Physicochemical Problems of Mineral Processing, 42 (2008), 223-236

Fizykochemiczne Problemy Mineralurgii, 42 (2008), 223-236

Justyna uczak, Monika Joskowska*, Jan Hupka*

IMIDAZOLIUM IONIC LIQUIDS IN MINERAL

PROCESSING
Received June 18, 2008; reviewed; accepted July 31, 2008
Imidazolium ionic liquids (ILs) represent promising potential for industrial and technological applications - considering ILs as a new class of compounds. Usability of ILs in the mineral processing area
described in the literature is up to now limited. Their application was indicated for minerals leaching,
solvent extraction as well as electrochemical processes showing that these compounds may play an
important role in the recovery and purification of high-value metals from water as well as ores. Imidazolium derivatives may be used as either efficient solvents or active compounds promoting separation. Environmental impact and recycling possibilities were also described. Nevertheless, their potential industrial applications in mineral processing require further detailed examination.
key words: imidazolium ionic liquids, minerals leaching, extraction, micelle formation

INTRODUCTION
Majority of chemical processes are carried out mainly in water as generally available solvent. Application of alcohols, halogen derivatives and condensed gases (SO2,
NH3) has also found application to carry out chemical reactions. Volatile organic solvents (VOC), liquid ammonia are still in common use in the laboratory scale as well
as in the chemical industry. There is tendency to eliminate organic solvents by projecting new, environmentally friendly technologies. One of the groups of compounds,
which could replace traditional solvents, are ionic liquids (ILs) - organic salts with
melting point lower than 100oC. As distinct from organic solvents, ionic liquids are
entirely composed of ions. Moreover, conventional salts such as sodium chloride consist of small, close packed cation and anion which form a solid with high melting
_________
Department of Chemical Technology, Chemical Faculty, Gdask University of Technology, 80-952
Gdansk, Poland, [email protected]

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J. uczak, M. Joskowska, J. Hupka

point, that limit their application as a reaction media. On the contrary, ILs are composed of bulky organic cation and small/large anion (Fig. 1). More difficult packing
and weaker attractions between ions result in a liquid state of matter (Deetlefs et
al.,2006; Blesic et al.,2007).

R
N

+ Me

Fig. 1. Chemical structure of 1-alkyl-3-methylimidazolium ionic liquid

Their properties (selectivity, negligible volatility, inflammability, thermal stability

ect.) cause that ILs may play promising role as alternative media in a number of
industrial applications like catalytical (Welton, 2004; Sheldon, 2001), separation
(Visser et al., 2002; Huddleston et al., 1998), electrochemical processes as well in
combined reaction-separation processes. ILs are often called designer solvents or taskspecific ionic liquids (TSILs) because of possibility to being tailored to fulfil technological demands of the variety applications. IL properties can be significantly adjusted
e.g. hydrophobic vs. hydrophilic by interchange of the anion type, or a slight modification of the number or length of alkyl chains in the cation (Visser and Rogers, 2003).
Selection of anion may significantly change the miscibility of ILs with water, whereas
manipulation in alkyl chain length may have only a slight effect. Moreover, solubility
in water might be increased by addition of e.g. short chain alcohols or chaotropes
(Welton, 2004; Alfassi et al., 2003; Huddleston et al., 2001).
In this paper we reviewed the literature on ILs application in mineral processing,
since ILs may offer potential for development of efficient, environmentally friendly
metal recovery technologies from ores and wastes. Some own data on ILs surface
properties are also included.

MINERALS LEACHING
The most important step of metallurgical processing is efficient separation of metals from ores followed by metals recovery from concentrate. Depletion of resources
leads to using more lean ores and favours the hydrometallurgical approach.
ILs were examined as solvents (either as a neat liquid or as aqueous mixtures) for
the leaching of gold, silver, copper and base metals from sulphidic ores (Whitehead et
al., 2004; Whitehead et al., 2007). At present, mainly cyanides are used for the commercial hydrometallurgical leaching of gold and silver from ores and concentrates.
However, due to the highly toxic nature of cyanide and environmental consequences,
the process is very controversial and provokes examination of new leaching species.

Imidazolium ionic liquids in mineral processing

225

C4MIM HSO4 (1-butyl-3-methyl-imidazolium hydrogen sulphate) and similar compounds in the presence of thiourea (or other S-containing compounds) and iron(III) as
oxidant were used to separate gold and silver from ores.
The extraction of gold was achieved to be >85% from synthetic oxidic ore as well
as natural sulphidic ore at 20-50oC using ionic liquid as a solvent. Gold extraction was
close to results achieved for aqueous system H2SO4/tiourea/Fe2(SO4)3, whereas recovery of silver from the natural sulphidic ore was significantly higher (60%) for the
neat IL compared with an aqueous acid solution (<10%) as presented in Fig. 2. Moreover, high selectivity for the extraction of gold and silver was reported, with minimal
selectivity of other metals (Cu, Zn, Pb and Fe).
100
90

% extraction

80
70
60
50
40
30
20
10
0
0

10

20

30

40

50

60

time (hrs)
Fig. 2. Comparative leaching of gold and silver from ore using aqueous H2SO4 or C4MIM HSO4 in presence of Fe2(SO4)3 and tiourea

Extension of n-alkyl chain length in imidazolium cation resulted in decreasing extraction efficiency of gold and silver, that might resulted from the increasing viscosity
of ILs. The analysis of leaching results obtained for ILs with varied chain length and
different types of anions showed that C4MIM HSO4 was the most effective medium
that is important taking into account relatively low price of this compound.
Table 1. Effect of C4MIM HSO4 concentration on copper extraction
from chalcopyrite at 70oC (Whitehead et al., 2007)
C4MIM HSO4 [%w/w]

Cu extracted [%]

10
20
50
100
1 M H2SO4

55.7
58.1
82.2
86.6
23.2

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Copper extraction from chalcopyrite showed selective extraction of copper towards iron in the ionic liquid medium at 70 C. Application of neat IL was more efficient (efficiency 87% of copper) than its solution (55% for 10%w/w) as shown in Table 1. Moreover, the recycling ability of C4MIM HSO4 by separation of gold and
silver on activated charcoal was proposed without decomposition or significant
change in the structure of IL (Whitehead et al., 2004; Whitehead et al., 2007).

MINERALS BENEFICIATION
One of the most important beneficiation processes is froth flotation of minerals,
which requires hydrophobicity of the mineral particle. Only a few minerals naturally
posses hydrophobic surface, hence, variety of reagents (collectors) providing hydrophobicity of the surface are used (Drzymaa, 2001; Fuerstenau et al., 1985). The difficulty in the recovery of oxide-containing minerals causes that search of the new collectors is of utmost importance. So far some research involved application of pyridinuim salts (which are also describes as ionic liquids) in potash ores, phosphate rock,
sulphide, oxide, silicate ores and coal (Madaan et al., 2008). Similarities in the composition of pyridinium and imidazolium salts allow assuming that imidazolium ILs
may also behave like cationic collectors being suitable for oxide ores. ILs may form
films at the surface of negatively charged particles by ion-ion interaction or interact
by free electron pair of the nitrogen atom in cation with the ore surface that might increase hydrophobicity of ore particles. However, there is lack of research including
application of the imidazolium ILs in flotation.

R
N

+ Me
N

N+
R

Fig. 3. Comparison of the structures of 1-alkyl-3-methylimidazolium and alkylpyridinium cation

SOLVENT EXTRACTION OF METAL IONS FROM AQUEOUS

SOLUTION
Another consideration is given to application of ionic liquids in separations in order to replace organic solvents used in traditional liquid-liquid extraction of metal

Imidazolium ionic liquids in mineral processing

227

ions from aqueous solutions. Some properties which make ILs attractive as alternative
media in extraction processes are tunability, negligible vapour pressure, good thermal
stability, and a wide liquid range. Since the partitioning of metal ions from aqueous
solutions into ionic liquids is inefficient as a result of the tendency of the metal
cations to remain hydrated in the aqueous phase, additional extractants, type of crown
ethers (Dai et al., 1999; Chun et al., 2001), calixarenes (Luo et al., 2004), ditizone
ditizone (Wei et al., 2003) and others (Visser and Rogers, 2003) were used. These
species significantly enhance the partitioning of metal ions by forming complexes.
The variety of tests were curried out in regard to extract heavy metals (Dai et al.,
1999; Wei et al., 2003), alkali metals (Chun et al., 2001), actinides (Visser and
Rogers, 2003) and lanthanoid ions (Kozonoi et al., 2007).
Modification of commonly used ILs by including a metal ion-ligating functional
group in structure of one of the ions provides TSILs which play dual role of both hydrophobic solvents and extractants. Visser presented new thiourea, urea and thioether
derivative of ILs designed to extract heavy metal ions (e.g. Hg2+ and Cd2+) (Visser et
al., 2001; Visser et al., 2002). According to the literature, preliminary research indicates that the application of ILs as an alternative solvent to replace traditional organic
solvents in liquid - liquid extraction of metal ions is very promising.
ILs may also offer potential for the development of efficient processing of nuclear
materials. The method for treating or reprocessing spent nuclear fuel using ionic liquids, and in particular to recover uranium and plutonium, was patented (Thied et al.,
1999).

OTHER APPLICATIONS
We have also indicated several applications of ILs which not necessarily refer to
mineral processing, however, are important in neighbouring technological areas such
as metal electrowinning and waste material recycling. ILs may have potential to reduce energy consumption due to their low melting point.
Preliminary research on ILs in the electrorefining and electrowinning technologies
pertains mainly aluminium processing (Nogrady, 2006; Kamavaram et al., 2003). The
possibilities of aluminium refining is limited due to a strong affinity to oxygen, and
cannot be electrolyzed in an aqueous solution due to its negative reduction potential
(Zhang et al., 2003). Aluminium production through electrodeposition needs dissolvation of alumina in molten cryolite (Na3AlF6) bath. To keep cryolite liquid the temperature of 1000C is needed consuming large amounts of energy. Application of ILs instead of cryolite might diminish energy demand in a significant way. Electrorefining
of aluminium alloy in acidic C4MIM AlCl4 (1-butyl-3-methylimidazolium tertachloroaluminate) was curried out, resulting in obtaining high purity aluminum (99.89%).
Energy consumption was estimated to be about 3 kWh/kg-Al in comparison to 17-18
kWh/kg-Al for the existing industrial refining process (Kamavaram et al., 2003).

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Moreover, aluminium was also recovered from waste aluminium metal matrix
composite by electrolysis in C4MIM AlCl4 at 103oC. A high purity product (>98%Al)
was obtained (Kamavaram et al., 2005). What is characteristic for electrolysis in ILs
is high purity of metal deposits obtained, high current densities possible as well as
low energy consumption.
The possibility of application of ILs in processing of copper sulfide ores and base
metal sulfides supported by preliminary findings in the use of ionic liquids in the electrorefining of chalcopyrite (CuFeS2) was also indicated (McCluscey et al., 2001).
The possibility of electrolytic purification and electrowinning is a results of the
immiscibility of selected ionic liquids with water and some organic solvents and
theirs electrical conductivity. Especially wide electrochemical windows make ILs
predominant towards conventional aqueous and organic electrochemistry in the electrodeposition of certain metals (Nogrady, 2006).

POSSIBILITY OF RECYCLING
Despite a number of advantages successful commercialization of ILs will depend
on price and possibilities of recycling. Due to chemical stability and negligible volatility, ionic liquids are amenable to multiply recycling which allows decreasing the
cost of a process. Solubility contributes most likely to the transport in environment
and resulting spreading of contaminates. However, the loss of ILs into aqueous solution during e.g. solvent extraction will be important factor in process cost estimation
(Alfassi et al., 2003). It was shown, that supercritical as well as relatively lowpressure gaseous CO2 can be used to separate ILs from organic mixtures and water
(Scurto et al., 2003; Blanchard and Brennecke, 2001). Additionally, the ionic liquid
can be recycled following separation of metals e.g. gold or silver on activated carbon
(Whitehead et al., 2004).
Presently ILs are very expensive, however, when production on a mass scale will
start the price of ILs is expected to drop significantly.

ENVIRONMENTAL IMPACT
The wide range of possible industrial applications requires an evaluation of ionic
liquids with respect to their (eco)toxicity. The impact should be assessed before they
enter the environment as a part of sustainable development of chemical production.
Toxicity of the common class of imidazolium ionic liquids was measured using the variety of bioassay tests including bacteria, algae, mammalian cell lines
(Ranke et al., 2005; Zhao et al., 2007) as well as their biodegrability using activated
sludge (Garcia et al., 2005; Gathergood et al., 2006). Imidazolium derivatives were
found to be more toxic than selected organic solvents (acetone, acetonitrile, metha-

Imidazolium ionic liquids in mineral processing

229

nol), poorly biodegradable and relatively resistant to photodegradation (Stepnowski

and Zalewska, 2004). Increasing toxicity with elongation of alkyl chain length was
also observed. The high level of biodegrability was achieved by the incorporation of
an ester in the side chain of the imidazolium cation and combination with octylsulfate
anion (Gathergood et al., 2006). As an effective disposal method for difficult biodegradable ionic liquid cations - the electrochemical wastewater treatment was proposed. The electrolysis results in complete destruction of 1-butyl-3methylimidazolium cation to easily biodegradable products (Stolte et al., 2008).

SURFACE ACTIVITY
Imidazolizum ionic liquids with long chain are generally seen to behave as amphiphilic compounds, displaying interface interaction. Likewise surfactants, ionic liquids
also depend on chain length regarding the interface ordering phenomena (Blesic et al.,
2007; Miskolczy et al., 2004; Vanyur et al., 2007; Jungnickel et al., 2008). Amphiphilic ILs possess significant promise in miscellaneous industrial applications, where
high surface areas, modification of the interfacial activity or stability of colloidal systems are required. However, the state of knowledge of ILs structure and behaviour in
an aqueous solution is so far limited. The phenomena of ILs self-organization in
aqueous solutions are currently under investigation by our group as well as other authors (Vanyur et al., 2007; Inoue et al., 2007; uczak et al., 2007). The length of the
alkyl chain substituents, the degree of substitution, type of counterion as well as temperature were found to have vital effect on the CMC values of ILs. There is lack of
studies concerning more composed systems including e.g. electrolytes or cosurfactants.
In our previous research we have determined CMC of 1-alkyl-3-methylimidazolium ionic liquids with alkyl chain lengths 4 -18 and chloride anion (CnMIM
Cl) by surface tension and electrical conductivity measurements. The results of the
surface tension measurements for the aqueous solutions as a function of the ILs concentration are presented in Fig. 4.
Discontinuities are observed only for compounds possessing the alkyl chain equal
or longer than 8 carbon atoms, suggesting that only these imidazolium derivatives
may be able to form micelles at 298K. The CMCs for [C4MIM] Cl and [C6MIM] Cl
were not observed, even though the surface tension measurements of high concentrated solutions were conducted. The micelle formation in these ILs cannot be positively confirmed in the current conditions of measurements (298 K) that might result
from theirs composition - too short alkyl chain in cation or high Krafft point of these
compounds. The experimental results of the break points indicating CMCs are presented in Table 2.

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J. uczak, M. Joskowska, J. Hupka

Surface tension [mN/m]

80

70

60

50

40

30
0.01

0.1

10

100

1000

10000

Concentration [mM]

Fig. 4. Surface tension data versus IL concentration isotherms measured at 298 K for aqueous solutions
of [C4MIM] Cl (
), [C6MIM] Cl (), [C8MIM] Cl (), [C10MIM] Cl (), [C14MIM] Cl (+), [C16MIM]
Cl (
) and C18MIM Cl ()
Table 2. Comparison of CMC results of CnMIM Cl and literature data of CnMIM Br, cationic surfactants
of the alkyltrimethylammonium chlorides and bromides and sodium alkylsulphates in 298K
Nr of C atoms

CnMIM Cl

CnMIM Br

220[1]
234[1]
59.9[1]
53.8[1]

150[2]

10

12

41[7]

94.7[6]
96[9]

9.8[7]
9.5[8]

22.2[6]
22[9]

3.38[1]
2.5[7]
[1]
3.15
2.6[8]
[1]
16
1.26
0.61[7]
[1]
1.14
0.65[8]
18
0.40[1]
0.45[1]
[1]our previous work (Jungnickel et al.,2008)
[2] (Goodchild et al., 2007)
[3] (Derrico et al., 2001)
[4] (Shaw, 1992)
[5] (Huibers et al., 1997)
[6] (Perger and Bester Rogac, 2007)
14

CnTAC

5.63[6]
5.5[9]
1.3[10]**

CnTAB

SAS*

225[3]

140[4]
139[5]
33[4]
33[5]

62[3]
62.7[11]
60.2[11]
14.3[3]
14.8[12]**
15.7[12]**
4.08[12]**
3.94[12]**
0.93[12]**
0.92[12]**

8.6[4]
8.59[5]
2.2[4]
2.12[5]
0.58[4]
0.58[5]
0.23[4]
0.16[5]

[7] (Vanyur et al., 2007)

[8] (Inoue et al., 2007)
[9] (Hayami et al., 1998)
[10] (Blesic et al., 2007)
[11] (Chakraborty and Moulik, 2007)
[12] (Basu Ray et al., 2005)
*313 K, **296 K

Imidazolium ionic liquids in mineral processing

231

Described results show that elongation of the carbon chain decreases the CMC
meaning that increasing the hydrophobic part of the IL cations favours micelle formation - as has been shown in the literature (Hunter, 1989). For homologous series of 1alkyl-methylimidazolium chlorides, linear relationship between the logarithm of CMC
and the number of carbon atoms in the alkyl chain of the cation has been found to be:
y = 4.5 0.28x (logCMC =A Bx)
where A, B are constants for a particular homologous series and temperature, and x is
number of carbon atoms in the hydrocarbon chain. Constant A varies with the nature
and number of hydrophilic groups while B is a constant which reflects the effect of
each additional methylene group on the CMC. This equation is in good agreement
with the relationship calculated for values published by Belsic (y = 4.7 0.29x) (Blesic et al., 2007).
Comparison of CMC data of imidazolium derivatives with the common surfactants
let to conclude that we can observe similar CMC vs. number of carbon atoms in chain
relationships between ILs and surfactants. The CMC values of [CnMIM][Cl] ionic
liquids were found to locate between those of CnTAC and SAS possessing alkyl moiety with the analogical number of carbon atoms. An analogical relationship was also
found for [CnMIM][Br], CnTABr and SAS, as shown in Fig. 5. The lower CMC values of ILs in comparison to the alkyltrimethylammonium salts might be attributed to
the structure of the imidazolium head group which has weaker affinity to the hydrogen bond formation with water. On the other hand, IL as salt possessing some ionic
strength may have tendency to stronger salting-out effect. Moreover, it may be also
the result of interactions between anion and aromatic ring in imidazolium derivatives
which did not occur in the case of typical surfactants. The lower values for compound
with Br- than Cl- anions can be explained by the influence of the anion size. The larger
ion is, the weaker hydration occurs. The weaker hydrated anions are easily adsorbed
on the surface of the micelles which decreases electrostatic repulsion and in this way
facilitates aggregation (Hunter, 1989).
A linear relationship between the CMC values and carbon atoms number for mentioned ILs as well as surfactants is presented in Fig. 5.
As mentioned before, the CMC determination may strongly depend on the solubility of surfactant. For ionic surfactants, there is a temperature called the Kraft temperature (KT), below which the solubility decreases dramatically. It is necessary to measure the CMC of surfactants above the Krafft temperature since there is no micelle
formation below the KT. With rising the temperature the solubility slowly increases
until at the Krafft temperature CMC is reached. The Krafft temperature and CMC of
the surfactants provide information about the conditions at which the compound acts
as an amphiphile (Hunter, 1989; Holmberg, 2002).
Fig. 6 presents an exemplary result of Krafft temperature determination by the
conductivity method. During temperature transition the electrical conductivity increases with the increasing temperature, due to larger dissolution of the IL until the KT

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J. uczak, M. Joskowska, J. Hupka

is reached. After KT the conductance increases slowly due to the increase in ionic
mobility.
1000

CMC [mM]

100

10

0,1
6

10
12
14
16
Number of carbon atoms

18

20

Fig. 5. CMC dependence on alkyl chain length in 298 K:

CnMIM Cl (), CnMIM Br (), CnTAC (
), CnTAB () and SAS ()
350
300

[S/cm]

250
200

KT

150
100
50
0
270

275

T [K]

280

285

290

Fig. 6. The Krafft temperature determination of [C16MIM]Cl

The Krafft temperatures listed in Table 5 show that determination of KT by this

method was only possible for ILs possessing more than 16 carbon atoms in chain
length. The KT for the rest of the compounds could not be determined as there was no
visible turbidity even at a few degrees below 0C. In Table 3 we report the Krafft temperatures for 1-alkyl-3-methylimidazolium chlorides, alkyltrimethylammonium
bromide as well as sodium alkyl sulphates compounds. Results show that the Krafft

Imidazolium ionic liquids in mineral processing

233

temperatures of ILs are lower than those of the CnTAB and much lower than SAS
homologues, presenting behaviour opposite to CMC dependence, meaning that imidazolium derivatives behave like surfactants at lower temperatures.
Table 3. The Krafft temperatures of imidazolium ILs
and alkyltrimethylammonium bromides compounds
Number of
Carbon atoms
CnMIM Cl

< 273

< 273

< 273

< 273

279.5

297

CnTAB

< 273[1]

< 273[1]

< 273[1]

~273[1]

297[2]

308-309[1]

281[3]

289[3]

303[3]

318[3]

329[3]

SAS

10

12

14

16

18

[1] (Davey et al., 1989)

[2] (Adam and Pankhurst, 1946)
[3] (Shaw, 1992)

CONCLUSIONS
The application of imidazolium ionic liquids as media for separation (e.g. leaching) is growing promptly mainly because of the adjustable nature of both cation and
anion. The separation possibilities are very wide including recovery of valuable metals from waste waters, ores as well as organic molecules and gases. Moreover, they
offer potential to projecting and developing processes with reduced energy consumption as a result of their low melting point.
Ionic liquids are considered as promising compounds mainly thanks to their negligible vapour pressure, hence, there is no loss of ILs through evaporation. However,
most of ILs described nowadays in literature for catalysis, electrochemical and separation processes consist of halogen containing anions which might be toxic and corrosive. Therefore, it is important to find methods to take advantage of the nonvolatile
nature of ionic liquids that is untypical for wide used liquid media.
For the sake of many advantageous properties and successful initial experiments
considering potential applications projecting of inherently non-toxic, hydrolysis stable
and biodegradable compounds is crucial.

ACKNOWLEDGEMENTS
Financial support was provided by the Polish Ministry of Science and Higher Education in the years
2007-2010 grant No.: N205 041 32/2340 and Gdask University of Technology contract No.: BW
014694/039.

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J. uczak, M. Joskowska, J. Hupka

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uczak, J., Joskowska, M., Hupka J., Imidazoliowe ciecze jonowe w mineralurgii, Physicochemical
Problems of Mineral Processing, 42 (2008), 223-236 (w jz. ang)
Imidazoliowe ciecze jonowe (ILs) stanowi now klas zwizkw o szerokich moliwociach przemysowego zastosowania. Z przegldu dostpnej literatury wynika, e ILs mogyby zosta wykorzystane
do odzysku i oczyszczania metali ze rodowiska wodnego oraz rud w procesach ugowania, ekstrakcji
rozpuszczalnikowej oraz w procesach elektrochemicznych. Pochodne imidazoliowe mog by wykorzystywane zarwno jako rozpuszczalniki jak i aktywne czynniki separujce. W pracy uwzgldniono take
wpyw na rodowisko oraz moliwoci odzysku ILs. Wykazano, e potencjalne zastosowanie w mineralurgii wymaga dalszych systematycznych bada.
sowa kluczowe: imidazoliowe ciecze jonowe, ugowanie mineralne, ekstrakcja, formowanie miceli