EXCHANGE

IN HYDROMETALLURGY: AN OVERVIEW
Kathryn C. Sole
Consulting Hydrometallurgist, Johannesburg, South Africa
(kathysole09@gmail.com)
Michael B. Mooiman
Franklin Pierce University, Manchester, New Hampshire, USA
Edmund Hardwick
Cwenga Technologies, Johannesburg, South Africa
ABSTRACT
Ion exchange has traditionally been employed for water purification and for the removal of
metal contaminants from waste-waters or dilute streams. In the last 25 years, however, its use
for removing various trace metallic impurities from hydrometallurgical process streams (with
background metal concentrations typically ranging from 50 to 100 g/L) has increased
substantially. It is also used as a primary recovery and concentration unit operation for certain
commodities, where cost and technical advantages become available for complex flowsheets.
This overview discusses selected modern applications of ion exchange in hydrometallurgical
processes for uranium, precious metals, copper, cobalt, nickel, zinc, and the rare-earth
elements, and identifies some opportunities for the future.
Keywords: ion exchange, hydrometallurgy, review, uranium, precious metals, copper, nickel,
cobalt, zinc, rare-earth elements
1. INTRODUCTION
Ion exchange (IX) has traditionally been employed for the deionisation of water and the
removal of metals contaminants from waste waters or dilute streams. In the last quarter
century; however, its application in removing trace metallic impurities from
hydrometallurgical process streams (typically with background metal concentrations from 50
to 100 g/L) has increased substantially. It is also used as a primary recovery and concentration
unit operation for certain commodities.
The historical arc of IX applications in hydrometallurgy is interesting and worthy of

consideration. As part of the Manhattan project during World War II,1 IX was used for
extraction of uranium from leach solutions and for separation of the transuranium elements.
IX has since had a long history in uranium processing and many large-scale applications
operating today are for uranium recovery. This industry pioneered the development of resins
for metals extraction and specialized contactors and contacting approaches, such as resin-in-
pulp (RIP). IX for gold recovery from cyanide solutions received attention in the 1950s; first
reports of successful application came out of the Soviet Union in the 1970s. With the advent
of activated carbon and carbon-in-pulp (CIP) technologies in the 1970s and 1980s, resin
applications for precious metals (PM) recovery received renewed attention and have since
been steadily supported and advanced by researchers and resin manufacturers.
1
Uranium and gold recovery by IX involve primary extraction of the metals from dilute
leach liquors and take advantage of the high upgrade ratios that the technology permits. More
recent applications, coupled with the development of highly selective and specialized resins,
have seen clean-up and scavenging applications in the base metals industry, where IX is used
to recover low levels of impurity metals from concentrated solutions, such as the removal of
contaminating zinc and copper from concentrated cobalt electrolytes prior to electrowinning
(EW). Scavenging applications are increasingly relevant in the PM industry, where resins are
used to recover low concentrations of valuable metals from spent process and waste waters.
This overview discusses some modern applications of IX in hydrometallurgical processes,

from primary recovery of uranium and gold, to complicated separation schemes for PM,
through to a growing number of scavenging applications. Knowledge has improved regarding
the cost and process advantages that this technology can provide in complex flowsheets. In
general, IX shows technical advantages at low metal concentrations in comparison with
precipitation, solvent extraction (SX), membrane processes, and activated carbon. Most IX
processes are inherently safe, owing to the low toxicity of the media, and pose negligible fire
or explosion risk. IX readily lends itself to a high degree of automation. Contributions from
manufacturers that have improved the selectivity and durability of the resins are highlighted
and some future opportunities are identified.
2. URANIUM
Uranium has been commercially recovered by IX since the 1950s, using fixed-bed (FBIX),
semi-continuous, and resin-in-pulp (RIP) configurations, sometimes in combination with SX.
Technologies for the primary processing of uranium have not changed significantly during the
past half-century: all flowsheets involve an upfront leaching step to solubilise the metal and a
subsequent recovery step that produces ammonium (or, less often, sodium) diuranate (ADU,
SDU), commonly known as yellow cake, which is calcined to give U3O8 as the final product.2
Uranium ores are typically leached in acidic (pH 1.2–2.5) sulfate medium, solubilising
uranium as cationic UO22+, which combines with sulfate present in the leach liquor to form
the uranyl sulfate anions, UO2(SO4)22– and UO2(SO4)34–. The aggressive leaching conditions
(high temperatures and high redox potentials of 600–700 mV wrt SHE) also dissolve many
other impurities, including the anions of Si, Mo, Bi, W, Sb, As, Mn, V, Zr, and P.3 Other
anions, such as Cl–, NO3–, SCN–, S2O3–, SO42–, HSO4–, and Fe(SO4)2–, are also generated
during leaching. The weakly acidic leach liquor is typically subjected to one of three
processing routes: IX for concentration and purification; IX for concentration, followed by
SX for purification (the so-called Eluex or Bufflex process); or direct SX (the Purlex or Amex
process). For high acid-consuming ores, leaching is carried out in an alkaline medium, using a
basic mixture of sodium carbonate and sodium bicarbonate (pH 9.5–11) that dissolves
uranium as an anionic carbonate complex. Amine functionalities are used for the recovery of
uranium from both sulfate and carbonate leach liquors by SX and IX.4
2.1 Purification of uranium liquors by ion exchange

IX is typically used for uranium recovery from lower-grade ores or systems with difficult
liquid–solid (L/S) separation characteristics, either by operating with unclarified solutions or
2
in an RIP system. Strong-base anion-exchange resins, with quaternary ammonium functional

groups, are most commonly used:
UO2(SO4)34– + 4 P–NR3X → P–NR3UO2(SO4)3 + 4 X– (1a)
UO2(CO3)34– + 4 P–NR3X → P–NR3UO2(CO3)3 + 4 X– (1b)
where P represents the resin backbone (typically a polystyrene matrix), R is an alkyl group,
and X is the counter-ion. Typical modern examples of quaternary amine resins include PFA
600/4740 (Purolite)5 and Amberjet 4400 (Dow).6
Strong-base resins are poorly selective for the uranium anions and can be poisoned by
irreversible loading of strongly complexed anionic species, such as Mo, Si, polythionates, Ti,
Zr, V(V) and Th, and by organics, all of which reduce reactivity and loading capacity.7
Sulfates and bisulfates (and carbonates and bicarbonates) of the leach matrices compete for
resin sites and reduce the resin capacity for uranium. These resins also typically lose
effectiveness at chloride levels above 3 g/L. Co-loading of Fe(III), present as Fe(SO4)n(3–2n) or
Fe(OH)(SO4)22– in sulfate media, also depresses uranium extraction. In South Africa, where
most uranium is recovered as a byproduct of gold processing, cobalticyanide and polythionate
species have proved particularly troublesome. Cobalticyanide polymerises on the resin under
high-acid conditions and thereby poisons it,8 so common practice is to first acid-leach
uranium before cyaniding the residue to recover gold. This so-called ‘reverse leach’ improves
the efficiency of gold recovery (however, recycling of any water that still contains cobalt
cyanide from the gold circuit to the uranium circuit would cause a similar fouling problem).
Elution of uranium loaded from acidic media is usually carried out using sulfuric acid (100
g/L), where the bisulfate anion displaces the uranium complex. Upgrading of a leach solution
(0.1–0.8 g/L U3O8) to as high as 120 g/L U3O8 on the resin and 35 g/L U3O8 in the eluate can
be achieved by judicious selection of the operating conditions,9 although strong equilibrium
constraints exist. It is more common to employ a much lower upgrading factor and then
further process the eluate by SX. In alkaline leaching flowsheets, resins can be eluted using
NaNO3 or NaCl, often in the presence of Na2CO3 or NaHCO3.10
A significant limitation to the use of resins is the occurrence of silica fouling in cases
where the leach liquors have a high silica content.11 The mechanism and avoidance of this
phenomenon remain poorly understood, but silica is known to retard the kinetics of loading
and stripping, to increase reagent consumption due to the higher resin flowrates required, can
cause crud formation in a subsequent SX circuit, and can compromise the yellow cake quality
by silica contamination. Silica-fouled resin can be regenerated by treatment with caustic
solution, but this has to be minimised to limit the costs and the osmotic shock to the resin.
Today, weak-base resins (based on secondary- or tertiary-amine functionality) are also

employed for acidic circuits, although these are only suitable for treatment of low-silica
liquors. They are more selective and more resistant to abrasion than strong-base resins, but
their kinetics of loading is slower and they are more expensive. These resins now allow eluate
purities that approach those of SX.12
3
2.2 Comparison of SX and IX for the purification of uranium sulfate leach liquors
Tertiary amines (usually tricaprylylamine) extractants are widely used for SX applications
because they have the greatest selectivity for uranium over iron(III) and can treat solutions
with a wide range of acidities: varying from pH 2 for leach liquors to >100 g/L H2SO4 when
treating IX eluate in an Eluex process.10 Extraction is very rapid and stripping occurs readily
under mild conditions. SX flowsheets can be configured to be selective over many impurities,
including Fe, V, and Mo. Tertiary amines are weak bases (in contrast to the strong-base
chemistry of most resins used for uranium reocvery) so, although poisoning by anionic
contaminants (Fe, As, Mo, V, Zr, Th, nitrates, chlorides) does occur, regeneration using a
Na2CO3/NaOH mixture is relatively easy and valuable secondary products can be produced.
SX is generally preferred if the ore contains contaminants that could report to the final
product. SX systems are sensitive to the presence of suspended solids, flotation reagents, and
oils: phase disengagement can be slow.13 SX and IX both have advantages and limitations in
the processing of uranium. The combination of IX and SX systems in sequential operating
mode (the Eluex process) offers greater selectivity, and therefore higher product purity, than
either of the individual processes. Using IX alone is usually only possible if the leach solution
is relatively free of impurities that are deleterious to product purity and it is costly if all of the
acid in the eluate has to be neutralised prior to precipitation: generating a higher grade eluate
lowers the acid consumption for direct precipitation. Silica fouling of resins remains a hurdle
to widespread acceptance of this technology.10
The flowrate of the pregnant leach solution (PLS) is a major factor affecting process
selection, and has a significant impact on both the capital and operating costs, particularly for
SX and FBIX, and to a lesser extent for NIMCIX or fluidised-bed IX. The use of an Eluex
circuit, incorporating strong-base CCIX followed by SX using mixer-settlers, is often
considered for flowsheets where the uranium tenor of the PLS is low and that would require a
very large stand-alone SX plant: IX enables upgrading of the uranium tenor at lower cost.14,15
Of the 15 uranium plants operating in South Africa in the 1980s, it is interesting that the only
three plants to survive to 2015 all use Eluex flowsheets.
The advantage of CCIX as a low-cost uranium pre-concentration step is not realised unless
the size of the downstream SX circuit can be significantly reduced (or completely
eliminated).6 The pre-concentration ability of CCIX is limited by the maximum concentration
that can be achieved in the CCIX eluate (4–7 g/L U3O8) and the upper limit of the loading
capacity of amine extractants (phase separation problems may occur above organic loadings
of 8–10 g/L U3O8). In the treatment of high concentration PLS, the direct SX route becomes
more attractive and gives superior economic returns at tenors greater than 0.9 g/L U3O8,14,15
although SX has been used to treat feed tenors ranging from 0.07–14 g/L U3O8. SX requires
phase contact times of less than 30 s for equilibrium to be reached, while IX kinetics are slow
and require a high resin inventory, adversely affecting the capital cost of a plant (although this
can be minimised by use of a counter-current configuration).
Clarification of the leach solution is very important ahead of both SX and IX, particularly
if silica is present. Extensive clarification, including counter-current decantation (CCD) and
belt filters, is typically employed to mitigate such issues (although silica cannot be effectively
removed in L/S separation equipment, because conditions may cause it to precipitate
4
subsequent to clarification). Studies have indicated that L/S separation equipment can
comprise up to 25% of the cost of a uranium plant.16 IX is more tolerant of the presence of
solids than SX (which requires <20 ppm and preferably <10 ppm total suspended solids
(TSS)). The potential ability of CCIX to handle unclarified leach solutions offers a substantial
advantage to this process, particularly for ores that contain clays or other slimes that are
difficult to settle. Several authors have studied this topic in some detail.11,13,17,18
RIP, resin-in-leach (RIL), and in-situ leach processes have been widely used in the Central
Asian Republics, mainly due to low ore grades, a fragmented industry, and in preference to
using a CCD or filter circuit.19 In RIP, the resin is added into the slurry after leaching to
recover solubilised uranium, while in RIL, the resin is added directly into the leach process to
scavenge uranium as it is leached and thereby drive the equilibrium of the leach reaction. RIP
can be applied to both acid and carbonate leach pulps, where particle sizes up to 80% passing
75 μm and pulp densities up to 50–55% solids can be tolerated. Uranium losses can be
minimised because of lower adsorption losses (so-called ‘preg-robbing’) on shales, clays, and
zeolites. Water use and bleed volumes are minimised because RIP/RIL can typically recover
almost all of the soluble losses that would occur if CCD were used.20
RIP is generally considered more cost-effective for low-grade ores or high throughputs.
Flowsheets using RIP followed by direct precipitation from the eluate have lower capital and
operating costs than CCD–filtration and SX circuits: no L/S separation is required and no
clarification of the leach liquor (as for SX and FBIX) is necessary. The use of a batch process
allows control of resin inventory, but introduces other metallurgical constraints, such as the
resin residence time in the adsorption circuit. One of the main limitations of RIP is the high
acid consumption when neutralisation of the eluate is required prior to uranium precipitation:
strategies such as increasing the uranium content in the eluate or recovering the acid prior to
uranium precipitation can circumvent this. In FBIX applications, the uranium concentration
can be upgraded by a factor of 10–30: using split elution with partial recirculation of a portion
of eluate can be used to increase the eluate concentration. When using a carousel-type
contactor, continuous elution also offers the possibility of achieving a higher grade eluate.21–24
Counter-current continuous elution processes claim more efficient elution, achieving a higher
uranium concentration, which, in turn, allows for direct precipitation from the eluate and
avoids the additional capital and operating costs of a downstream SX circuit.25
IX systems are, in general, inherently safer than SX systems due to the fire risk associated
with the use of organic solvents, potential for organic contamination of the environment and
downstream processes, and attack by organics on materials of construction. In SX circuits, the
loss of entrained organic in the raffinate and uranium loaded strip liquor (known as OK
liquor) (up to 200 mg/L) can also increase reagent usage if not properly engineered. However,
IX suffers from physical breakdown of the resin beads due to mechanical attrition and
osmotic shock: long-term integrity of the resins can be poor, particularly under conditions
where the acidity of the aqueous phase is cycled by variations of up to 100 g/L H2SO4. Resin
durability is the primary challenge in the use of RIP or RIL, with conservative estimates of
resin make-up due to attrition as high as 40% per annum.22 In recent years, significant
manufacturing advances have been made in improving the size distribution and durability of
strong-base resins. Today, resin technologies have progressed to the point that the costs of
5
resin losses in an RIP process are low compared with solvent losses for an equivalent SX
system.11 Resin losses are estimated to contribute less than 0.02% of the annual operating cost
for a typical plant.11 Other important factors influencing flowsheet selection include the
project size and location, as well as availability and cost of associated reagents. An excellent
overview of process options, design criteria, and equipment selection for the
hydrometallurgical processing of uranium is presented by Ivanova et al.25
2.3 Selected process descriptions

2.3.1 Sulfate-based Eluex processes
Rössing Uranium (Namibia): This is the longest-running (operating since 1976) and third
largest open-cast uranium mine in the world. In 2014, it produced 1543 t U3O8 (or 2.3% of the
world’s uranium).27 Uranium is extracted from the crushed ore by atmospheric leaching in
dilute sulfuric acid with an average leach efficiency of 89%. Following L/S separation,
uranium is recovered from solution (0.18 g/L U3O8) by IX using Dow RPU resin. Multiple-
tank fluidised bed IX is carried out in four trains of Porter contactors, each with six units. PLS
and resin are continuously moved counter-currently: resin is transferred upstream between
stages by airlift. The Porter contactor is suitable treating for slimes with several percent solids
although it has higher resin loss than fixed-bed designs (due to the number and nature of resin
movements) and also has a larger footprint. Loaded resin is transferred to one of three elution
columns, where uranium is eluted with 100 g/L H2SO4 derived from the SX raffinate. The
eluate, containing 3–5 g/L U3O8, is pumped to an SX plant where it is further concentrated
and the remaining impurities removed.10 pH-controlled stripping is carried out using an
ammonia/ammonium sulfate system, giving an OK liquor containing 15–20 g/L U3O8. ADU
is precipitated by ammonia addition to the OK liquor. This is dried and calcined to produce
Rössing's final product – grey-black powdered uranium oxide (U3O8).
Vaal River (South Africa): The South Uranium Plant at Vaal River has been operating since
1978 using an Eluex flowsheet. It currently treats uraninite ore (0.45 kg/t U3O8) from Noligwa
gold plant. The gold slurry is processed for uranium recovery in an agitated leach using
sulfuric acid, MnO2 (as an oxidant), and steam (~55oC). Following CCD, the leach liquor is
purified by IX, SX, and ADU precipitation, achieving an overall 70% uranium recovery.
The original stainless steel CCIX loading circuit and Himsley fluidised-bed elution circuits
were replaced with graphite-reinforced polymer NIMCIX columns in 2009. Each loading
column comprises 14 1-m stages, each containing 7 m3 of resin. The resin employed is
Amberjet 4400Cl (Dow), which allows very high recovery of uranium (>99%).The IX circuit
treats a PLS flow of 200 m3/h and elution is carried out with 100 g/L H2SO4. The equipment
upgrade enabled the eluate concentration to be increased from 2 to 7 g/L U3O8. A small
regeneration column, in which silica loading is controlled by the addition of 6% NaOH
solution, is also included in the circuit.
Operating conditions in the subsequent SX step have also been recently modified to
accommodate increased uranium throughput. The extractant is Alamine 336, with isodecanol
as a modifier.9 The SX product is purified and upgraded to ~10 g/L U3O8, which is
precipitated as ADU for further processing at a nuclear site.
6
Husab Uranium (Namibia): Only discovered in 2008 (previously known as Rössing South),
this will soon become the second largest uranium mine in the world (after MacArthur River in
Canada), producing 7000 t/a U3O8.28 The mine is majority Chinese-owned and represents the
single largest Chinese investment in Africa to date. Mining started in 2015 and the processing
plant is being commissioned in 2016. The process comprises a sulfuric-acid leach, IX using
NIMCIX columns, followed by SX upgrading and ADU precipitation. The resin selected is
Purolite PPA800SO4. When this operation reaches full capacity, Namibia will become the
third-largest uranium producer in the world.
2.3.2 Sulfate-based resin-in-pulp process

Kayelekera (Malawi): This was the first flowsheet in the western world to use RIP for the
production of uranium without the use of SX.29 Production of uranium began in April 2009,
treating an ore (mainly coffinite (U(SiO4)1-x(OH)4x), with an average grade of 0.11% U3O8.
The plant capacity is 2250 t/a U3O8.
Atmospheric leaching at ambient temperature is conducted in six mechanically agitated

tanks, where concentrated H2SO4 is used for pH control and H2O2 is employed as an oxidant.
The screened slurry is processed by RIP using ten Kemix pump cells30,31 that allow counter-
current carousel movement of the slurry and the resin beads. The resin currently employed is
a mixture of Dow’s 920U and Purolite’s A500/2788. Following strong-acid elution and
removal of some impurities by precipitation, the uranium-rich solution is treated using H2O2
with NaOH for pH control to precipitate uranyl peroxide.32
This flowsheet claimed to offer lower capital and operating costs and better plant
operability with reduced project risk than a conventional CCD–SX–ADU precipitation
route.33 The operating cost was estimated at USD 23/lb U3O8 over the life of mine.33
Unfortunately, the uranium industry has suffered a severe setback since the Fukushima
nuclear accident associated with the Great Tōhuku Earthquake of 2011, and this plant was
placed on care and maintenance in February 2014.34
2.3.3 Carbonate-based ion-exchange process

Langer Heinrich (Namibia): Production started in 2007 as the first new uranium mine in 20
years.35 It has subsequently gone through two further expansions, and current capacity is 2360
t/a U3O8. In 2015, this was the lowest-cost open-pit uranium operation in the world.36
The carnotite (K2(UO2)2(VO4)2) ore is hosted in calcite so the process uses an alkaline
leaching flowsheet. The beneficiated ore is leached in 40 g/L Na2CO3, 10 g/L NaHCO3 at
90oC and pH 10.5, with a residence time of 36 h required due to the slow leach kinetics.
Following L/S separation in a six-stage CCD circuit, the PLS (~0.6 g/L U3O8) is purified by
IX. The original plant used a fixed-bed configuration, although NIMCIX columns (developed
by Mintek, South Africa) were used for the expansion. An advantage of this equipment is that
it can treat unclarified solutions (up to 300 ppm TSS) with low capital and operating costs,
recoveries are high, and resin losses are low. The UO2(CO3)34– anion in solution is loaded
onto a strong-base anion exchanger, Purolite’s PPA800HCO3. Fixed-bed elution takes place
using 1 M NaHCO3 before returning to the loading cycle:
Na4UO2(CO3)3 + 2 (P–NR3)2CO3 → (P–NR3)4UO2(CO3)3 + Na2CO3 (2)
7
(P–NR3)4UO2 (CO3)3 + 4 NaHCO3 → 4 (P–NR3)HCO3 + Na4UO2(CO3)3 (3)

NaOH is added to precipitate SDU and produce Na2CO3 by reaction with excess NaHCO3:
NaHCO3 + NaOH → Na2CO3 + H2O (4)
This allows the barren solution to be recycled to the leach as a reagent source and represents a
significant operational cost saving because little additional Na2CO3 make-up to the circuit is
required. In the second precipitation step, the SDU is acidified with H2SO4 and H2O2 is added
to precipitate a hydrated uranium peroxy product.
3. PRECIOUS METALS
The high value of the PM and their selectivity for IX resins, coupled with shortcomings of
traditional recovery and refining techniques have made for intriguing and promising research
topics devoted to studying PM separations and recoveries by IX. A large number of
investigations37–40 have been undertaken and it is notable that, for so much research devoted
to such a promising technique, the number of successful applications is remarkably limited.
There are three main areas where IX finds application: (i) recovery of PM from primary leach
liquors, e.g., gold from cyanide leach solutions; (ii) refining of PM, normally involving
chloride solutions of higher concentrations; and (iii) scavenging of PM from dilute solutions,
such as those produced by traditional refining methods, and PM chemical applications, such
as electroplating or catalyst production.
3.1 Recovery of precious metals from primary leach liquors

In primary applications, the need is to selectively and quantitatively recover PM from leach
liquors that usually contain low concentrations of PM and high concentrations of base metals.
Many separation approaches, each with advantages and shortcomings, have been proposed
and implemented, including cementation, SX, IX, and adsorption on activated carbon.
Leaching of gold and silver from ores is typically carried out in cyanide solutions and the
PM are recovered from solution via the Merrill–Crowe zinc cementation process or by
adsorption on activated carbon in the carbon-in-pulp (CIP), -leach (CIL), or -column (CIC)
processes. Since the 1970s, there has been a great deal of research and implementation of
activated carbon processes due to their effectiveness and advantages. Activated carbon is
highly selective for gold and silver adsorption and the separation of the loaded carbon from
the leached pulp requires only a simple physical screen; however, interferences from preg-
robbing ore constituents, such as organics and high base metal concentrations, do occur.
Additionally, stripping of the PM from carbon is a chemical- and energy-intensive process.
IX offers many of the advantages of activated carbon, such as direct adsorption of leached
PM from the pulp, high loading capacity, good selectivity, and physical separations, but does
not require the elution to be carried out at high temperatures or thermal reactivation (activated
carbon requires thermal regeneration at 600–700oC, which contributes significantly to
operating costs). Resins are, however, more expensive than activated carbon and their
particles are smaller, requiring smaller-aperture screens to separate resin and pulp and hence a
larger surface area requirement to achieve the same screening efficiency. Despite these
drawbacks, these costs are more than offset by the improved capacity and reaction kinetics of
8
IX resins over activated carbon.41 Considerable research has been devoted to IX recovery of
PM from cyanide solutions.42–44
The use of resins to recover PM from cyanide solutions goes back to the 1950s,42 but the
earliest success occurred in the implementation of RIP technology in the then Soviet Union.45
Much research was carried out at Mintek (South Africa) to refine the process, develop new
resins, and improve stripping.42–44 Two types of resins are advocated for gold recovery from
cyanide leaching—strong-base and weak-base resins.42 Strong-base resins incorporate
quaternary amine groups with a permanent positive charge: they show no pH dependency and
will adsorb gold from solution, even at very high pH levels:
P–NR3(SO4)1/2 + Au(CN)2− → P–NR3Au(CN)2 + ½SO42− (5)
However, this same lack of pH dependence makes these resins very difficult to strip: the
elution process invariably involves destruction of the loaded aurocyanide anion. In contrast,
weak- or medium-base resins have primary, secondary, or tertiary amine functional groups
that first require a protonation step to create IX functionality, before loading can take place:46
P–NR2 + ½H2SO4 → P–NR2H(SO4)1/2 (6)
P–NR2H(SO4)½ + Au(CN)2− → R–NR2HAu(CN)2 + ½SO42− (7)
Stripping of these resins is straightforward and involves contact with alkaline solutions to
deprotonate the resins:
P–NR2HAu(CN)2 + NaOH → P–NR2 + NaAu(CN)2 + H2O (8)
These reactions give these resins their distinctive pH functionality: high loadings at low pH
values and low loadings at high pH values. Because gold cyanide leach solutions have high
pH values (necessary to avoid the production of HCN gas), use of weak-base resins often
involves a compromise between the pH of loading, the degree of gold extraction, and the
extent of resin loading, as indicated by Figure 1.
Figure 1. Schematic illustration of the compromise between gold extraction,

gold loading on resin, and pH of leach liquor (adapted from van Deventer41).
9
Much of the early investigative work on RIP technology involved generic and
commercially available strong- and weak-base resins;42,43 however, research evolved to the
development and use of specialized resins for specific applications, which has led to some
important commercial applications.44 In 1999, the Penjom Mine in Malaysia, at that time
owned by Avocet Mining, implemented an RIL process using a specialty resin developed by
Mintek and manufactured by Dow.47 The strong-base resin contains tributylamine functional
groups, the loading reaction for which is given as follows:44
P–NBu3(SO4)½ + Au(CN)2− → P–NBu3Au(CN)2 + ½SO42− (9)
The loaded resin is first stripped with H2SO4 to remove any absorbed base metals; gold is then
stripped using an acidic thiourea (TU) solution to convert the anionic aurocyanide complex to
a cationic thiourea complex:
P–NBu3Au(CN)2 + 2TU + H2SO4 → P–NBu3(SO4)½ + Au(TU)2(SO4)½ + 2HCN (10)
HCN evolved during the acidic stripping processes is recovered in an alkaline scrubber and
returned to the leach circuit.44
This RIL process was implemented at Penjom to improve gold recovery to above 80%:
prior to the conversion to RIL, recovery had dropped to mid-60% due to the presence of preg-
robbing carbonaceous material in the non-oxidized sections of the deposit. This operation is
believed to be the first RIL installation outside of the Central Asian Republics. The Mintek
strong-base resin has also been used at the Gedabek gold and copper deposit in Azerbaijan.48
Purolite’s medium-base resin, S992, has been implemented in an RIP application at
Petropavlovsk’s Pioneer gold mine in Russia.49 These resins both offer high selectivity for
gold from solutions containing very high copper concentrations.
Gold and silver are usually stripped from activated carbon with concentrated cyanide
solutions at elevated temperatures. PM are then recovered from the eluate by EW, followed
by smelting of the loaded cathodes to produce a doré material that is sent to a refiner.50 An
alternative, known as the WINIXTM process, was developed to avoid the energy-intensive EW
and smelting steps.44 In this process, the eluates from activated carbon are passed over an IX
resin to reabsorb the PM. The resins are then stripped to produce a highly concentrated PM
solution, which can be treated by a simple precipitation process, such as copper cementation,
to produce a high value product suitable for direct shipping to a refiner. The process offers
full automation, improved security, faster gold throughput time, lower costs, and the
production of a doré product of >90% purity.44
Heap leaching of low-grade ore bodies has gained recent popularity due to the savings in
leaching costs. IX offers many advantages in processing the resultant clarified solutions,
including faster kinetics and high operating capacities, which result in smaller plant
footprints. It is envisaged that IX resins will also find future application in niche operations,51
such as treatment of preg-robbing ores (considerable improvement in gold recovery by resins
compared with carbon), new operations (negating the need for thermal regeneration kilns),
and remote operations (with limited availability of electrical power).
10
In recent years, considerable research interest has been devoted to investigating alternative
lixiviants, owing to increasing environmental and occupational safety concerns associated
with the use of cyanide in gold processing.52–54 Alternatives include thiourea, thiocyanate,
thiosulfate, and the halides. Particular success has been achieved with the use of thiosulfate,
which is non-toxic, can have lower cost, and has potentially faster leaching kinetics, although
the instability of the thiosulfate ion results in the formation of polythionates during leaching
which leads to reagent loss and the resultant tetrathionate and trithionate complexes that
compete with gold for active adsorption sites. The gold thiosulfate complex does not load
onto activated carbon, so this process requires use of a resin.49 The first commercial
implementation of the thiosulfate leaching process, at Barrick’s Goldstrike plant (Nevada),
was successfully commissioned in 2014.55,56 The ore is double-refractory, i.e., it contains both
naturally occurring carbonaceous material and gold occluded by sulfide minerals. Gold is
recovered from the thiosulfate leach liquor by an RIL process using a Purolite strong-base
anion resin.49
3.2 Refining of the precious metals

PM refining invariably treats concentrates of the metals (except for high-silver materials)
in chloride-based processes. Two basic refining schemes exist for gold and silver: pre-
refining, followed by electrorefining or dissolution and then by selective precipitation.50
Refining of the platinum-group metals (PGM) (Pt, Pd, Rh, Ir, Ru, Os) is more complex
because it involves the selective extraction or removal of each metal from solution in a
sequence specific to different refiners. These flowsheets are based on SX, IX, or precipitation
processes.57
Selective extraction of PM from concentrated solution can be carried out by precipitation.

This classical process is still used by Krastsvetmet (Russia) and Lonmin (South Africa) and
extensively by small-scale PGM refining operations; however, most PGM refineries,
including those of Vale (United Kingdom), Anglo American Platinum (South Africa),
Hereaus (Switzerland), and Johnson Matthey (United Kingdom), use SX processes, which
involve the sequential extraction of each PGM from solution.57 In contrast, Impala Platinum
PGM refinery (South Africa) has made a notable commitment to the use of IX technology,
using this to selectively recover gold, palladium, and iridium from solution.57 The flowsheet,
shown in Figure 2, is a very good example of the combination of technologies, including IX,
being superior to any single technology on its own. This process has economic benefits in
terms of reducing the pipeline inventory of the more valuable metals.
The leach liquor is first treated with Amberlite XAD-7 to remove gold from solution in a
lead–lag–lag FBIX configuration. Gold is stripped from the resin by a chlorinated caustic
solution and then precipitated from the eluate using hydroquinone. In an important
development, IBC Advanced Technologies, the developers of molecular recognition
technology (MRT), and Impala implemented the large-scale recovery of palladium from
solution using SuperLig 2, a macrocycle affixed to a silica matrix.58 Solution composition,
especially redox conditions, are tightly controlled to avoid the co-extraction of platinum as
PtCl42−. A lead–lag column configuration is used, with relatively small columns required
owing to fast extraction kinetics. Pd is eluted from the columns with an ammonia/ammonium
11
metabisulfite solution, which converts the PdCl42− species to the cationic Pd(NH3)42+; HCl is
then added to precipitate Pd as the Pd(NH3)2Cl2 salt:
H2PdCl4 + 6 NH3 → Pd(NH3)4Cl2 + 2 NH4Cl (11)
Pd(NH3)4Cl2 + 4 HCl → (NH4)2PdCl4 + 2 NH4Cl (12)
Figure 2. Simplified schematic of the Impala Platinum Precious Metals Refining process
(adapted from Crundwell et al.57).
After Pd extraction, the liquors are processed through cation exchangers to remove base
metals. Following several process steps, including the distillation of ruthenium and osmium
and precipitation of rhodium and iridium as hydroxides, the hydroxide cake is re-dissolved
and iridium is selectively recovered from solution by IX.57
12
Perhaps the most significant recent advance in PGM refining has been the use of metal-
selective macrocyclic ligands attached to a solid support, such as silica gel. The essence of the
MRT process is specific tailoring of the macrocyclic ligands for the different PM that allows
highly selective separations from solutions containing a wide range of base and precious
metals.59 A variety of tailored extractants for precious and base metal extraction are now
available. One commercial application of MRT is the recovery of rhodium from spent
catalysts and other feed materials at Tanaka Kikinzoku Kogyo (Japan).60 The process is
reported to be highly selective for rhodium (except in presence of large amounts of Pt, in
which case pretreatment of the solution with another Pt-selective MRT reagent is advocated),
allowing small-scale equipment, lower rhodium residence times, and reduced production of
wash and eluate solutions.
Many other resins have been considered for recovery of PGM from chloride resins.61 Their
effective extraction and recovery is very dependent on the complicated nature of the PGM-
chloro complexes, which change depending on the acidity of the solutions, the chloride
concentration, temperature, redox conditions, and solution ageing. As a consequence,
designing effective PGM extraction and recovery systems requires intimate understanding of
their aqueous chemistry and speciation.
There are many advantages of IX over precipitation and SX processes for PGMs.57 IX
materials are highly selective and yield barren solutions with very low residual PM
concentrations. Phase separations are uncomplicated compared with SX or filtration, the
reaction kinetics are fast, and first-pass yields are good, permitting faster throughputs and/or
smaller scale equipment and lower residence times. The process equipment is simple and is
amenable to a great deal of automation. This increases process security and reduces worker
exposure to allergenic platinum salts. The main disadvantage of IX-based processes is the
generation of large volumes of low-concentration downstream solutions arising from
displacement washes:52 energy and equipment costs of the associated evaporation–
concentration step can contribute significantly to operating and capital costs, respectively.57
3.3 Scavenging from dilute solutions and value recovery from waste streams
PM refining and processes using PM chemicals in solution, such as catalyst production or
electroplating, inevitably produce spent solutions containing low PM concentrations. Refining
processes, in particular, produce multiple dilute solutions as byproducts of incomplete
precipitation and extraction reactions. Because of their value, refineries generally specify
extremely stringent waste-water discharge limits (typically <0.1 mg/L PM). These solutions
are often subjected to bulk cementation, using iron or zinc, to remove the trace PM; however,
this requires the highly acidic solutions to be pH-adjusted to a moderate range (pH 2 to 4) and
cementation often coprecipitates considerable amounts of base metals (such as copper). A
low-grade PM concentrate is produced, which complicates in-process recycling operations,
increases costs, and extends PM refinery pipeline times.
IX is ideal for such applications, because it is one of the few technologies capable of
achieving the target barren concentrations, selectivity for PM can be good, and high resin
loadings can be achieved. In theory, IX could produce a concentrated eluate that would permit
easier process reintroductions; however, industry experience indicates that, in most
13
scavenging applications, the resin is not stripped—instead it is simply incinerated to recover

the loaded PM. The final ash product containing the PM is then reintroduced into the process
via the initial leaching step.
These applications usually use generic strong- or weak-base resins. The challenge is that
the spent solutions often contain high concentrations of base metals, so resin selectivity for
scavenging PM is poor. Alternatives, such as commercially available chelating resins based
on thiouronium62,63 functional groups and others,37 have found application in the recovery of
trace PM from spent solutions.
Substrates other than the typical polystyrene matrix have recently been commercialised.
PhosphonicS, a UK company, has developed a range of silica-gel substrates functionalized
with different groups (including amino and mercapto alkyls and alkyl thioureas) for a variety
of applications.64,65 Fibrous substrates have also found commercial applications for PM.
Johnson Matthey has developed a range of extractants based on viscose and polypropylene
fibres, known as Smopex®, that are functionalized with various metal-selective groups,
including sulfonic acid, pyridine, thiol, and mercaptoethylacrylate (Figure 3).66 These
materials are useful for recovering PM from dilute multicomponent process streams, such as
those produced in refining operations.67,68 Both the silica-gel and fibrous materials can be
used in organic media and have high surface areas to promote PM extraction from dilute
solutions. Final PM recovery is usually accomplished by incineration of the loaded material.69
Figure 3. Smopex fibres for scavenging of precious metals

(adapted from Johnson Matthey66).
These newer materials have found applications, but their widespread use is inhibited by
their high cost: efforts to seek less costly materials continue. Recent investigations of non-
specialized, commercially available materials in both granular and fibrous forms have been
undertaken and their effectiveness for scavenging low concentrations of PM from mixed
refinery streams has been demonstrated.70 Materials with triethyltetramine or strong-base
tributylamine functional groups are most effective. Fibrous materials appear to offer distinct
advantages over granular materials, due their faster kinetics and higher selectivity under some
circumstances; however, their costs are ~25% higher.70 Tributylamine resins, such as those
specifically developed for cyanide-based RIP applications,44 are particularly effective for gold
recovery from dilute chloride refinery streams and could have application for the selective
extraction of gold from PGM solutions.71
14
4. COPPER
Modern copper hydrometallurgical flowsheets rely heavily on the use of SX to produce
high-purity cathode;72 however, IX is increasingly receiving attention for value recovery from
the processing of high-volume, low-concentration mine waste streams, as well as for primary
production from dilute heap-leach solutions.73–75 Selective chelating resins also offer
opportunities for the recovery of valuable trace impurities from electrolytes during copper
cathode production76,77 and the removal of heavy metals from mine waste waters.78
4.1 IX combined with SX in heap-leaching flowsheets

The concentration and separation of copper from leach solutions is one of the key
operations in the hydrometallurgical processing of copper ores.72 This is typically achieved by
treating the PLS (1–25 g/L Cu) through an SX process that selectively extracts and upgrades
the copper to an electrolyte containing ~50 g/L Cu, from which the final copper cathode
product is recovered by EW. Although widely employed in modern flowsheets around the
world, SX is economically less attractive for processing PLS with lower copper tenors (<1
g/L), which are often generated from heap-leaching processes. Efforts have therefore been
directed to evaluating alternative technologies that can address these challenges. Buchim
Mine (Macedonia) is an example of innovative use of a flowsheet incorporating both SX and
IX to cost-effectively process very low Cu content materials.78
Buchim Mine has been operating since 1979, producing copper, gold, and silver
concentrates, and had accumulated significant amounts of residual ores that still contained
some 0.2–0.3% Cu. Efforts to recover value from these stockpiles yielded PLS typically
containing 0.5–1.0 g/L Cu. The process developed (Figure 4) included an IX step prior to SX.
In this flowsheet, copper is selectively removed from the PLS by adsorption on an
iminodiacetic-acid resin (Lewatit TP 207). The feed is split between four trains, each
consisting of two columns operated in a lead–lag configuration. Typical operating capacities
are 35 g Cu/L resin. The resin is eluted with 15–20% sulfuric acid, giving an eluate with a
copper tenor of 15–18 g/L. This concentration is unsuitable for direct EW, so it is further
upgraded in a subsequent SX step to achieve the desired electrolyte concentration (~50 g/L
Cu). The final EW step yields London Metal Exchange (LME) Grade A copper cathodes. The
IX/SX/EW plant at Buchim Mine has been successfully running since 2012.78
Figure 4. Flow-scheme of the Buchim Mine combined ion exchange and solvent extraction
flowsheet for copper recovery (adapted from Neufeind et al.78 and Savov et al.79).
15
In contrast, Asarel Medet (Bulgaria) uses a conventional leach/SX/EW flowsheet, but has
very similar copper contents of the ore and PLS and similar annual copper cathode
production, so it provides a useful reference to compare a conventional SX/EW process with
the complementary IX/SX/EW at Buchim Mine.78 As shown in Table 1, the inclusion of the
IX circuit reduced both the initial SX diluent and extractant fills by 86% and 63%,
respectively, while the smaller organic inventories also reduced the annual losses of these
reagents by 73% and 60%, respectively. The resulting cost savings reportedly more than
compensate for the cost of the first resin fill, as well as annual resin top-ups (usually <10%),
and ultimately lower the operating costs.79 The significantly lower volume of the SX
operation has a significant effect on the plant footprint (~50% less), which translates to
substantially reduced capital cost. Use of this combined IX/SX concept offers considerable
promise for cost-effective processing of low-grade copper leach solutions.
Table 1. Comparison of IX/SX/EW and SX/EW processes (adapted from Neufeind et al.78).
Buchim Asarel Medet

Production Nameplate Cu cathode production (t/a) 2400 2000
Leaching PLS flow rate (m3/h) 650 500
pH of PLS 2.5 – 3.0 1.5–2.5
Copper PLS concentration (g/L) 0.7 0.6
Iron PLS concentration, max. (g/L) 0.3 <5.0
IX First fill of IX resin (m3) 80 —
Resin top-up (m3/a) 7 —
SX Flow rate to SX plant (m3/h) 40 422
First diluent fill (m3/a) 60 440
Diluent consumption (m3/a) 38 140
Initial fill of extractant (m3) 15 40
Solvent extractant consumption 4 10
EW No. of cells 24 10
Total cathode area (m2) 900 736
Current density (A/m2) 280 300
Flow rate of electrolyte (m3/h) 110 100
Average copper electrolyte conc. (g/L) 38 38
Summary Plant footprint (m2) 1500 3000
4.2 Removal of iron from copper electrolytes

During purification of copper leach solutions by SX, small amounts of iron and other
impurities are continually transferred by entrainment to the EW circuit. Although low levels
of iron (1–2 g/L) can be beneficial to copper EW circuits in which manganese is present in the
electrolyte (by maintaining this species in the benign Mn(II) form), iron contributes to
reduced current efficiency through the cycling of the Fe2+/Fe3+ redox couple at the anode and
cathode, so its concentration needs to be limited. This is typically achieved by bleeding a
portion of the electrolyte from the circuit and recycling this to the upstream leach circuit
where the contained acid can be used and copper recovered. Cobalt, which is added to the
electrolyte (50–200 mg/L Co) to minimize anode corrosion, is, however, irretrievably lost
16
from the circuit with the electrolyte bleed (except in African plants that have a separate
cobalt-recovery circuit), along with acid-mist suppression agents; their replacement represents
a significant operating cost.
The so-called FENIX process was developed to address this issue. The original process
used Eichrom’s DiphonixTM resin (Figure 5(a)): the main exchange group is a diphosphonic
acid, which forms very stable complexes with several metal ions under conditions of high
acid strength that would usually not be possible for most other ion exchangers.80–82 Because of
the very strong complexation required to load iron from such acidic solutions, the elution
conditions were correspondingly onerous: a reductive strip, using sulfurous acid and cuprous
ions, was required. The process was commercialized in 1997, using a carousel configuration
designed to remove approximately 1 t/d iron from the electrolyte at Mexicana de Cananea
(Mexico), a plant then producing 35 000 t/a cathode copper.83 After several improvements,
the system removed 600 to 700 kg/d of iron, although the design capacity was never
consistently achieved. The resin performance was affected by contamination with solids and
inadequate control of the SX circuit that allowed organic through to the tankhouse. The
system was discontinued a few years later.
Today, the improved process uses a sulfonated monophosphonic-acid resin (Figure 5(b)),
which selectively extracts Fe3+ from copper (and cobalt) under the highly acidic conditions of
the electrolyte (~180 g/L H2SO4), thereby minimizing the bleed volume required to control
the iron levels, but stripping conditions are less difficult and less corrosive to equipment. Use
of a fixed-bed single-column configuration has also reduced the complexity and capital cost
of the system. The reactions are as follows, where –HR represents the resin in its acid form:84
Ferric loading from spent electrolyte:
Fe2(SO4)3 + 6 P–RH → 2 P–R3Fe + 3 H2SO4 (13)
Generation of cuprous sulfate from electrolyte bleed:
CuSO4 + Cu → Cu2SO4 (14)
Cuprous sulfate reductive stripping of iron‐loaded resin at 65–70°C:
2 P–R3Fe + Cu2SO4 + 3 H2SO4 → 2 FeSO4 + 2 CuSO4 + 6 P–RH (15)
Figure 5. Structures of (a) original Diphonix resin and (b) current sulfonated
monophosphonic-acid resin used in the FENIX process.84
A flowsheet for the integration of the FENIX iron‐removal system into the overall process
is illustrated in Figure 6. Commercialisation of this improved technology was successfully
17
implemented at Mount Gordon Western Metals (Australia) in 2004.85,86 This plant

subsequently closed down during the global financial crisis of 2008/9.
Figure 6. Integration of the FENIX process into a hydrometallurgical copper circuit.
4.3 Copper recovery from mine waste streams

As with almost all mining and process operations, large volumes of waste streams are often
generated that contain very low concentrations (0.1–10 mg/L) of valuable metal.87 Such
streams represent ideal opportunities for IX recovery of these metals that would otherwise be
lost. Globally, there are over one thousand IX applications of copper recovery from industrial
process wastes, mainly using inexpensive strong-acid functionalities. IX readily handles large
fluctuations in feed concentrations and can consistently produce a low-volume, high-purity,
high-concentration product stream that can be used to produce LME Grade A copper cathode
or other value-added copper chemicals. Although some competing precipitation and
biological treatment technologies have been proposed for the recovery of Cu from mine
wastes, IX has been demonstrated to be a straightforward, reliable, and low-capital
technology for this application, which can be profitably operated to create additional revenue
for operating sites.75
4.4 Value recovery from copper refinery electrolytes

In the electrorefining of copper anodes produced by pyrometallurgical processing of copper
sulfide concentrates, control of the levels of various impurities in the electrolyte is essential to
maintaining cathode quality. This is typically achieved by bleeding a portion of the
electrolyte, removing the impurities by IX, SX, precipitation, or electrodeposition, and then
returning the electrolyte to the main electrorefinery circuit.
Chelating resins are used for the removal of metalloids, such as As, Sb, and Bi.77,88–91 The
combined concentrations of these three elements must be limited to less than 5.0 g/L: above
this, the solubilities of BiAsO4 and SbAsO4 are exceeded and they precipitate from solution;
the resulting suspended solids are detrimental to the current efficiency of the electrorefining
process. Hitachi and Tamano refineries (Japan) use an aminophosphate chelating resin to
selectively adsorb Sb and Bi from the electrolyte.92 Following elution with HCl, the eluate is
neutralized with Ca(OH)2 to collect Sb and Bi as the respective metal hydroxides. The
neutralized sludge is sold as a raw material for the production of electrical-quality bismuth.
MRT is also used for Bi removal.93 The Port Kembla Copper refinery (Australia) uses
SuperLig 83 to selectively remove bismuth from their electrolyte. Bismuth is stripped from
the resin with sulfuric acid, and pure bismuth sulfate is produced as a saleable product.
18
Acid from spent copper liberator electrolytes can also be recovered by IX in an acid-
retardation process prior to the recovery of nickel by precipitation with carbonate.76,94
4.5 Rhenium recovery in copper processing

Rhenium is an expensive and rare element, typically associated with South American
copper ores. It is an important advanced material component of nickel-based superalloys used
in jet engines and catalysts. Rhenium is volatile at elevated temperatures, so pyrometallurgical
processing of copper usually results in rhenium deporting to the sulfuric acid produced by
smelting or roasting of copper sulfide ores and subsequently scrubbed out of the flue gases.95
Rhenium also occurs in solutions originating from high-pressure acid leaching of copper–
molybdenite concentrates and has been detected in measurable amounts in copper oxide heap-
leaching solutions.96 The concentration of rhenium in these solutions is typically low (<10
mg/L) against a high (50–100 g/L) sulfuric acid or moderate (5–10 g/L) copper background.
IX provides an efficient method for the recovery of rhenium from low-grade solutions using a
weak-base anion-exchange resin,97 according to the following reactions:
Protonation: 2 P–NR3 + H2SO4 → P–NR3H+HSO4− (16)
−
Loading: P–NR3H HSO4 + HReO4 → P–NR3H
+ +
ReO4− + H2SO4 (17)
−
Elution: P–NR3H ReO4+
+ NaOH → P–NR3 + H2O + NaReO4 (18)
95
Remarkable upgrading is possible: from a feed solution containing 0.5–8 mg/L Re, the
resin can be loaded to 20 g/L, and the final eluate can contain up to 160 g/L Re, which can
then be converted to ammonium or sodium perrhenate crystals. When processing molybdenite
concentrate, both rhenium and molybdenum exist in sulfuric acid as anions: molybdenum
forms monomeric and polymeric anions (MoO42–, Mo7O246–, Mo8O264–), while rhenium is
present as the monomeric perrhenate ion (ReO4–). Purolite’s gel-type resin, A172/4635 is
highly selective for Re over Mo (Figure 7) because the tight structure of the gel rejects the
larger molybdenum molecules while the perrhenate anions can still penetrate the matrix
freely.41 This selectivity ensures a final product of high purity.
Figure 7. Kinetic selectivity of Purolite A172/4635 gel resin for Re over Mo (Feed: 3200
mg/L Mo, 12.5 mg/L Re, 100 g/L SO42– at pH 1.2) (adapted from van Deventer41).
19
A rhenium-recovery facility was recently installed in Poland by KGHM.97 In 2009, their

daughter company Ecoren, treating the captured flue dusts from the pyrometallurgical process
for its recovery, became the third-largest rhenium producer in the world. The process uses IX
technology with Purolite A170/4675 as the rhenium-selective resin.95
The piloting of an IX process for rhenium recovery from a copper heap PLS containing <1
mg/L Re has been reported using the weak-base resin, Purolite A170.96 Rhenium extractions
of 90% were achieved, even in the presence of more than 70 g/L total sulfate. Rhenium was
effectively eluted from the resin using 1 M NaOH solution.
5. COBALT, NICKEL, AND ZINC

Because of their position in the electromotive series, cobalt, nickel, and zinc EW processes
are far more difficult than that of copper and therefore require much higher purity electrolytes.
IX offers excellent potential for removal of trace quantities of base-metal cations to levels
below 1 mg/L from concentrated (up to 120 g/L M) electrolytes.
5.1 Copper and zinc removal from cobalt electrolytes

Aminophosphonic-acid resins exhibit the selectivity sequence Fe(III) > Pb > Cu > Zn ~ Al
> Mg > Ca > Cd > Ni > Co > Sr > Ba > Na for metal cations, and are therefore suited to the
removal of small quantities of copper and zinc from nickel or cobalt electrolytes.
Bulong Nickel (Western Australia) was commissioned in 1998 with a design capacity of
9000 t/a Ni and 720 t/a Co.97–99 Although it closed in 2003, the original flow sheet remains of
interest, not least because of its innovative combination of SX and IX processes.
Figure 8. Flowsheet of the downstream purification process at Bulong Nickel, Australia.100
Figure 8 shows a simplified flow sheet of the Bulong downstream purification process.
Following autoclave leaching of the laterite ore at 4500 kPa and 250°C, the leach liquor was
20
processed directly for the recovery of the valuable metals.100 Fe(III), Al, and Cr(III) were
removed to <1 mg/L by precipitation with limestone. In the first of three SX operations, Co,
Cu, Zn, and Mn were separated from Ni by Cyanex 272. The raffinate (cobalt-barren stream)
was refined by nickel SX using Versatic acid to produce a high-grade solution suitable for the
production of nickel cathode of >99.5% purity. Cobalt was precipitated as the sulfide from the
cobalt-containing SX product liquor to reject Mn and some Mg, before the filter cake was
dissolved in dilute acid. Zn was then removed from the resulting liquor by a third SX step
using di(2-ethylhexyl)phosphoric acid (D2EHPA). Cobalt EW requires <1 mg/L Zn and Cu in
the electrolyte, a target not easily achieved by SX: IX, using an aminophosphonic-acid resin,
was therefore used to purify the cobalt electrolyte prior to cobalt EW. Cu was reduced from
360 to <0.5 mg/l (>99.8% removal) while limiting the associated cobalt loss to 0.4%.101 Trace
quantities of Pb were also removed.
IX has also been successfully proven at a pilot scale for the removal of Cu and Zn from a
20 g/L Co electrolyte at Kamoto Copper’s Luilu plant in Democratic Republic of Congo
(DRC).102,103 Copper was first removed using an iminodiacetic-acid resin and then zinc was
removed from the pH-adjusted barren using an aminophosphonic-acid resin. Using a lead–lag
FBIX configuration, a cobalt electrolyte containing <1 mg/L each Cu and Zn was consistently
produced. Purolite’s S950 aminophosphonic-acid resin was successfully piloted for the
Kakanda (DRC) flowsheet for the removal of trace amounts of copper (~70 mg/L) and zinc
(~2 mg/L) from a cobalt electrolyte (50 g/L Co) using a lead–lag fixed-bed
configuration.104,105 This resin was similarly employed in the development of the Kolwezi
Mine Tailings (DRC) flowsheet.106 In assessing flowsheet options for the processing of
African Copper Belt ores, Swartz et al.107 also recommended the simultaneous removal of
copper and zinc, using an aminophosphonic-acid resin, for purification of cobalt electrolytes.
5.2 Nickel removal from cobalt electrolytes

Chambishi Metals refinery (Zambia) treats a liquor derived from the acid leaching of
roasted sulphide concentrates for the recovery of copper and cobalt as cathode products.108
The flowsheet (Figure 9) incorporates an IX process to reduce nickel from ~900 mg/L to <160
mg/L in the 40 g/L Co electrolyte to ensure levels of <0.1% Ni in the cobalt cathode.52 One of
the biggest challenges of this flowsheet is minimising associated Co losses to the Ni waste
stream. This is achieved using a split elution process:109 co-loaded Co is first removed from
the resin using 2% H2SO4, followed by Ni elution with 20% H2SO4.
The original commercial-scale operation, installed in 1988, comprised three fixed-bed
columns110 and used Dow’s M-4195 bispicolylamine resin (Figure 10(a)). This was then
changed to an ISEP carousel, with a series of slowly rotating columns fed from a single
point,52 which is more cost-effective for this expensive resin. The current configuration has
been modified to a series of multiple fixed-columns with a rotating valve (rather than a
rotating carousel of columns), i.e., a simulated moving-bed configuration.
21
Figure 9. Simplified flowsheet of Chambishi Metals copper–cobalt refinery.
A significant disadvantage of the chemistry of M-4195 is that it loads copper very strongly,
and which can only be eluted effectively with 500 g/L H2SO4 or concentrated ammonia.52
More recently, Dow’s hydroxypropylpicolylamine (HPPA) XUS-43605 and bispicolylamine
XUS-43578 resins (Figure 10(b)) have overcame this issue, allowing use of much lower acid
concentrations.111,112 The co-loading of cobalt is also significantly lower than that of M4195:
easier selective elution of cobalt prior to that of nickel and copper further minimizes cobalt
losses.52
Figure 10. Commercial nickel-selective (a) bispicolylamine (Dow M4195 and XUS-43578)
and (b) hydroxypropylpicolylamine (HPPA) (XUS-43605) resins (from Rodgers et al.112).
Vale’s cobalt refinery at Port Colbourne (Canada) similarly uses M4195 for the removal of
nickel and an iminodiacetic-acid resin for removal of copper from cobalt electrolyte.113
5.3 Zinc and copper removal from nickel electrolytes

Goro (New Caledonia): This laterite process includes two IX steps in the recovery of nickel
(Figure 11).114 Nickel and cobalt are co-extracted from the pressure-acid leach liquor by SX
using the sulfur-substituted organophosphinic acid, Cyanex 301. This extractant has the
unique ability to extract Ni and Co selectively from Mn, Mg, and Ca (the main impurities)
under highly acidic conditions, but is irreversibly poisoned by copper, which catalyses its
oxidation:115 it is essential to remove copper to very low levels ahead of this SX step.
Residual copper is reduced to levels of <0.04 mg/L using Lewatit TP 207, a chelating resin
with iminodiacetate functionality. A fixed-bed arrangement treats a flowrate of 470 m3/h.
22
Cyanex 301 cannot be stripped with H2SO4, so HCl is required. The conversion from a
sulfate to a chloride matrix serves a useful purpose in that cobalt and zinc exist as anionic
MCl42– species in solution, while nickel is present as the neutral NiCl2 species. Zinc is first
removed using a weakly basic tertiary-amine anion-exchanger Lewatit MP 62, which has high
operating capacity and high mechanical stability. A fixed-bed configuration treats a flowrate
of 600 m3/h. CoCl42–is then separated from NiCl2 using the tertiary amine anion 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.
Figure 11. Simplified flowsheet of the Goro process for recovery of nickel from laterites
(adapted from Mihaylov et al.114)
Rustenburg Base Metals Refiners (South Africa): Process flowsheet changes and increasing
zinc content of the feed materials to Rustenburg Base Metals Refinery caused increasing
deportment of zinc to the nickel product. This necessitated installation of a dedicated zinc-
removal circuit to ensure continued consistent quality of the nickel cathode. The selected
process removes 30 mg/L Zn from a stream containing 70 g/L Ni, 0.2 g/L Co, using the
D2EHPA-impregnated resin, Lewatit VP OC 1026.116 D2EHPA is well-known in SX
applications for both the bulk recovery of zinc and its removal as an impurity from cobalt and
nickel sulfate liquors.117 Its selectivity as a function of increasing pH is: Fe3+ > Zn2+ > Cd2+ >
Ca2+ > Mn2+ > Cu2+ > Fe2+ > Co2+ > Ni2+. A 15 m3/h FBIX plant was installed in 2011. Zinc
contamination of the nickel cathode was reduced by 40%, allowing consistent production of
nickel conforming to the LME specification of <50 ppm Zn (Figure 12).118
23
Figure 12. Zinc contamination of the nickel cathode before and after commissioning
(mid-March 2011) of the RBMR zinc ion-exchange plant.118
Lewatit VP OC 1026 and now OC 1029 have similarly operated successfully since the
1980s at Vale’s Port Colbourne (Canada) refinery for the removal of zinc from a cobalt–
nickel electrolyte prior to EW.113,119 A major advantage of this system is the relatively low co-
loading of cobalt at the pH of effective zinc removal.52 These resins are also used in several
nickel plating bath systems for the removal of ferric iron and zinc.52,120
The analogous phosphinic-acid extractant, Cyanex 272, has also been prepared in the form
of a solvent-impregnated resin, manufactured by Lanxess as TP 272. As with the liquid
extractant, this resin offers excellent selectivity for Co over Ni, especially from Ca-saturated
solutions. It can also be used for Zn removal from Co solutions. To date, however, this resin
has not been commercialised because of its high expense and low loading capacity.
Although solvent loss has often been considered a disadvantage of solvent-impregnated

resins, this risk is minimised if the acidity of the aqueous streams (adsorption, elution, and
wash liquors) is maintained below pH 4.52 Recent improvements in the resin manufacturing
process have also largely mitigated this risk.
6. RARE-EARTH ELEMENTS
Rare-earth elements (REE) (lanthanides and actinides) were amongst the first species to be
separated on a large scale by IX, specifically for the production of high-purity uranium and
other radioactive elements for the Manhattan project.1 Although use of IX for REE has been
neglected for several decades since then, mainly in preference to SX, renewed interest is now
being shown in potential separations in new flowsheets. Although there are no currently
known commercial applications of IX for REE separations, it is likely that this situation will
change in the near future as China relinquishes its monopoly on REE production and
alternative flowsheets are developed. Modern production techniques for resins produce finer
and more uniform-sized beads that lend themselves to chromatographic separations, while
new adaptations of chelating eluants and developments in engineering of simulated moving-
24
bed reactors have opened up the possibility of separations using low-cost commercially
available ion-exchange resins.
7. CONCLUSIONS
IX is playing an increasingly important role in the hydrometallurgical industry for the
purification, separation, recovery, and scavenging of metal ions, and is often the preferred
separation method to use when the concentration of the target metal is less than 500 mg/L.117
Primary limitations of this technology for hydrometallurgical applications include its
relatively low capacity for adsorption, low selectivity for some metal ions, poor mechanical
stability of the resins, potential for fouling, and the wash-water requirements when used for
high-grade applications; however, unlike most analogous SX processes, IX does not require
pH adjustment during the process and complete automation of the process is readily achieved;
it also uses relatively benign reagents and likely contributes less to carbon emissions and
environmental damage.
This review has discussed some applications in which IX has been successfully
demonstrated for a variety of commercial hydrometallurgical flowsheets around the world,
involving a wide range of base, precious, and specialty metals. Many potential applications
are likely to receive renewed interest as the mining cycle turns. Applications range from
primary value recovery from leach liquors, to treatment of mine wastes and tailings, to
impurity removal from highly concentrated electrolyte streams. Of specific current interest are
the upgrading of heap-leach solutions (U, Au, Cu); recovery of Co and Cu from CCD
overflows and dam water returns that have been contaminated by bleed disposal; Ni, Cu, and
Zn removal from cobalt and nickel electrolytes; and Cu and Cd removal from zinc
electrolytes.121 Myriad potential RIP applications also exist for metal recovery from difficult-
to-wash pulps (thereby avoiding costly L/S separation steps; recovery of soluble (adsorbed)
metal losses in pulps, leach residues, and precipitation filter cakes; treatment of laterite leach
pulps (the rheological characteristics of which make them extremely to separate); and
retreatment of dump materials. IX readily lends itself to possibilities of add-ons to existing
processes that can be both environmentally friendly and economically attractive. It is
anticipated that the development of new resins with improved and more selective
functionalities, as well as the proliferation of new substrates, will lead to new and interesting
applications of IX for metal extractions and value recovery in the next decade.
Acknowledgements
Johanna van Deventer (Purolite), Marthie Kotze (Lanxess), and Indje Mihaylov (Vale) are
thanked for their assistance in confirming various information presented in this work.
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Present and future applications of ion exchange in hydrometallurgy: An

Conference Paper · July 2016

Kathryn C. Sole Michael Mooiman

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PRESENT AND FUTURE APPLICATIONS OF ION EXCHANGE

The historical arc of IX applications in hydrometallurgy is interesting and worthy of

This overview discusses some modern applications of IX in hydrometallurgical processes,

2.1 Purification of uranium liquors by ion exchange

in an RIP system. Strong-base anion-exchange resins, with quaternary ammonium functional

Today, weak-base resins (based on secondary- or tertiary-amine functionality) are also

2.3 Selected process descriptions

2.3.2 Sulfate-based resin-in-pulp process

Atmospheric leaching at ambient temperature is conducted in six mechanically agitated

2.3.3 Carbonate-based ion-exchange process

(P–NR3)4UO2 (CO3)3 + 4 NaHCO3 → 4 (P–NR3)HCO3 + Na4UO2(CO3)3 (3)

3.1 Recovery of precious metals from primary leach liquors

Figure 1. Schematic illustration of the compromise between gold extraction,

3.2 Refining of the precious metals

Selective extraction of PM from concentrated solution can be carried out by precipitation.

scavenging applications, the resin is not stripped—instead it is simply incinerated to recover

Figure 3. Smopex fibres for scavenging of precious metals

4.1 IX combined with SX in heap-leaching flowsheets

Buchim Asarel Medet

4.2 Removal of iron from copper electrolytes

implemented at Mount Gordon Western Metals (Australia) in 2004.85,86 This plant

Figure 6. Integration of the FENIX process into a hydrometallurgical copper circuit.

4.3 Copper recovery from mine waste streams

4.4 Value recovery from copper refinery electrolytes

4.5 Rhenium recovery in copper processing

A rhenium-recovery facility was recently installed in Poland by KGHM.97 In 2009, their

5. COBALT, NICKEL, AND ZINC

5.1 Copper and zinc removal from cobalt electrolytes

Figure 8. Flowsheet of the downstream purification process at Bulong Nickel, Australia.100

5.2 Nickel removal from cobalt electrolytes

Figure 9. Simplified flowsheet of Chambishi Metals copper–cobalt refinery.

5.3 Zinc and copper removal from nickel electrolytes

Although solvent loss has often been considered a disadvantage of solvent-impregnated

4. Nicol MJ, Fleming CA, Preston JS, Applications to extractive metallurgy, in

79. Savov G, Angelov T, Tsekov A, Grigorova I, Nishkov I, Combination of ion exchange

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