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1039/9781849737340-00059

CHAPTER 3

Ionometallurgy: Processing
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of Metals using Ionic Liquids

ANDREW P. ABBOTT* AND GERO FRISCH

Department of Chemistry, University of Leicester, Leicester, LE1 7RH,

United Kingdom
*Email: [email protected]

Metallurgy is the foundation of the greatest technological advances made by

mankind, where for every major metal, significant progress has followed the
discovery of extraction and processing methods. Metals are predominantly
found in nature as oxides, sulfides, carbonates or silicates and must be
reduced primarily from the liquid state, that is high temperature salt melts or
aqueous solutions, into a metallic form. In addition to naturally occurring
ores there is an increasing demand for metallurgical processing of finished
metal items and recycling waste from end of life goods, sludges, slags
and tailings. The recent discovery of ionic liquids, that is salts which are
molten at or around ambient temperature, has generated new metallurgical
methods, which combine low temperature processing with the advantages
of working in ionic media. These techniques constitute the new field of
ionometallurgy.1

3.1 Metal Extraction and Recovery

Traditionally, metallurgical processes centre on three main methods: pyro-
metallurgy, electrometallurgy and hydrometallurgy. The principles underlying
all three methods are the same: the metallic species is taken into a liquid state
and then reduced. The method chosen depends upon the abundance of the

RSC Green Chemistry No. 22

Element Recovery and Sustainability
Edited by Andrew J. Hunt
r The Royal Society of Chemistry 2013
Published by the Royal Society of Chemistry, www.rsc.org

59
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60 Chapter 3

metal in the ore, its chemical form and the value of the metal. Metals can be
split into four main categories:

 rock-forming metals, such as Al, Fe, Mg, Ti;

 major industrial metals, such as Cr, Cu, Ni, Zn, Sn and Pb;
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 rare earth metals, such as La, Ce, Pr, Nd, Sm, Eu, Gd, Dy and Lu;
 precious metals, such as Ru, Rh, Ag, Pd, Re, Os, Ir, Pt and Au.
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The abundance of the rock forming metals is about 103 to 104 times larger
than the industrial metals, 105 to 106 times more than the rare earth elements
and 109 to 1010 times larger than the precious metals. Extraction of rock
forming metals tends to be by using pyrometallurgy or electrometallurgy and
the technologies are relatively mature. Metal concentrations in workable ores
can be as low as 1 to 10 ppm, so the large volume of waste created, in both
liquid and solid form, is a significant issue in metal processing. Finished
metallic objects tend to be processed using low temperature aqueous solutions,
for example pickling, polishing, anodising or plating and this can also result in
large volumes of dilute waste. Commonly used processing steps for metal
extraction and recovery are shown in Figure 3.1.
The dissolution/melting step is dependent on the chemical state of the metal
in the source material. If the source material contains the metal in an ionic form
it can be introduced into the solution by acidic or basic digestion methods in
either salt melts or aqueous solution. In the case of very insoluble salts, the
anionic component can sometimes be removed by oxidation, for example
digestion of sulfides by oxidising acids. If the sample is already in the metallic
form, like it is in the recycling of metal scrap, it needs to be dissolved either by
electrolytic or by chemical oxidation.

Figure 3.1 Flow chart showing steps involved in metallurgical processing of an ore,
metal or alloy.
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Ionometallurgy: Processing of Metals using Ionic Liquids 61

Electrolytic dissolution is a generic and efficient method of dissolving metals

but is only feasible if the raw material can be cast into suitable anodes. This is
often not the case for scrap sources like printed circuit boards. Digestion and
chemical oxidation in aqueous solution is usually achieved using mineral acids,
most commonly sulfuric acid or aqua regia. These have two advantages: the
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protons act as good oxygen acceptors for metal oxides and HNO3 and H2SO4
are good oxidising agents for metals or sulfides. In some cases the medium
chosen for extraction (the lixiviant) can be selective for a given fraction of the
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sample. For example, for silver purification HNO3 is first added to extract the
base metals but it does not dissolve silver. Once the solution has been removed
concentrated HNO3 or aqua regia is added to digest the silver.
Once in solution, a variety of extraction techniques can be used to convert
the metal ions into either a metal or an insoluble salt. This process is shown
schematically in Figure 3.1. Electrowinning uses an electrode to supply the
electrons to reduce the metal ions in solution, in other words the opposite of the
anodic dissolution stage. The metal crystallises on the electrode surface and is
mechanically removed at the end of the process. Anodic oxidation and elec-
trowinning can often be carried out in the same apparatus and this is called
electrorefining. This is a common purification technique, for example for raw
copper. Cementation uses a chemical reducing agent, for example a sacrificial
metal like zinc, to exchange with the metal of interest in solution. Gold, for
instance, can be cemented from ammoniacal thiosulfate solutions using copper
as a sacrificial metal.2 Ion exchange uses an ionic polymeric resin which in the
case of metal extraction usually has acidic moieties. It exchanges the metal ions
for protons and binds the metal ions to the polymer support. The precipitation
of metal ions from solution requires the addition of a counter-ion which binds
to the cation to render it insoluble. An alternative technology is to use a
chelating agent in an immiscible solvent to extract the metal ions from a dilute
aqueous solution into a more concentrated (usually non-polar) environment.3
The chelating agents therefore contain a non-polar and frequently fluorinated
moiety to enhance solubility in low dielectric constant media.4

3.2 Speciation and Phase Control

Metal ions in solution are often dilute and this can make extraction inefficient.
The concentration of water molecules in an aqueous solution is in excess of
50 mol dm3. Given that the concentration of any ion or neutral ligand is usually
at least an order of magnitude smaller it is evident to see why aquo-species
dominate in solution. In order to give an ionic solute the desired chemical
properties its speciation must be adapted, for example by complexation:
h ixþ  xz
MðH2 OÞy þ zL Ð MðLÞz þ yH2 O

In order to compete against the high activity of water, that is to shift the
equilibrium to the product side, ligands must either form a strong bond to the
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62 Chapter 3

metal or be present in very high concentrations. Strong binding ligands are

usually toxic and the use of cyanide in gold extraction processes is probably the
best known example. In weaker, less toxic ligands the required high concen-
tration is commonly achieved by using concentrated acids or bases, for example
concentrated HCl for high chloride concentration. Both methods have clear
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disadvantages regarding handling, safety and environmental impact.

These issues can be circumvented in an ionometallurgical process: the desired
ligand can be tailored into the ionic formulation of the solvent whilst keeping
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the concentration of water at an insignificant level. The effect that concen-

tration of ionic and molecular species has upon speciation and reactivity can be
seen in Figure 3.2. The difference in the reactivity of CuCl2 in a deep eutectic
solvent (DES) of choline chloride:ethylene glycol (1 : 2 ratio), an ionic solvent
with properties similar to ionic liquids, compared to water can clearly be seen.
In the former, [CuCl4]2 is the dominant species whereas in water [Cu(H2O)6]21
is present. In the chloride-based ionic solvent, transfer in Cu21 þ e-Cu1 can
be distinguished from Cu1 þ e-Cu, whereas in water a complex redox
response is observed owing to the instability of Cu1.
Superimposed on this voltammogram is the effect of adding LiCl to the
aqueous solution. The addition of 12.5% LiCl (molar fraction) clearly pushed
the species equilibrium from [Cu(H2O)6]21 towards [CuCl4]2 and the addition
of 25% LiCl produces an electrochemical response which is almost indis-
tinguishable from that of the DES. This is confirmed by the UV–vis spectra of
solutions shown in Figure 3.2(b). This clearly reinforces the difficulty of
defining an ionic liquid as simply a system which consists only of ions.
The generality of this approach can be seen from Figure 3.3 which shows
solutions of various transition metal ions in water, the chloride-based DES
ethaline and aqueous solutions of concentrated HCl. It can be seen that the
aqueous solutions are different in colour from the solutions containing chloride
ions. The colour of the metal ions in concentrated HCl solutions shows that
chloride ions dominate ligation over water in cases where the concentration of
chloride is very high or the concentration of water is low.

3.3 Current Issues

Hydrometallurgy understandably dominates ambient temperature metal
processing: water was a convenient and cheap solvent when we could afford to
ignore the consequences of direct waste water discharge into the environment.
Today more responsible conduct is required and waste water is purified by
energetically and chemically rather demanding methods. The main issue in
hydrometallurgy is that dissolution of metal compounds usually involves the
use of either toxic additives, for example CN, or concentrated mineral acids
and bases, principally aqua regia, HNO3, H2SO4 and caustic soda. These are
needed to attain the requisite concentrations of metals in solution either by
oxidation, oxide protonation or metal complexation. This results in large
volumes of acidic and basic waste containing low but significant levels of
metals. A comparison of metallurgical methods is shown in Table 3.1.
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Ionometallurgy: Processing of Metals using Ionic Liquids

Figure 3.2 (a) Normalised cyclic voltammograms of CuCl2 in choline chloride : 2 ethylene glycol (ethaline), in an aqueous solution and in an
aqueous solution containing a molar fraction of 0.125 and 0.25 of LiCl, respectively. All voltammograms were measure using a Pt
working electrode and a silver wire pseudo reference electrode. (b) UV-Vis spectra of the solutions shown in (a). In the above
diagrams, I is electric current, E is electrode potential, e is molar absorptivity and l is wavelength.

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64 Chapter 3
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Figure 3.3 In each photograph, solutions from left to right, are MnCl2, CoCl2, FeCl2,
FeCl3, NiCl2, PdCl2, PtCl2, CuCl2 in (a) ethaline (b) water and (c)
concentrated HCl.

Table 3.1 Comparison of process traits.

Advantages Disadvantages6,7
Hydrometallurgy Low temperature Large volumes of aqueous
Useful for small scale waste streams
Can be selective Limited potential windows
Pyrometallurgy Avoids oxo-chemistry High temperature
Fast reaction rates High plant costs
Ability to reduce reactive metals Less suitable for small scale
Wide potential windows Significant atmospheric pollution
Inexpensive
Large scale possible

One specific issue associated with the extraction particularly of rare earth and
precious metals is the similar chemistry of the related and generally co-located
metals. The large demand for these metals in electronic, magnetic and catalytic
applications has pushed the extraction of ever leaner ore sources. Modern
techniques involve processes such as in situ leaching. Ores such as copper
carbonate and uranium oxide are leached using acid or carbonate solutions.5
This can clearly lead to pollution of ground water, co-dissolution of heavy
metals and destruction of delicate ecosystems.
Separation of mixed metal solutions can be achieved either at the digestion step
or any of the recovery steps owing to differences in redox potential, speciation
(charge or ligation) or solubility of the various metal-containing species.

3.4 Ionometallurgy: A Potential Solution

Ionometallurgy is the study of metal processing using ionic liquids. This
includes not only solvents which consist solely of ions but any solution where
the chemistry of solutes is dominated by solvent ions. It seeks to gain the
advantages of low temperature processing methods while predominantly
avoiding aqueous chemistry. It has the potential to benefit from the advantages
of classic molten salt methods, for example wide potential windows, whilst
avoiding the issues associated with high temperature. The desire to replace
aqueous solutions is not an academic curiosity, but is driven by a need for
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Ionometallurgy: Processing of Metals using Ionic Liquids 65

facile, efficient methods of separating complex metal mixtures. Properties of

ionic solvents can be varied for the application, for example they can be made
immiscible with water or tuned to be polar and hydroscopic. The flexible
architecture of anion and cation means that the chemical and physical
properties of the ionic phase can be tailored to the specific digestion, extraction
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or recovery technique. High selectivity can be obtained by judicious choice of

the anionic component in particular. This can be achieved with much less
aggressive constituents or additives than in aqueous solution, where chemistry
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is dominated by a large excess of water molecules.

3.5 What is an Ionic Liquid?

Ionic liquids are officially defined as systems composed solely of ions which are
liquid below 100 1C.8 This is a rather arbitrary classification which is easy to
define but impossible to achieve and does not describe useful systems since
molecular species are omnipresent. Even very hydrophobic ionic liquids can
support up to 1.4 wt% water.9 A more useful definition could be based upon
the physical properties of ionic liquids whose conductivity differs from dilute
salt solutions in molecular solvents because mass transport is limited by hole
size and mobility.10 Alternatively, an ionic liquid could be defined as a solvent
in which the chemistry of solutes is dominated by the ionic components of the
solvent. As for metals, this is usually the anion.
Traditionally, ionic liquids are classified as either having one discrete anion
and one cation or a series of complex anions formed from the interaction
between a Lewis basic anion and a Lewis or Brønsted acidic constituent. The
majority of cations are based on aromatic or aliphatic ammonium salts and
the most studied systems involve either ethyl- or butyl-methyl imidazolium
(C2mim or C4mim) as these tend to have the lowest viscosity and the highest
conductivity.11 Table 3.2 lists some of the anionic and cationic systems studied.

3.5.1 Properties of Ionic Liquids

The eco-toxicity of many of these liquids has been determined and reported
with very varied results.12 In general the toxicity of the ionic liquid increases as

Table 3.2 Common anions and cations used in ionic liquids.

Cations Alkyl methyl imidazolium (Cnmim),
Alkylpyridinium (CnPy),
Alkylpyrollidinium,
Alkylpiperidinium
Ammonium
Phosphonium
Cholinium HOC2H4N1 (CH3) (Ch)
Beatine HOOCC2H4N1(CH3) (Hbet)
Anion (discrete) BF4, PF6, CF3SO2, [(CF3SO2)2N], C2H5SO4, Cl, (CN)2N
Anion (complex) AlCl4, Zn2Cl5, [Cl  2urea]
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66 Chapter 3
13
the alkyl chain length on the cation increases. A range of ionic liquids with
low eco-toxicity are now available and some have been applied to metal
extraction. The versatility of the ionic liquid design has meant that benign
cations have been produced and these include functionalised imidazoles to aid
biodegradation,14 lactams,15 amino acids16 and choline.17 Our group has
focussed on the last of these and taken them to the 102 to 103 kg scale for metal
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processing.18
The physical properties of ionic liquids span a wide range, for example
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density 1.00–2.40 g cm3, viscosity 5–20 000 cP, mp 40 to 100 1C and the
properties change with temperature more than most molecular liquids.19
However, the viscosity of ionic liquids is considerably higher than that of
most molecular liquids and this will be a significant issue for industrial scale-up.
As a consequence, although most texts state that most ionic liquids
have relatively high conductivities, they do in general fall in the range
0.1–50 mS cm1. This is considerably lower than aqueous acidic solutions
which are in the range 100–500 mS cm1 and is particularly important for the
electrowinning step of the recovery.
The other important parameter is naturally one of cost which is harder to
quantify as process scale is the controlling variable. It is however easy to
speculate that the cost of most aqueous lixiviants will be in the range 1–10 h per kg,
whereas the most optimistic projections for ionic liquids would put the cost in
the region 10–100 h per kg. This clearly affects the areas into which this tech-
nology will reach. This also dictates that a recycling stage is essential and this
must include at least 10 cycles for the process to be viable.
Ionic liquids are not a metallurgical panacea and they are not inherently
green, however, through judicious design of the appropriate lixiviant they have
the potential to introduce improved selectivity for some difficult to separate
systems. This therefore offers the ability to decrease environmental emissions
and energy consumption through process intensification. The most probable
application will come where ionic liquids decrease the number of processing
steps and the volume of lixiviant or where they are used primarily for high value
metals. Potential candidates include platinum group metals, rare earth metals
and trans-uranic elements.
The requirements of a medium in which to carry out metallurgical processing
are:

 chemical and electrochemical inertness

 high solubility for solutes
 facile tuning of solvent properties
 immiscibility with water for biphasic extraction
 high temperature stability
 insensitivity to water.

With over 1018 ionic liquids available20 and 102 available on a commercial
scale it is pertinent to investigate properties systematically in order to predict
suitable solvents for given applications. The cation tends to dominate the
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Ionometallurgy: Processing of Metals using Ionic Liquids 67

physical properties of an ionic liquid, whereas the anion controls the chemical
properties. By selecting the appropriate anion–cation combination, a liquid
with suitable chemical and physical properties can be produced. This does not
simply allow the ultimate solvent to be created since physical, toxicological and
financial constraints have to be considered. It is, however possible to identify
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classes of ionic liquids which may be suitable for a particular application.

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3.6 Previous Studies in Ionometallurgy

3.6.1 General Observations
The practicality of using ionic liquids for metal processing on a large scale can
be easily assessed. Given that metal solubility will usually not exceed 10 wt% in
any solvent a 10–100 fold excess will be needed for processing. The cost of the
liquid will have to be a fraction of the value of the metal to be economical since
physical losses alone are likely to be in the range of 2–10 wt%. Given that the
cost of most viable ionic liquids will be in the range 10–100 h per kg the
recovery of 1 kg of metal may result in the loss of more than 1 kg of ionic liquid,
at which point there are only a limited number of metals which can be
recovered in this manner. Absorption losses during ore extraction will tend to
be larger than those experienced using solvent extraction, however mutual
solubility in the aqueous phase can also be significant. The high cost and
viscosity of these liquids means that they are better suited to small volume, high
value applications. The prospect of concentrating metals from large volumes of
dilute aqueous solution into small volumes of ionic liquids is clearly beneficial.
This is where most of the prior studies have focussed.

3.6.2 Systems Studied

While ionic liquids were first shown to be useful for metal processing more than
15 years ago they have only been applied to show proof of principle for the
fundamental aspects, for example extraction, digestion cementation and so on.
Numerous, often unrelated systems have been studied and these are covered in
detail in other reviews.21–24 Some typical examples are summarised in Table 3.3.
In most cases, ionic liquids have been applied to biphasic extraction processes
as a direct replacement for non-polar, water-immiscible phases but other
aspects of the digestion and recovery processes have been probed.
The first systems studied were based on a chloroaluminate anion simply
because these were the only ones commonly used at the time. Dai et al.25 were
the first to study dissolution in ionic liquids using imidazolium chloroaluminate
to investigate the dissolution of UO3. Ideally the digestion medium should not
contain metal as it could lead to contamination of the extracted metal. Most of
the complexing agents investigated are classically used in organic biphasic
extraction and the results are relatively similar in most cases. The miscibility of
ionic liquids with aqueous solutions is often worse than that with most organic
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Table 3.3 Summary of metal digestion and extraction studies using ionic
liquids.
Complexing
Metal species Ionic liquid agent/oxidant Reference
Digestion
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UO3 C4mim Al2Cl7 18

Zn C4mim PF6 37
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V2O5, Cr2O3, CrO3, ChCl  2urea 38

MnO, FeO, Fe2O3, ChCl  2ethylene glycol
Fe3O4, CoO, Cu2O, ChCl  oxalic acid
ZnO
Eu2O3, yttrium oxide ([Hbet][Tf2N]) Hbet1 39
Uranium oxide C4mim Tf2N 40
Au C4mim HSO4 Fe2(SO4)3 41, 42
Au ChCl  2ethylene glycol I2
Extraction
Cd(II) Pb(II) Ni(II) C4mim PF6 2-Pyridinealdoxime 43
Zn(II)
Mn(II), Cd(II), Co(II), C4mim Tf2N Thenoyltrifluoroacetone 44
Ni(II), Zn(II)
Ag(I) Pb(II) Various PF6 and Tf2N Dithizone 45
Ce(IV) Th(IV) La(III) C8mim PF6 None 46
Ni(II), Cu(II), Pb(II) C4mim PF6 2-Aminothiophenol 47
Ca(II), Sr(II), Ba(II) C4mim Tf2N tetraocty-3-oxapentane 48
diamide
Y(III), Eu(III), Zn(II) [Cnmim][Tf2N] n ¼ 4, 8, N,N-Dioctyldiglycol 49
12 amic acid
U(VI), Sr(II), Cs(I) C4mim BF4, PF6 and Dicyclohexyl-18-crown-6 50
Tf2N
Zn(II), Cd(II), Cu(II) N1888 Cl and BF4 None 51
Fe(III)

solvents which does not make sense either from an environmental or a financial
point of view.
One aspect of ionic liquids which has gained considerable attention is the
ability to engineer the architecture of the anion or the cation to make it specific
to the solution species with which it is designed to interact. As a concept,
Davis26 is credited with task-specific ionic liquids (TSIL) where the liquid
plays a dual role as both solvent and complexing agent. Many studies
have chosen to functionalise the cation, primarily because the chemistry is
relatively easy. It could be as simple as taking a ligand with an amine func-
tionality and quaternising it. The simplest functionalised cation is beatine
HOOCC2H4N1(CH3) where the carboxylate functionality is an effective
complexant for a variety of metals. Nockemann et al.27 used the bistriflamide
salt to extract a variety of metals from aqueous solutions. They showed a useful
temperature induced phase behaviour which improved extraction efficiency
although ionic liquid loss in the aqueous phase is a significant issue.28 Other
classical complexants such as monoaza-crown ether fragments29 or urea- and
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Ionometallurgy: Processing of Metals using Ionic Liquids 69

thiourea functionalities have been covalently attached to imidazolium cations

and used for biphasic extraction.30,31 As many complexing agents are also
anionic, their incorporation into a liquid formulation requires the choice of a
suitable cation which delivers the appropriate physical properties to the liquid.
In general the cations control the physical properties of the liquids whereas the
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anions tend to complex the metal and therefore control the chemistry.
Probably the most studied area is that of lanthanides and actinides as the
facile separation of uranium from fission products is one of the most pressing
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issues in metal processing. A review by Binnemans32 covers the chemistry of the

f-block elements in ionic liquids. The extraction of lanthanides from aqueous
solutions was investigated by Jensen et al.33 using 2-thenoyltrifluoroacetone
(Htta) and the metals were found in the form Nd(tta)4 and Eu(tta)4 as
opposed to M(tta)3(H2O)n (n ¼ 2 or 3), which was found in non-polar
molecular solvents. Similar studies have used hexafluoroacetylacetonate34 and
salicylate anions35 to extract a variety of metals from aqueous solutions.
A comprehensive review of TSILs was written by Davis.36

3.7 Current Research and Future Direction

3.7.1 Oxidising Metals Electrolytically
One of the most important requirements is the ability to oxidise and reduce
metals in the operating medium. The most efficient method for doing this is
often anodic oxidation. While relatively common in aqueous solutions it has
barely been reported in ionic liquids. Oxidic surface passivation is a well-known
issue in aqueous electrodissolution processes. This can be addressed by the
addition of acids or bases which solubilise the oxides but these create further
problems concerning the environmental impact and by lowering the potential
window of the solvent. The high solubility of many oxides in ionic liquids26
suggests that anodic oxidation could become a key area for application of
ionometallurgy.
We have previously demonstrated electropolishing of a variety of nickel
based alloys in DES but not for the purposes of metal digestion. Figure 3.4
shows a nickel alloy which was anodically polarised for ca 8 h at a constant
voltage of 4 V. This electrodissolution was carried out at room temperature.
Figure 3.4(b) shows the solution after digestion and it is clear that two layers
have formed. Nickel is relatively insoluble in the ionic liquid because it forms a
complex with ethylene glycol and this means that the nickel is easy to recover by
simple filtration. The filtrate only contains nickel which allows facile separation
of the major component of the alloy from trace elements.

3.7.2 Oxidising Metals Chemically

In aqueous solutions a variety of organic and inorganic oxidants can be used to
oxidise metals, including H2SO4, HNO3, H2O2, chlorate, perchlorate and
hypochlorite. Many of these processes involve the transfer not only of an
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Figure 3.4 (a) Nickel alloy rod (left) before and (right) after anodic oxidation in a
DES. (b) shows the DES after digestion.

electron but also a proton or OH ion. This is clearly not an issue in aqueous
solutions but in aprotic ionic liquids common oxidising agents have not been
studied. In metal digestion it is important to have a pure electron transfer
oxidant that is not metal based. Oxidants such as H2O2 would become involved
in the complexation and oxidants such as Fe(III) salts would complicate the
extraction of metals at the end of the process. These restrictions rule out the
majority of commonly used oxidants. Trihalide anions have been studied in
ionic liquids with some success.
We have used I2 as an oxidation catalyst for the digestion of metals in DESs.
This was found to be ideal as there is a simple electron transfer where there are
no complex side products and iodine does not oxidise the ionic liquid, which
bromine, for example, would. I2 partitions very effectively into DESs owing to
the high concentration of Cl which produces I2Cl. The high solubility of I2 in
the DES can be seen clearly in Figure 3.5 where organic solutions, each
containing 0.5 M I2, were placed in contact with a DES consisting of choline
chloride : ethylene glycol (ethaline) (1 : 2 ratio respectively). All of the organic
solvents are effectively decolourised and the iodine partitions into the ionic
liquid. The redox potential of the I2/I couple is more positive than would be
expected from aqueous electrochemistry and it is above the oxidation potential
of most metals, including gold. This has led to the practical application of
stripping gold from microfossil scanning electon microcopy (SEM) samples.52
Iodine can therefore act as an effective oxidant for most metals. Experiments
have also attempted to use bromine, which oxidises the solvent constituents in
DESs but may be suitable for use with more redox-stable ions. The trichloride
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Ionometallurgy: Processing of Metals using Ionic Liquids 71

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Figure 3.5 Partition of iodine between the DES ethaline and a variety of non-polar
organic solvents.

Figure 3.6 Diagram of the recovery of alloys using iodine as the oxidising agent in a
solution of ethaline.

anion, Cl3 has even been reported to be a breakdown product of ionic liquids
and may exist in media with high ionic strength.53
This has led to its use as an oxidation catalyst for the digestion of metals and
particularly alloys. Ionic liquids effect a change in the relative redox potential of
metals owing to differences in solution speciation. This can enable systems to be
designed in which all the metals in an alloy can be digested using iodine and one
of the metals can then be retrieved by electrowining from the solution. The use
of iodine effectively avoids having to establish electrical contact between the
anode and the metal. Anodic reoxidation of iodine in solution is very fast. This
has been successfully achieved for a variety of alloys and is shown schematically
in Figure 3.6.

3.7.3 Solubility
In aqueous solutions approximate rules exist for the solubility of metal salts,
for example most hydroxides, sulfides and carbonates tend to be insoluble,
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72 Chapter 3

whereas halides, nitrates and acetates tend to be soluble with only a few
exceptions. Many of these general rules are pH and electrolyte dependent owing
to speciation, for example silver chloride is notoriously insoluble in water
owing to the high lattice energy compared to the energy of solvation, however
in concentrated HCl or chloride-based ionic liquids, AgCl is soluble owing to
the formation of AgCl2. This phenomenon could be thought of as a salting-in
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effect whereby an increase in the solubility of a non-electrolyte is observed when

a salt is added to the solution. Typically the non-electrolyte interacts with the
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electrolyte to produce an overall charged species.

No analogous consideration has been made for ionic liquids although the
AgCl example is one that is commonly found. Because ionic liquids typically
contain 44 M anions many salts which are insoluble in aqueous solutions are
soluble in ionic liquids. In contrast to aqueous solutions, salts of Na1, K1, Cs1
and most group 2 salts show relatively poor solubility in ionic liquids.54
Surprisingly, relatively few systematic studies of metal salt solubility in ionic
liquids have been carried out. The solubilities of metals have been previously
reviewed.55,56 On the other hand Branco et al. studied the solubility of LiCl,
HgCl2 and LaCl3 in imidazolium tetrafluoroborates and hexafluorophosphates
and found that it was relatively independent of the anion or cation.57 Func-
tional groups added to the cation can improve the solubility of metal salts. An
example of these TSILs is the addition of thioether and thiourea groups to the
side chain of the imidazolium cations, making Hg21 and Cd21 ions soluble in
the ionic liquids phase.58 TSILs have been discussed in greater detail above.
A study by Chiappe et al. studied the effect of the anion of the salt being
dissolved in the ionic liquid and observed a marked effect. The highest solu-
bility occurred when the anion of the metals salt was the same as that of the
ionic liquid.59

3.7.4 Precipitating Agents

Although the use of precipitating agents in ionic liquids is not a topic which has
been systematically studied, qualitative observations have been made albeit
from the opposite perspective. Studies have attempted to construct suitable
homogeneous catalysts for use in ionic liquids and it has been noted that
uncharged complexes tend to exhibit very low solubility.53
From the general rule that ‘‘like dissolves like’’ it could be concluded that
most ionic species should be soluble in ionic liquids whereas neutral molecules
should not. This is a rather simplistic model since the rule tends to apply to
small monophilic molecular solvents. Taking a simple ionic liquid such a
C6mim C2H5SO4, it will naturally have the ability to facilitate charge–charge
interactions and the cation’s aromatic ring will have a high degree of polar-
isability. The C1 proton on the imidazolium ring will be relatively acidic,
whereas the anion will be Lewis basic. Removing the charge–charge inter-
actions will clearly be the main effect on solubility which is the reason that the
more covalent oxides are less soluble in charged media. An alternative,
although as yet unproven way, would be to add an amphiphilic ligand, for
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Ionometallurgy: Processing of Metals using Ionic Liquids 73

example a fluorous surfactant which specifically interacts with the metal

forming a hydrophobic complex. An approach that has been applied
successfully is to use an anti-solvent. It has previously been shown that iron,
nickel and chromium salts could be precipitated from a choline chloride :
ethylene glycol DES by the addition of an equal volume of water. After
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filtration the water could be evaporated from the solution.

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3.7.5 Redox Potentials

An understanding of redox potentials is essential in metallurgy as it governs
the ease of oxidation for dissolution and reduction for deposition or cemen-
tation. It is possible to alter the redox potentials of metals significantly
through judicious choice of the ionic liquid, although this has not been
quantified in a systematic way. The difference in reactivity of metals in ionic
liquids depends primarily upon the complexation of the metal in solution, that
is the anionic component of the solvent. An example of this is that iodine can
oxidise gold in some ionic liquids but it will not oxidise it in water.
Complexation of the metal ion with the anion of the ionic liquid tends to result
in anionic complexes.
Comparison of redox potentials from one ionic liquid to another are
complicated owing to the lack of reliable reference electrodes for use in ionic
liquids; this is part of the reason for a lack of authoritative data. Most studies
have used either an electrode with a reference electrode that is unreliable owing
to unknown liquid junction potentials or a quasi-reference electrode (QRE).
Silver or platinum wires are the most commonly used QREs.60 The wires are
frequently put directly in the analyte solutions which may affect the reference
potential by reaction with the analyte or species that adsorb to the surface of
the electrode. Reference redox couples such as ferrocene/ferrocinium or
cobaltocene/cobaltocinium are also commonly added at the end of an
experiment to determine a reference potential.61,62 The instability of the
Ag|Ag1 couple has been studied by Torriero and MacFarlane63 and Rogers
et al.64 who suggested a standard approach for reference potentials in ionic
liquids which is similar to that adopted in non-aqueous solvents. This avoids
QREs except where they can be calibrated against a standard reference redox
system. The Ag|0.01 M AgOTf reference electrode is recommended, along with
the Fc|Fc1 and [Co(Cp)2]1 |[Co(Cp)2] reference couples.
The first hydrogen electrode for use in an ionic liquid was recently reported.
It was found that the Ag|Ag1 couple exhibited ideal Nernstian behaviour in
ionic liquids with anions such as Cl whereas anions such as SCN deviated
significantly from ideality. It was shown that other couples such as the Cu21/1
and H1/H2 were also Nernstian up to 1 mol kg1 in DESs.65
A recent paper introducing the concept of ionometallurgy published the
first electrochemical series in an ionic liquid.1 The redox potentials in ionic
liquids were compared to standard aqueous redox potentials and it was shown
that significant scatter existed between the two sets of data, as shown in
Figure 3.7.
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74 Chapter 3
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Figure 3.7 Plot showing the correlation between redox potentials in water and the
chloride-based DES ethaline.

3.8 Issues to be Addressed

3.8.1 Material handling
To date most studies in ionic liquids have used analogous handling procedures
to hydrometallurgy. One of the main differences between these media and
aqueous solutions is the viscosity and hence the mass transport. The intimate
contact of a solid particle and a viscous liquid phase generates difficulties
associated with slow extraction kinetics and material loss resulting from
entrapment or physical loss, particularly in processes like filtering. Since
evaporation of the solvent is not an option, excess ionic liquid has to be
extracted with a molecular solvent or left on the tailings of the digestion
process. If these are released to the environment, the residual ionic liquid will
have to have negligible environmental toxicity and be of low cost since mech-
anical losses could be in excess of 10 wt%. Filtration is the most common
separation technique used and so one technical issue that will have to be
addressed is how to filter viscous solutions containing suspensions of fine
particles. In the only scale-up study to date, the particulates were o1 mm dust
particles suspended in an ionic liquid with a viscosity of 20 cP. A double bag
filter was used but visible amounts of particles were still left in the ionic liquid
which became entrapped during the electrowinning stage of upstream
processing. The physical losses of ionic liquid on the filtrate were in the order of
10 wt%.5
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Ionometallurgy: Processing of Metals using Ionic Liquids 75

3.8.2 Material Recycling

The high cost and environmental incompatibility of many ionic liquids makes
the repeated recycling of these systems essential. Physical losses, as described
above, are an issue but so is the removal of extraneous waste like inert metal
ions, water and various organic materials. There will always be waste water
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streams used either up-stream or downsteam of the ionic liquid stages so

removal of ionic liquids from water is an issue that is relatively unaddressed.
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Biphasic extraction usually leads to the transfer of an ion from the ionic
liquid to the aqueous phase and the metal complex is taken up by the ionic
liquid. Methodologies for large scale cleaning of ionic liquids are not
given in the open literature although some are clearly known from the
handful of processes which are already carried out on a scale in excess of
1 tonne.

3.8.3 Fundamental Data

Little is known about speciation, reactivity, redox properties or solubility of
metals in ionic liquids. In aqueous systems hydrometallurgical processing is
greatly aided by Pourbaix diagrams,66 which show thermodynamically
preferred metal species in a variety of aqueous solutions as a function of pH
and electrode potential. These do not exist in ionic liquids, partially because of
the lack of reference potentials but mainly due to the lack of a suitable theory to
quantify Lewis or Brønsted acidities. The conventional concept of acidity
resulting from H3O1 does not work owing to the high ionic strength and the
number of different ionic species present. A review of Brønsted acidity of ionic
liquids67 suggested that the position of acid base equilibria in a wide range of
liquids correlates more closely with gas phase proton affinities (of the conjugate
base) than with aqueous pKa values because of the high aqueous solvation
energies. Definitive pH measurement could, in principle, be attempted by
potentiometric methods. This has been shown in the construction of a standard
hydrogen electrode in an ionic liquid but data has still to be collected for useful
acid systems.62

3.8.4 Environmental Impact

Some work on environmental impact was carried out by Matthijs and co-
workers who studied choline chloride and ethylene glycol DESs.68 They found
that the heavy metals present in the rinse solutions constituted the main
environmental impact but some electrolytic decomposition was also identified.
The advantages of DESs are that the liquids themselves can be designed to be
non-hazardous and biodegradable. Mechanical losses have been quantified but
much of the metal loss was treated in a standard method using ion exchange
resins to trap metal residues.69 This area still requires extensive research before
ionometallurgy can become successful on a large scale.
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76 Chapter 3

3.9 Conclusions
Ionometallurgy is a method of controlling the dissolution and recovery of metal
species from solution by dominating the environment surrounding the metal
cation with ionic species. It circumvents issues where metal separation and
solubility are limited by aquo-controlled speciation. The main areas of appli-
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cation appear to be for precious metals and rare earth metals primarily because
of the cost of the liquids but also due to the potential simplification of process
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chemistry resulting from tailored speciation in solution. Although the topic is in

its infancy, ionometallurgy is probably most tantalising for its ability to recycle
metals from complex composite materials. Significantly, more work needs to be
carried out to characterise the most suitable systems for each complex material
but some evidence exists already in the open literature that shows unprece-
dented tunability of ionic media over aqueous solutions. Ultimately, however it
is most probable that a hybrid system of molecular and ionic components will
be the most likely to deliver the optimum separation capability.

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