Mineral Processing and Extractive Metallurgy Review

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Review on the mineral processing in ionic liquids

and deep eutectic solvents

Guocai Tian & Hongwei Liu

To cite this article: Guocai Tian & Hongwei Liu (2022): Review on the mineral processing in ionic
liquids and deep eutectic solvents, Mineral Processing and Extractive Metallurgy Review, DOI:
10.1080/08827508.2022.2123322

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Published online: 18 Sep 2022.

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MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
https://doi.org/10.1080/08827508.2022.2123322

Review on the mineral processing in ionic liquids and deep eutectic solvents
Guocai Tiana,b and Hongwei Liua
a
State Key Laboratory of Complex Nonferrous Resources Clean Utilization, Kunming University of Science and Technolgy, Kunming, Yunnan Province,
China; bFaculty of Metallurgical and Energy Engineering, Kunming University of Science and Technolgy, Kunming, Yunnan Province, China

ABSTRACT KEYWORDS
Mineral processing is one of the important methods of resource utilization, and flotation and leaching are Ionic liquids; deep eutectic
the main methods of mineral processing. The conventional reagents used in these methods usually show solvents; mineral processing;
that they may lead to health, environment, safety, and other related problems. In order to make these mineral flotation; mineral
leaching
methods safer and cleaners, it is necessary to explore the use of more green and environmentally friendly
reagents. Ionic liquids (ILs) and deep eutectic solvents (DESs) are known as green solvents because of their
wide liquid temperature range, good solubility, high thermal and chemical stability, almost nonvolatile
and low toxicity. The application of ILs and DESs as agents in mineral flotation and extraction of valuable
metal can provide new alternatives to traditional methods and processes and realize green and clean
production. ILs and DESs have been successfully used to high-efficient float some minerals that are
difficult to float, such as rare-earth minerals, quartz, and quartz hematite, as well as carbonate asphalt
during recent years. Here we focus on the application progress, existing problems, and development
direction of ILs and DESs in mineral processing. We introduced characteristics of ILs and DESs, and the
research progress of ILs and DESs in green flotation of rare-earth ore, quartz and quartz hematite. The
research works of ILs and DESs in the green leaching of chalcopyrite, sulfide ore, gold, and silver ore is
summarized. Interactions of ILs and DESs with common minerals of soil also discussed to help understand
the impact of ionic liquids on soil and groundwater. Compared with the traditional flotation and leaching
reagents, the amount of ILs and DESs used is obviously smaller, and the selectivity and efficiency are
better than that of the traditional system. After further research and optimization, it is expected to be
developed into a new efficient and green mineral processing technology.

Introduction cannot effectively solve the separation problem of complex

Mineral resources have become very important basic materials
for the development of the national economy, national defense,
science and technology, and so on. They are key strategic
resources to enhance comprehensive strength of the country
and ensure national security (He 2017; Hu 2014; Qiu and Chai
2015; Qiu and Wang 2019; Wang 2017). Almost all mineral
resources have to be processed. Mineral processing plays a key
role in the process of industrialization and modernization in
the world. The development of mineral processing discipline
and technology provides technological support for the devel­
opment of mineral resources. With the rapid development of
economy and society, on the one hand, countries all over the
world are consuming high-grade and easily processed-ore
resources at an unprecedented scale and speed, and the
demand for mineral raw materials are increasing. On the
other hand, the rich mineral resources are decreasing, and
the poor, fine and miscellaneous complex and difficult to deal
with mineral resources are increasing. Moreover, the recovery
and separation efficiency of valuable components is relatively
low. The utilization rate of resources is depleted, and the
recovery rate of secondary resources is not high. In order to
effectively separate and enrich useful minerals from complex
refractory mineral resources and make full and rational use of
resources, traditional mineral processing methods alone
refractory mineral resources. Therefore, the development of
low-temperature, high-efficiency, and environment-friendly
mineral processing technology to reduce investment costs,
reduce energy consumption and reduce emissions of green­
house gas is a top priority (He 2017).
Flotation and leaching are two important methods in
mineral processing. Reagents are extremely important for
these two methods. Flotation reagents are used primarily in
mineral flotation, including collector, foaming agent, adjusting
agent, flocculant and dispersant. The hydrometallurgical pro­
cess also involves leaching agents and extractants. With the
increase in the development and utilization of mineral
resources, the ore dressing is characterized by low grade, com­
plex association, and fine particle size, and the processing
process tends to be complicated. The reagent used has also
changed from simple and single to mixed use of multiple
reagents, and the general total dosage has increased. During
the storage, transportation and use of these chemicals, there are
some phenomena such as material scattering, chemical decom­
position, and unorganized emission of tail gas. After the ben­
eficiation process, some are sent to the smelter together with
the concentrate, and some are discharged into the tailings pond
together with the tailings. The mineral processing reagent
attached to the tailings will also enter the mine environmental

CONTACT Guocai Tian tiangc@kust.edu.cn; tiangc@iccas.ac.cn State Key Laboratory of Complex Nonferrous Resources Clean Utilization, Kunming University of
Science and Technolgy, Kunming, Yunnan Province, China
© 2022 Taylor & Francis Group, LLC
2 G. TIAN AND H. LIU
water system under the rain wash, causing direct pollution to
the environment, leading to the rise of COD and BOD in the
water body. It may also generate secondary pollutants, includ­
ing persistent organic pollutants (POPs), endocrine disruptors
(EDCs), and compound pollution. Moreover, in recent years,
due to the protection of intellectual property rights, there have
been many minerals processing agents named by codes, where
the main components, main types and protective measures are
unspecified, there are hidden dangers to the safety of users and
the impact of the environment. In general, more and more
reagents are put into use, and the environmental problems
caused by them cannot be ignored. Strengthening the in-
depth research on the green comprehensive utilization tech­
nology of mineral separation and studying a large number of
basic problems of mineral green separation can fundamentally
provide solutions and technical prototypes, realize the rational
and maximum utilization of resources and environmental
friendliness, and also greatly improve the efficiency of the
development and application of mineral resources. It is
a strategic choice to alleviate the bottleneck of resources and
environment, with remarkable economic, social, and environ­
mental benefits. It is of great importance to the sustainable
development of society. It is the only choice to control and
reduce the impact of chemicals in the environment, adhere to
the core concept of green chemistry and take the path to
sustainable development.
In recent years, the green solvent-ionic liquids (ILs) and
deep eutectic solvents (DESs) are known as the most promising
alternatives because of their low toxicity and little effect on the
environment. The utilization of ILs and DESs as reagents and
solvents in mineral processing and valuable element extraction
can provide alternatives to traditional mineral processing and
metallurgical processes to achieve green and cleaner produc­
tion. In mineral processing, the flotation efficiency is easily
Table 1. Commonly used cations and anions for ILs and HBA and HBD for DESs.
ILs Type Cations
Type I: AlCl3 type ionic liquids
Type II: Non AlCl3 type ionic liquids
Type II: Other special ionic liquids
(functional ionic liquids)
DESs Type HBD
Type I: Cat+X-zMeClx, Me = Zn, Sn, Fe, Al,
Ga or In.
Type II: Cat+X−zMeClx·yH2O, Me = Cr,
Co, Cu, Ni or Fe.
Type III: Cat+X−zRZ, Z = CONH2, COOH
or OH and R=organic radical
Type IV: MeClx + RZ = MeClx−1 +·RZ +
MeClx+1, Me =Al or Zn and Z = CONH2
or OH.
affected by many factors. It mainly includes ore properties,
flotation reagent system, flotation equipment, flotation process
flow, and operation factors in the flotation process, such as
grinding fineness, pulp concentration, pulp pH value, aeration
and agitation, reagent type and concentration, flotation time,
water quality, and temperature. The main influencing factors
of mineral leaching include ore properties, ore particle size,
type and concentration of leaching agent, leaching time, liquid-
solid ratio, stirring speed, pH value, etc. In recent years, many
kinds of ILs and DESs are applied in high-efficient floatation
and leaching of some minerals that are difficult to float or
leaching, such as rare-earth minerals, quartz, and quartz hema­
tite, as well as carbonate asphalt. The influence factors men­
tioned above for mineral processing are considered and studied
to find the most optimum condition to achieve the best floata­
tion or leaching efficiency. (Barton and Hiskey 2022; Quijada-
Maldonado et al. 2020; Zante and Boltoeva 2020).
The characteristic features of ILs and DESs
Ionic liquids are liquid at room temperature (Welton 2002),
known as green solvents and electrolytes, which are completely
composed of organic (or inorganic) anions and larger organic
cations. The commonly used cations and anions for ILs are
shown in Table 1. There are many kinds of ionic liquids. At
present, there are three classification methods. According to
different cations, they are mainly divided into imidazole ionic
liquids, pyridine ionic liquids, quaternary ammonium ionic
liquids, and quaternary phosphonium ionic liquids.
According to different anions, it is mainly divided into AlCl3
type ILs, non AlCl3 type ILs, and other special ILs (as showed
in Table 1). According to the different acidity and alkalinity, it
can be divided into acid functionalized ionic liquids, alkali
functionalized ionic liquids and neutral ionic liquids.
Anions
F−, Cl−, Br−, I−, AlCl4−, A12C17−, Cu2Cl3−, Fe2Cl7−, NO3−, PF6−, NO2−, HSO4−, SO42-,
N(CF3SO2)2−, CH3SO3−, BF4−, PO43-, CH3COO−, C3F7COO−, CF3SO3−, (C2H5SO3)2
N−, C4F9SO3−, C2H5BF3−, C3H7BF3−, C4H9BF3−, C5H11BF3−, CH2CHBF3−, FSI−, CH3
BF−, N(CN)2−, C3F7BF3−,C4F7BF3−
HBA

ILs have many special characteristics (Deng 2006; Li 2004;
Zhang 2008; Zhang and Reddy 2010). 1) Low melting point and
wide liquid range. Ionic liquids have a low melting point and
can remain liquid in a wider temperature range of −200°C to
300°C. Therefore, using ILs as the reaction solvent can study and
control the reaction in a wider temperature range. 2) Negligible
or very low vapor pressure. Negligible vapor pressure means
that the volatility of the solvent can be ignored, reducing pollu­
tion and harm. Low vapor pressure makes ILs can be applied in
high-vacuum environment for distillation and sublimation of
the by-products and products, which cannot be achieved by
traditional organic solvents. It will not evaporate during use
and storage, and can be recycled, eliminating the environmental
pollution of volatile organic compounds. Therefore, it is consid­
ered as a green solvent. 3) Good solubility. IL can dissolve many
organic and inorganic substances, polymer and minerals, etc. At
the same time, since most of them are aprotic solvents, solvation
can be greatly reduced, and the compounds dissolved in them
can have high reactivity. 4) Nonflammable and high thermal
stability. ILs can widen its temperature range and make the
power control huger, so they are particularly valuable for
exothermic reactions. This property can also play a valuable
role in temperature-dependent separation technologies, such as
precipitation, crystallization, or extraction. 5) Wide electroche­
mical stable window and high ionic conductivities. It makes
the previous electrochemical processes beyond the limit of sol­
vents can be observed. It can also be used to replace traditional
solvents and electrolytes, and has been successfully and widely
used in the field of electrochemistry, such as metal electrodepo­
sition (especially active metals), electrochemical devices such as
super-capacitor, Li-ion cell, solar cells, and fuel cells. 6)
Designed solvents. Different anions and cations can form var­
ious different ILs. By changing cations, or anions, or varying the
functional groups, the properties of the ILs can be adjusted to
meeting the needs of specific processes. These properties of ILs
have attracted great attention and have been widely and success­
fully utilized in many fields, such as material preparation and
synthesis, catalysts, metal electrodeposition, fuel cells, and so on.
Deep eutectic solvents(DESs) were firstly introduced in
2001 (Abbott et al. 2001). DESs is a new kind of ionic liquid
analogues, which is a mixture of eutectic components formed
by Brønsted or Lewis acids and bases, and its melting point are
lower than that of pure components. They have many similar
characteristics and properties to ionic liquids. But they are, in
fact, two different types of solvents. DESs have low lattice
energy and large asymmetric ions, resulting in low melting
point. They are obtained by complexing compounds (usually
ammonium salts) that act as hydrogen bond receptors (HBA)
with metal salts or organic compounds that act as hydrogen
bond donors (HBD). Since the combination of HBA and HBD
may be large, it can be adjusted according to the user’s purpose.
The commonly used HBA and HBD for DESs, as well as its
classification are shown in Table 1. Therefore, it is considered
as a design solvent and can be customized according to specific
types of chemistry. As same ILs, DESs have many special
characteristics. It has relatively wide liquid range, low vapor
pressure, and non-flammability, easy preparation, low pro­
duction cost (easy to obtain from relatively cheap ingredi­
ents), low toxicity and high tunability, low chemical inertia,
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 3
high biodegradability, easy shipment for large-scale proces­
sing (Abbott et al. 2001, 2003; Smith, Abbott, and Ryder 2014).
In recent years, ILs and DESs have been widely and success­
fully applied and studied in many fields (Figure 1), such as
extraction (Devi and Sukla 2019; Dietz 2006; Erust et al. 2021;
Erust, Karacahan and Uysal 2022; Krishnamurthy and Gupta
2002; Liu, Chen, and Li 2012; Meshram and Abhilash 2020;
Kubota, Baba and Gotoet 2012; Dwamena 2019; Dedzo 2019;
Perna, Vitale and Capriati 2020; Yuan et al. ban 2022; Nguyen
and Lee 2019), catalysis, metal oxides and mineral processing
(Tian, Li, and Hua 2009, 2010; Abbott et al. 2011; Richter and
Ruck, 2020), batteries, secondary resource recovery (Chandra
et al. 2022; Jafari et al. 2022; Jdid et al. 1995; Tran, Moon, and
Lee 2021, 2022) and separation of compounds (Meindersma
et al. 2006) etc.
In this paper, we mainly focused on the utilization of ILs and
DESs in mineral processing. We first introduced the characteristics
of ILs and deep DESs, then introduces the progress of the flotation
research in ILs and DESs for rare-earth ores, quartz, quartzite, and
so on, and then discusses the research progress of ILs and DESs in
the leaching of valuable metals in chalcopyrite, sulfide ores, gold
and silver ores and so on. Then, the interaction between ionic
liquids and common minerals in soil is analyzed, which provides
help in understanding the impact of ionic liquids on Soil and
groundwater. Finally, a summary and outlook are made.
Mineral flotation
Mineral flotation is one of the most common and important
methods in mineral processing. Its introduction has greatly
improved the utilization and productivity of mineral resources,
greatly reduced the cutoff grade of mineral resources develop­
ment, and thus improved the guarantee of mineral resources
for the development of the world economy. One of the impor­
tant factors to ensure the success of mineral flotation is to
choose efficient and selective flotation reagents. Flotation
reagents have traditionally been an important research direc­
tion in mineral processing. In recent years, lots of efficient
flotation reagents have been synthesized and developed for
different minerals processing, including collectors, foaming
agents, activators, inhibitors, dispersants, modifiers, etc., to
recover valuable minerals from ores (Hu 2014; Wang 2017;
Wills and Finch 2016). A variety of inorganic and organic
reagents such as xanthate, black medicine, mercaptan, alkyl
carboxylate, sulfate, sulfonate, phosphate, amine, alkyl phos­
phoric acid, hydroxamate, and chelating agents with different
excellent properties are used in mineral flotation. (Wills and
Finch 2016; Hu 2014; Wang 2017). However, in view of the
increasingly complex mineral resources and the strict require­
ments of environmental protection, these flotation reagents
appear monotonous in variety and small in quantity, which is
difficult to meet the requirements of various complex pro­
cesses. Moreover, with the less and less single mineral
resources and the increase in the development and utilization
of poor, fine and miscellaneous mine resources and secondary
resources, higher diversified technical requirements are put
forward for beneficiation reagents. Therefore, the research
and development, preparation and application of high effi­
ciency, low toxicity, and environmental friendly beneficiation
4 G. TIAN AND H. LIU
Figure 1. Application of ILs and DESs.
reagents have become the focus of mineral flotation and
mineral leaching research. ILs and DESs, which are green
solvents with the characteristics of an adjustable structure,
non-flammability, low vapor pressure, and almost nonvolatile,
have been used to process some minerals that are difficult to
float and some progress has been made (Chen et al. 2021; Eney
de Matos et al. 2022a, 2022b; Kowalczuk et al. 2018).
Rare earth ore
Rare Earth (RE) is the general name of 15 Lanthanides and the
Scandium and Yttrium (a total of 17 elements) in the Periodic
Table of chemical elements (Abaka-Wood, Addai-Mensah, and
Skinner 2017; Jordens, Cheng, and Waters 2013;
Krishnamurthy and Gupta 2016; Zhang et al. 2016). Rare
Earth is an important strategic resource, many of which are
used in cutting-edge electronic equipment. Among the 35
high-tech elements published by the U.S. Department of
Defense, and the 26 high-tech elements selected by the Japan
Science and Technology Agency, 16 rare-earth elements except
PM are included. The rare-earth sources that have been dis­
covered in the world are mainly distributed in a few countries.
China is the one that has found the most rare-earth resources,
followed by the USA and Russia, and then India, Australia,
Canada, and other countries. The most important rare-earth
minerals are monazite ((REE)PO4), fluorocarbon cerium
(Lanthanum) ore ((REE)FCO3), Yttrium phosphate ore,
Xenon irons ore (YPO4), ion adsorption rare earth ore,
brown yttrium niobium ore, etc. Some of the major deposits
are found, such as Bastnäsite of Bayan Obo in China and
Shankouin the United States, Xenotime of Lehat in Malaysia,
the Monazite of Green Cove Spring in the USA and Mount
Weldin Australia, and the rare-earth carbonate deposits con­
taining Bastnäsite and Monazite in St Honoré in Canada.
Common collectors used in the flotation of RE minerals
include carboxylates (fatty acids), hydroxamates, and some
organic phosphoric acids (Abaka-Wood, Addai-Mensah, and
Skinner 2017; Jordens, Cheng, and Waters 2013;
Krishnamurthy and Gupta 2016; Suli et al. 2017), which face
problems such as non selectivity and sensitivity to impurity
ions. ILs and DESs have attracted much attention since their
design-ability, low vapor pressure, non flammability, and basi­
cally nonvolatile characteristics, and are employed in the rare-
earth ores flotation and the extraction of rare-earth elements.
Freiderich et al. (2015) used 1-Butyl-3-MethylImidazolium
bis(trifluoromethyl-sulfonyl)imide ([Bmim]Ntf2) and acidic
N-dimethylacetamide bis(trifluoromethyl-sulfonyl)imide
([DMAH]Ntf2) ILs for the flotation of best concentrate and
the synthesis of Bast like minerals (RECO3F) and RE2O3 and

RE2(CO3)3 (Freiderich et al. 2015). The results show that
bastnäsite will use two acidic protons and then forms soluble
HREE and insoluble REF3 in the dissolution process. HREE
such as Eu, Ho, and Y dissolves faster in ILs than light HREE
such as La and Nd, and this process allows HREE to be
enriched in ILs for a short time. They found that an average
% RE dissolved value of 60% for RECO3F solids in ILs, whereas
the almost all RE were quantitatively dissolved in Nd2(CO3)3
and Nd2O3 solids after 24 h. Although the ILs system has dense
ions and shows potential solvation ability and ionic interaction
with Re3+ ions, the precipitation of ReF3 is not inhibited. In
addition, the release of CO2 from the dissolution process is
necessary to advance the reaction. This work is the first report
on the application of pure ionic liquids in the dissolution of
rare earth ores. ILs can provide a good environment for a larger
re-separation scheme of bastnäsite flotation concentrate.
Azizi, Larachi, and Latifi (2016) and others studied the
flotation of bastnäsite minerals and model monazite with tetra­
butyl bis(2-ethylhexyl)-ammonium phosphate ([N4444]DEHP)
ILs aqueous, Aero-6493 (6–10 carbon alkyl chains) and Aero-
9849 (10–18 carbon alkyl chains) as collector by micro-
flotation test, Zeta potential measurement, FTIR and XPS.
Compared with quartz, dolomite, and calcite minerals as typi­
cal gangue minerals, ILs have superior flotation performance
for these two models rare earth (RE) minerals. In the micro-
flotation test of two minerals, it is found that [N4444]DEHP has
a stronger collection capacity than the collector containing
hydroxamic acid. The recovery (Nd+Ce+La)% are 64.6, 54.5,
and 74.5, while the enrichment ratios are 1.05, 1.01, and 1.43
for Aero-6493 and Aero-9484 and [N4444]DEHP respectively.
It has weak affinity with calcite, dolomite, and quartz (as typical
gangue). In addition, [N4444]DEHP is superior to niobec rare
earth ore flotation with hydroxamic acid collector. It was found
that [N4444]DEHP was chemically adsorbed on the surface of
bastnasite and monazite through the P = O and P-O groups of
the anionic part. The IL anion layer through electrostatic
attraction and/or chemisorption interacts with the hydropho­
bic chain of the cationic alkyl chain to promote the absorption
of the cationic moiety. The most sensitive calcite surface in
gangue minerals has weak interaction with IL.
Azizi, Sarvaramini, and Larachi (2017) studied the enrich­
ment potential of [N4444]DEHP, tetraethyl-ammonium dioc­
tyl-phosphate ([N2222]DioctP) and tetraethylammonium bis
(2-ethylhexyl)-phosphate ([N2222]DEHP) for monazite, calcite,
dolomite, and bastnäsite containing rare-earth minerals. The
multiphase beneficiation system consists of mineral water
slurry, in which ILs/n-hexane and ILs/kerosene nonpolar
phases are emulsified with three kinds of ammonium/phos­
phonium-based ILs to assess the chelation potential. It is noted
that liquid–liquid mineral separation is suitable for the bene­
ficiation of coarse and fine REM particles. The pH value of
aqueous pulp plays a major role in mineral recovery. When the
pH value is 4–7, the recovery rate of rare earth minerals is the
highest. When the pH value is less than the isoelectric point of
mineral, the liquid–liquid mineral separation test of kerosene
as an organic solvent is better than that of n-hexane. The
electrokinetic properties of IL/coal water or IL/n-hexane
water lotion can be adjusted by changing the nonpolar phase,
IL type, or IL concentration. It was found that the cationic part
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 5
of ILs participated in the weak Coulomb van der Waals inter­
action, while the anionic part played a key role in the surface
complexation of minerals, which directly interacted with the
active center of metal cations by forming covalent bonds. The
order of mineral recovery is bastnaesite > monazite > calcite >
dolomite, which is independent of pH value, IL concentration,
particle size, or solvent. The >90% REM recoveries are achiev­
able provided the REM particles are in the −38 μm range. This
is illustrated in the case of bastnäsite −38 μm fraction at pH = 4
and 150 ppm IL in n-hexane or kerosene which exhibited
virtually the lowest REM leftovers (<7%) in the aqueous pulp
as compared with the +38–105 μm fraction. This beneficiation
method is effectively applied to practical rare earth bearing ore
and technical grade single model minerals. The separation of
liquid–liquid minerals depends on factors such as pH, type of
organic solvent and ILs, IL concentration, and mineral particle
size. The author believes that if the superior ability of ionic
liquids in mineral separation is confirmed, its large-scale pro­
duction and commercial application in mineral processing will
certainly help to reduce its cost intensity, which is far lower
than the cost intensity of these atypical reagents in the current
exploration and research stage.
Then, they studied the potential enrichment of minerals
containing rare earth elements by the ILs–ILs mineral separa­
tion process in a new ILs system (Azizi and Larachi 2018). The
mineral separation test of complex rare earth ores whose main
constituent minerals are monazite, bastnäsite, dolomite, cal­
cite, and ankerite in the [N4444]DEHP, [Bmmim]BF4 (1-butyl-
2,3-dimethylimidazolium tetrafluoroborate), [EtNH3]NO3
(ethylammonium nitrate), and [Emim]SCN (1-ethyl-3-methy­
limidazolium thiocyanate) was studied. The partial results
shown in Figure 2. The beneficiation system uses two immis­
cible ILs as continuous phase and dispersed phase. Using
[N4444]DEHP as the droplet phase and [EtNH3]NO3,
[Bmmim]BF4, and [Emim]SCN as the continuous phase, this
beneficiation method for rare earth complex ore was evaluated.
The recovery of monazite, bastnäsite, calcite, ankerite, and
dolomite are 83.9, 82.2, 21.4, 15.7, and 79.8 for [EtNH3]NO3,
while that is 90.7, 87.9, 29.5, 21, and 86.6 for [Emim]SCN,
respectively. The recovery in [bmmim]BF4 was basically 0. It
is found that the order of the intensity of IL mineral interaction
is: bastnaesite > monazite > ferridolomite > calcite > dolomite,
which is consistent with the results of ILs–ILs separation. It was
found that the anionic part of [N4444]DEHP interacted with the
mineral surface through the inner sphere interaction, while the
cationic part of IL participated in the outer sphere interaction,
and the cationic and anionic IL parts presented cis conforma­
tion on the mineral surface.
Davris, Marinos, and Balomenos (2018) used betainium
bis(trifluoromethylsulfonyl)imide ([Hbet]Ntf2) ionic liquids
leaches a low-grade rare earth (REE) ore named Rödberg
from the Fen carbonate complex deposit in Norway. The ore
mainly exists in the form of fluorocarbonate of bastnäsite
group minerals. The effects of pulp density (%w/v), leaching
temperature, moisture contents of ionic liquid and residence
time on leaching were studied. It is found that the recovery rate
of heavy rare earth and light rare earth in Rödberg ore leached
with [Hbet]Ntf2 is 65–100% and 40–60%, respectively. In addi­
tion, more than 80–90% of calcium and magnesium are
6 G. TIAN AND H. LIU
Figure 2. Recovery of calcite, monazite, bastnäsite, dolomite and ankerite in IL-IL separation. [Reprinted (Azizi and Larachi 2018) with permission from Elsevier].
dissolved. [Hbet]Ntf2 is selective for iron and silicon, resulting
in silicon/iron rich residues. The REE metal dissolved in
[Hbet]Ntf2 can be enriched by acid stripping with acidic aqu­
eous solution, and the ionic liquid can be regenerated for reuse.
It is showed that the carboxylic acid functional group on the
cation side of [Hbet]Ntf2 can dissolve bastnäsite well. So it is
possible to develop new alternative methods for treating low-
grade REE primary resources.
Li et al. (2020a) used tetraheptylammonium linoleate (TL)
and tetraheptylammonium oleate (TO) ILs to recover REEs
from ion adsorption REE ore leaching solution. It was showed
that the system has good extraction performance. It was found
that less than 1 min was enough for the extraction equilibrium
of rare earth elements, and the extraction efficiency of TO and
TL was close to 100%. This shows that high efficiency of the
extraction process can be obtained from the kinetic aspect,
which shows the potential of industrial application. The extrac­
tants reveal better extraction abilities for heavy REEs than light
REEs in TO and TL. Comparative study of commercial extrac­
tants and precipitants (P507, NA, H2C2O4 and NH4HCO3)
indicated that TC had higher extraction capacity of REEs
from the leaching liquor. REEs recovery yield by TC was nearly
100%, which was the highest efficiency. The extraction order of
TL follows, Lu > Yb > Tm > Er > Ho > Dy > Tb > Gd > Sm > Nd
> Y > Pr > Ce > La, which is similar to some other carboxylic
acid type extractants. The naturally occurring anion, sustain­
ability, biocompatibility, and non-toxicity, as well as simple
synthesis route and excellent extraction performances make
these cooking oil-based ILs promising for REEs recovery
from the leaching liquor.
Dong et al. (2020) prepared two kinds of ionic liquid func­
tional cellulose microspheres 1-aminopropyl-3-methyl imida­
zolium chloride ([FC]Cl) and 1-aminopropyl-3-methyl
imidazolium nitrate ([FC]NO3) by radiation technology, and
studied their performance of separating RE(VII). The partial
results shown in Figure 3. [FC]NO3 and [FC]Cl have the
characteristics of fast adsorption speed, high adsorption
capacity ([FC]NO3 of 581 mg/g and [FC]Cl of 552 mg/g) and
good reusability for high concentration RE(VII). It is found
that ILs is recovered four times, and its capacity loss is basically
negligible. The obtained maximum adsorption capacities from
the Langmuir model were 581 mg/g and 552 mg/g for [FC]NO3
and [FC]Cl, respectively. Their maximum adsorption capaci­
ties were much higher than that of reported adsorbents
[FC]NO3 can recover the trace RE(VII) from aqueous solution
and shows good rare earth/uranium selectivity.
Li et al. (2021) used [N2222]EHEHP (Tetraethylammonium
mono-(2-ethylhexyl) 2-ethylhexyl phosphonate) as a flotation
collector for the main rare earth mineral (REM) source of rare-
earth production of bastnäsite, studied its collection perfor­
mance, and compared it with two common gangue minerals of
quartz and hematite in rem deposit. The partial results showed
in Figure 4. It is found that the floatability of hematite is higher
than bastnäsite in [N2222]EHEHP. A highest recovery about
50% is obtained at pH 5, however relatively high IL dosage of
500 g/t is needed. At the same condition, the recovery of
hematite is over 80% and ∼10% for quartz. It was found that
the phosphonic acid group of the collector is adsorbed on
bastnäsite and hematite through chemical adsorption, while
ILs is hardly adsorbed on quartz. The collecting capacity of
[N2222]EHEHP for hematite is larger than the capacity of
bastnäsite, and the recovery is more obvious with the increase
of IL dose. The recovery rate of bastnäsite can reach more than
90%, and the maximum upgrading ratio is 1.7. It is found that
the ionic liquid has a huge potential for the processing of low-
grade rare-earth ore.
Quartz and quartz hematite
Quartz is an oxide mineral with stable chemical and physical
properties, mainly composed of SiO2. It is primarily used for
preparing silica refractories, silica sand, and sintered ferrosili­
con, as well as purification and separation materials of high-
purity silica. Quartz is a widely used and widely distributed
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 7

Figure 3. Influence of competing cations (a) and anions (b) on the Re(VII), and metal extraction (c) in [FC]NO3 and [FC]Cl. [Reprinted (Li et al. 2020a) with permission
from Elsevier].

Figure 4. Flotation recoveries of synthetic mixture of 50–500 g/t (a, c) and 100–1000 g/t (b, d) of ILs at pH of 5. [Reprinted (Li et al. 2021) with permission from Elsevier].
8 G. TIAN AND H. LIU
mineral resource that can meet the global industrial demand.
However, quartz is one of the impurity minerals in the separa­
tion process of the most natural ores, such as iron ore, phos­
phate rock, feldspar, cassiterite, kaolin, etc. Therefore, the
enrichment and separation of quartz minerals are very impor­
tant for industry. Foam flotation is one of the effective methods
to selectively separate the required minerals released from fine
particles. In this technology, collectors play a major role in
enhancing the quality of the required mineral species. The
selection of collectors plays an important role in enriching
the required flotation minerals in the flotation process (Shen
et al. 2016; Wang et al. 2015; Yang et al. 2019; Zhang et al.
2021). At present, dodecyl amine chloride and acetate are the
most widely used collectors of flotation desilication, such as
cetyltrimethylammonium bromide (CTAB), dodecylamine
chloride (DDA), ester amine or ether, and quaternary ammo­
nium salt, which are applied as collectors of for quartz flotation
(Wang et al. 2015). The final beneficiation efficiency selectivity,
and collection capacity of collectors are affected by various
factors. Some works have been performed to study the effects
of carbon-chain length, and anion type on amine collectors
(Shen et al. 2016). Researchers have been looking for more
effective reagents and using various methods to reduce the
dosage and improve the effect of flotation (Yang et al. 2019;
Zhang et al. 2021).
Ammonium-based ionic liquids have recently been used as
quartz collectors to separate quartz from hematite (Sahoo et al.
2015a, 2015b, 2016; Sahoo, Rath, and Das 2014, 2020). It is
found that the interaction between the groups of ammonium-
based ILs and quartz are essentially physical adsorption, which
is caused by the attractive van der Waals interaction between
the surface and the long alkyl chain and the electrostatic inter­
action between the positively charged ions and the negatively
charged quartz surface. In this case, the length of an alkyl chain
will affect the attraction between minerals and imidazole, and
pyridine-based ILs have also recently been used as quartz
flotation collectors to separate the mineral from hematite.
The result of all these studies is shown that ammonium and
pyridine can contribute to better quartz flotation because of the
longer chain length of alkyl and the promotion of more hydro­
phobicity. Subsequently, the flotation contrast experiment
between pyridine, imidazole-based ILs and quaternary ammo­
nium salt, and traditional flotation reagents were also carried
out (Sahoo et al. 2016).
Sahoo, Rath, and Das (2014) used TOMAS (a tricapryl­
methyl ammonium salicylate) as a trapping agent for quartz
flotation. It is found that the electromotive potential of quartz
in all pH ranges is negative, while the electromotive potential of
processed quartz is positive, indicating that there is a strong
interaction between quartz and Thomas at all pH values.
Thomas can improve the hydrophobicity, and it will adsorb
on quartz. Thomas has stronger adsorption with quartz. When
the same flotation capacity is achieved, the dosage of Thomas is
less than DDA. Then, the flotation experiments of low-grade
BHQ (banded hematite rock) ore and pure quartz were con­
ducted, and the overall performance of Thomas and DDA on
pure quartz was compared. It is found that the concentration of
Thomas is lower than that of DDA when 100% quartz is
recovered. The effects of pulp concentration, pH value, and
Thomas concentration on the grade and recovery of Fe were
investigated. It was found that the recovery of Fe decreased
with increasing of Thomas concentration, while the grade of Fe
was just the opposite. The taste of Fe in alkaline is higher than
that in acidic, but the recovery rate of Fe will decrease with
increasing of the pH value; With increasing pulp concentra­
tion, the taste of Fe enhances first and then decreases gradually.
When pH = 7 and pulp concentration is 500 g/t, the concentra­
tion of Thomas is 3.71 × 10−5 M), the recovery of Fe is 66.6%,
and the highest grade of Fe is 67%.
The ionic liquid Aliquat-336 (a mixture of decyl/trioctylam­
monium chloride) was used for flotation separation of quartz
and hematite (Sahoo et al. 2015a). Flotation experiments of
quartz, hematite, and their synthetic mixtures show that
Aliquat-336 has a selective collection effect on quartz. When
the dosage of Aliquat-336 is 280 g/t, 97% of quartz floats in
weak alkaline pH (8), while the recovery rate of hematite is only
8%. Using starch as a hematite inhibitor and Aliquat-336 as
a quartz floatation collector, the synthetic mixture of quartz/
hematite (1:1) was floated to obtain an iron concentrate with an
iron content of 63–65% and a recovery of 85–88%. The reverse
flotation with Aliquat-336 as a collector was performed for
low-grade banded hematite quartzite (BHQ). A 65% iron can
be obtained from iron ore with a recovery rate of 60%. The
adsorption between Aliquat-336 and quartz is electrostatic
adsorption in system.
They studied the performance of six quaternary ammonium-
based ionic liquids of Tetrahexylammonium iodide (THEX),
Tetrabutylammonium hydroxide (TBUT), Tetraoctylammonium
chloride (TOCT), Tetraheptylammonium bromide (THEP),
Tetradodecylammonium bromide (TDOD), and
Tetrakisdecylammonium bromide (TDEC) as quartz flotation
collectors (Sahoo et al. 2015b). The influence of the carbon num­
ber in four ILs with the same alkyl chains on flotation was studied.
It found that THEX has the maximum capacity of adsorption. The
results compared with the commonly used CTAB and DDA
collectors. Some results are presented in Figure 5. The results
show that by applying ILs from TBUT to THEX, the recovery of
quartz flotation increases, and decreases with a further increase of
alkyl-chain length. It is observed that the recovery of CTAB
flotation is better than that of DDA, but the recovery of DDA
and CTAB is lower than that of THEX and THEP ILs. This shows
that ionic liquids had better performance as quartz collectors.
When the concentration of THEX is 4.8 × 10−5 M, 100% of quartz
floats, while 92% for THEP. The recoveries of quartz in CTAB and
DDA are 52% and 32%, respectively. ILs collector also used for
low-grade banded hematite quartzite (BHQ) iron ore flotation. It
is found that iron grade increases with increasing the collector
concentration (Figure 5). The THEX and THEP showed a good
response in all reagents. The iron concentrates with iron content
of 63.6% and recovery of 63.2% could be obtained with 4.1 × 10−5
M of collector. Iron recovery decreases gradually with increase of
the collector concentration. ILs is adsorbed on the quartz surface
by the van der Waals force and electrostatic interaction.
Compared with the traditional quartz collector, the ionic liquid
collector has better quartz collection effect, and no foaming agent
is necessary for flotation. After repeated use and regeneration, the
flotation effect of ionic liquid has not changed significantly.
Therefore, it has the potential for further industrial application.

Figure 5. Flotation results of Quartz (a) and BHQ (b) with different concentration and types of collector. [Reprinted (Sahoo et al. 2015b) with permission from Elsevier].
They studied the performance of five imidazole, ammo­
nium, and pyridine ionic liquids, such as 1-octyl-3-methylimi­
dazole chloride ([Omim]Cl), 1-decyl-3-methylimidazole
tetrafluoroborate ([Dmim]BF4), 1-hexyl-3-methylimidazole
chloride ([Hmim]Cl), benzyl-dimethyl-tetradecyl ammonium
chloride (BDTA), and cetyl-pyridine bromide (CPA) as quartz
flotation collectors (Sahoo et al. 2016). Flotation studies were
performed on pure quartz, low-grade BHQ ore, and synthetic
mixture of quartz hematite. The partial results are presented in
Figure 6. It is found that the pure quartz flotation in pyridine-
based ILs and ammonium collectors showed excellent perfor­
mance. The order for foam flotation experiment follows CPA >
BDTA > [Dmim]BF4 > [Omim]Cl > [Hmim]Cl. In the reverse
flotation process of BHQ ore and synthetic hematite quartz
mixture, ammonium, and pyridine-based collectors also
showed a better recovery and iron grade than imidazole-
based collectors. Use 5.2 × 10−5 M of CPA can float 100%
quartz, which is far lower than that of conventional collectors
(such as CTAB and DDA). The iron recovery of BHQ ore was
75% and 62–63% for BDTA and CPA with 2.7 × 10−5 M of
collector. It is found that the alkyl-chain length plays a key role
in deciding the floatability, and as a factor it is more dominat­
ing compared to the interaction pattern of the IL with the
quartz. In the case of ammonium and pyridine-based collec­
tors, the better flotation results can be related to the longer
alkyl chain which results in better hydrophobicity.
4-Methyl-4-octyloxymethylmorpholinium chloride ([C1-
MOR-C1OC8]Cl) and 1-Methyl-1-octyloxymethylpyrrolidi­
nium chloride ([C1-pyrr-C1OC8]Cl) ILs were used to study
their effects on the stability of quartz suspensions (Bastrzyk
and Feder-Kubis 2018). It was found that increasing the con­
centration of ILs. The adsorption of its molecules on the
mineral surface led to the change of mineral surface properties,
which increased the turbidity stability index (TSI) of morpho­
line salt and pyrrolidine salt. ILs adsorption on the quartz
surface leads to a more hydrophobic surface, which changes
the zeta potential of morpholine chloride and pyrrolidine
chloride greatly. These ‘green compounds’ have strong surface
activity and can replace harmful cationic surfactants com­
monly used in industry, creating opportunities for the use of
these environmental protection compounds in the mining
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 9
industry and helping to develop environmental protection
technologies in mining processing.
Four different ionic liquids, such as 1-dodecyl-3-methylimi­
dazolium bromide (DMB), 1-dodecyl-3-methylimidazolium
chloride (DMC), 1-dodecyl-3-methylimidazolium hexafluoro­
phosphate (DMH), and 1-dodecyl-3-methylimidazolium tetra­
fluoroborate (DMT), were used as collectors to carry out
flotation experiments on mixed ores of pure quartz and quartz
hematite (Chen et al. 2022). Some results are shown in Figure 7.
The flotation results of pure quartz show that all ionic liquids
have good collection performance, and more than 95% of quartz
are in a (8 × 10−5mol. L−1) when floating below the concentra­
tion, the capacity of collection in all ILs is much better than that
of traditional DDA collector. The order of collecting capacity is
DMH > DMT > DMB > DMC. The flotation test results of
mixed ore show that the flotation effect of the four ionic liquids
is better than that of DDA in the inhibitor test. When there is no
inhibitor, except DMH, the selectivity in other ILs is better than
DDA. DMH has the highest efficiency of beneficiation with
inhibitors inside because of its strongest capacity of collection.
The effect of imidazole ILs containing chlorine ligand as
a collector is the best. 61.9% grade iron ore can be obtained
from hematite/quartz mixed ore with a total ferrite of 51%, and
the recovery is 94.54%. Using a starch inhibitor, the highest
efficiency of beneficiation with 64.86% iron concentrates, and
86.07% recoveries were reached for imidazole-based ILs con­
taining hexafluorophosphate ligand. It is found that anions
affect the flotation performance of the system by affecting the
formation of semi micelles. The semi micelle formed by dode­
cylamine is unstable in adsorption, so its collection ability is
weak. Three of the four ionic liquids have higher collection and
selectivity at the same time, which is related to the higher charge
density of forming half micelles and the lower charge density of
a single adsorption site.
Asphalt carbonate rocks
Zhang et al. (2018) synthesized a new amino acid ILs based DESs
([Trp]BF4/U) from tryptophan fluoborate ([Trp]BF4) and urea
(U). TrpBF4/U were combined with ethanol and toluene to form
a non-aqueous surfactant-free microemulsion. [Trp]BF4/U based
10 G. TIAN AND H. LIU
Figure 6. The Fe grade and Fe recovery in the flotation of BHQ (a ,c) and synthetic mixture of quartz and hematite (b, d). [Reprinted (Sahoo et al. 2016) with permission
from Elsevier].
lotion was utilized to extract super-heavy oil from Indonesia
asphalt carbonate rocks. The results show that the recovery of
crude oil is improved by at least 11% comparing with [Trp]BF4/U
microemulsion. Compared with the traditional [Emim]BF4 ILs,
the quality of the new system oil (less entrained solids) and
residual solids (fewer attached solvents) also were improved. It
showed that the Bitumen recovery was up to 93.04% for [Trp]BF4
/U-based micro-emulsion, which was significantly higher than
those of traditional single toluene extraction (81.27%) and
[Emim]BF4-toluene hybrid extraction (90.12%). It was found that
[Trp]BF4/U microemulsion can be reused and recycled at least
four times without reducing efficiency.
From the above research works summary, it can be seen
that the application of ILs and DESs in the flotation of
some minerals has also been studied, and excellent results
have been achieved. The dosage used is obviously less than
that of traditional reagents, and the selectivity and effect of
flotation are better than those of traditional systems.
Compared with the traditional quartz collector, the ionic
liquid collector has better quartz collection effect, and no
foaming agent is necessary for flotation. The alkyl-chain
length plays a key role in deciding the floatability, and as
a factor it is more dominating compared to the interaction
pattern of the ILs with the quartz. Therefore, it has the
potential for further industrial application. In addition, ILs
and DESs have almost no vapor pressure, which will not
evaporate and leak during use, and are easy to be regener­
ated and recycled. Although ILs and DESs have very been
promising results for various mineral flotation systems, ILs
and DESs are completely different from traditional flotation
systems as a new green solvent. Therefore, the flotation
solution chemistry, the thermodynamics and dynamics of
flotation in ILs and DESs, the interaction between
particles and mineral surfaces, the adsorption/desorption
mechanism, and the migration of ions in the system must
be very different from the traditional system, and these
aspects are still lacking. At the same time, the research of
ionic liquids and deep eutectic solvent system in mineral
flotation is not much, and their further applications need to
be continuously studied and expanded.
Mineral leaching
Mineral leaching is to use appropriate solvents to dissolve one
or more valuable components in ore or concentrate or roasted
ore under certain conditions and separate them from gangue
and impurities. A good leaching system is one of the important
factors of mineral leaching process. Mineral leaching has
become an important method for the separation and extraction
of many valuable elements because of its advantages of envir­
onmental friendliness, simple operation, low energy consump­
tion, and low cost. However, there are many problems in
traditional mineral leaching or hydrometallurgy, such as low
metal recovery, large acid consumption, difficulty of recycling
waste acid and recovery of leaching residues. Therefore, it has
become an urgent task for today’s green metallurgy and envir­
onmental protection industry to find new leaching media to
reduce acid consumption and pollutant emissions. Compared
to traditional solvents, ILs and DESs can dissolve many inor­
ganic substances, especially metal oxides. They have selective
solubility, nonvolatile, combined variability of structure and
performance (strong designability), easy regeneration and
environmental-friendly. ILs and DESs as leaching agents was
used to leach the ores and waste minerals to extract various
metals from their main minerals (Barton and Hiskey 2022; Hu
et al. 2017; Hu, Zi, and Tian 2021; Park et al. 2014; Quijada-
Maldonado et al. 2020; Tian, Li, and Hua 2009, 2010; Zante and
Boltoeva 2020)

Figure 7. Flotation results of a mixture of quartz and hematite without inhibitors for A, B, C and with inhibitors for D, E, F. [Reprinted (Cheng et al. 2022) with permission
from Elsevier].
Chalcopyrite
Chalcopyrite is one of the most common copper sulfide ore,
and also the most difficult to leach copper sulfide ore. The
leaching of chalcopyrite is the core of copper sulfide ore hydro­
metallurgy. For many years, people have been committed to
various hydrometallurgical processes of chalcopyrite. At pre­
sent, various direct leaching methods of chalcopyrite leaching
mainly include: direct leaching method (materials are not sub­
ject to pre-treatment, and strong oxidants are directly added to
destroy the lattice of chalcopyrite, making copper easy to
leach), roasting leaching method. Although copper hydrome­
tallurgy has made remarkable progress, most of the existing
technologies and processes deal with oxidized ore and waste
rock, and there are still problems such as serious corrosion,
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 11
high-energy consumption, long cycle, and low selectivity.
Research on hydrometallurgy of chalcopyrite is less and still
very challenging. Therefore, it is still an urgent task for metal­
lurgists to develop new theories and methods of chalcopyrite
hydrometallurgy with strong adaptability to minerals, low
energy consumption, low emissions and operation under low
temperature and low pressure. The emergence of ILs and DESs
provides a new possible way to achieve this goal (Barton and
Hiskey 2022; Hu et al. 2017; Hu, Zi, and Tian 2021; Park et al.
2014; Quijada-Maldonado et al. 2020; Tian, Li, and Hua 2009,
2010; Zante and Boltoeva 2020).
McCluskey et al. (2012) used Fe(BF4)3 as an oxidant to
leach chalcopyrite in [Bmim]BF4 (1-butyl-3-methylimidazo­
lium tetra-fluoroborate). It was found that the copper
12 G. TIAN AND H. LIU
Figure 8. The effect of ionic liquid (a) and oxidants (b) on chalcopyrite leaching.
leaching rate exceeded 90% after leaching at 100℃ for 8
h. Whitehead, Lawrance, and McCluskey (2004) reported
the leaching of gold ore, copper sulfide ore, and silver ore in
the 1-butyl-3-methylimidazolium hydrogen-sulfate
([Bmim]HSO4) aqueous solution by using Fe2(SO4)3 as the
oxidant. It showed that the rate of copper leaching could
reach 85%, which was larger than that in H2SO4 solution
under the same conditions, and the leaching rate of iron
was less than 8%, indicating that ionic liquid has the potential
of selective leaching chalcopyrite. The chalcopyrite was oxi­
dized and leached with O2 in [Bmim]HSO4 medium by Dong
et al. (2009). After 24 h, the Cu leaching rate reached 89.1%.
The leaching process of chalcopyrite can be described by kt =
1-2/3x-(1-x)2/3 model. The leaching of chalcopyrite in present
system is diffusion determined process, with an activation
energy of 69.4 kJ/mol.
The leaching of chalcopyrite with two acidic imidazole
based ILs of [Bmim]HSO4 and [Hmim]HSO4 (1-hexyl-
3-methyl-imidazolium hydrogen sulfate) at different tempera­
tures was studied, and the copper recovery in the presence of
aqueous solution and sulfuric acid was monitored (Carlesi et al.
2016). When ionic liquids and acids are utilized in the same
time, a synergistic effect is found. The role of IL is to reduce the
resistance of hydrophobicity of solid solutions to electron

transfer, to achieve continuous acid leaching. The copper
recovery rate increases significantly as the temperature is larger
than 60 ℃ (the recovery rate of copper is as high as 70%). They
believed that the increase of temperature enhances the chemi­
cal decomposition rate of intermediates of metal sulfide and
reduces the mass transfer limitation in the solution. It is con­
sidered that ILs can be regarded as leaching additives or cata­
lysts rather than leaching agents themselves.
The effects of temperature, chloride and sulfuric acid,
[Bmim]HSO4 on copper extraction from CuFeS2 ore were
studied (Aguirre et al. 2016). The best copper extraction con­
ditions obtained is 90 ℃, 100 g.L−1 chloride, 20% (v/v) of
[Bmim]HSO4 aqueous. Temperature and chloride concentra­
tions play a synergistic role in promoting the dissolution of
chalcopyrite. A model was designed to predict the copper
extraction from CuFeS2 ore using [Bmim]HSO4, Cl-, H2SO4.
The activation energy is 60.4 kJ/mol (temperature range 30–90
℃) for leaching process, indicating it is a chemical-reaction
determined process.
We systematically studied the oxidation leaching of chalco­
pyrite in [Omim]HSO4 (1-octyl-3-methylimidazolium hydro­
gen sulfate), [Bmim]HSO4, [Emim]HSO4 (1-ethyl-
3-methylimidazolium hydrogen sulfate), and [Hmim]HSO4
aqueous solution. It is found that the leaching rate of chalco­
pyrite in pure ILs is very low. Oxidant addition in aqueous
solution can significantly enhances the leaching rate and
shorten the leaching time (Hu et al. 2017; Hu, Zi, and Tian
2021). At 70 ℃, the rotating speed of 400 r/min, and the
chalcopyrite size of −75 + 45 μm and 24 h leaching, the rate of
chalcopyrite leaching in different kinds of ionic liquid aqueous
solutions first decreases and then increases with the increase of
carbon chain. As showing in Figure 8a, the best ionic liquid is
[Emim]HSO4. We studied the effect of oxidants of (NH4)2S2O8,
KBrO3, KClO3, KMnO4, NaBiO3, KIO4, Fe2(SO4)3, NH4NO3
on the leaching rate of chalcopyrite in 10%(v/v) [Emim]HSO4
aqueous solution at 70 ℃. Some results are shown in Figure 8b.
The results show that the leaching effect is better when KBrO3
and KIO3 are used as oxidants in [Emim]HSO4 aqueous solu­
tion. It is found that the leaching results of different ionic
liquids is different under different oxidant conditions. We
systematically investigated the oxidative leaching of chalcopyr­
ite in ionic liquid with different oxidants (in Figure 8b).
We studied chalcopyrite leaching in ILs aqueous system
with H2O2 as the oxidant, and studied the kinetics, reaction
conditions, influencing factors (Hu et al. 2017). Partial results
are shown in Figure 9. It is found that the best ILs is
[Hmim]HSO4. Mineral particle size, [Hmim]HSO4 concentra­
tion, H2O2 concentration and temperature have important
effects, while the stirring rate has almost no effect on the
leaching of chalcopyrite. The influence of different leaching
temperatures on chalcopyrite leaching rate is illustrated in
Figure 9. It was showed that the leaching rate of chalcopyrite
increases with the increase of temperature and the kinetic
model of leaching process of chalcopyrite in [Hmim]HSO4
with H2O2 as the oxidant can be described by the chemical
reaction determined model with a activation energy of 52.06
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 13
kJ/mol. Under the optimal leaching conditions at a stirring
speed of 200 r/min, particle size −75 + 45 μm, 10% (v/v)
[Hmim]HSO4 solution, and 20% H2O2 as oxidant, copper
extraction can reach a 98.3% after 2 h.
We studied the leaching of chalcopyrite with K2Cr2O7 as
an oxidant in ILs aqueous system, and studied the reaction
conditions, influencing factors and process kinetics in detail
(Hu, Zi, and Tian 2021). The results are shown in Figure 10.
It is found that the best ILs for this oxidant is [Emim]HSO4
Reducing the particle size of the mineral, increasing the
concentration of [Emim]HSO4, the concentration and tem­
perature of K2Cr2O7 can enhance the leaching rate. The
stirring rate has a little effect on chalcopyrite leaching. The
influence of different leaching temperatures on the chalco­
pyrite leaching is illustrated in Figure 10. It was showed that
the rate of chalcopyrite leaching increases with increasing the
temperature. The process of chalcopyrite leaching in
[Emim]HSO4 solution with oxidant of K2Cr2O7 can be
described by diffusion-determined process with a activation
energy of 36.26 kJ/mol. It indicates that leaching of chalco­
pyrite in this system is diffusion determined process. The
optimum experimental conditions were obtained as
a temperature of 70 ℃, the stirring rate of 200 r/min, the
concentration of K2Cr2O7 of 0.1 mol/L, was 10%
[Emim]HSO4 (v/v), and the particle size of chalcopyrite of
45 μm. After 90 min, the copper extraction in chalcopyrite
can reach at 90.2%.
Copper and iron are leached from natural chalcopyrite
using aqueous solutions of imidazole and ethyl ammonium
cations and ionic liquids formed by bisulfides, nitrate, acetate,
or dicyandiamide anions (Kuzmina et al. 2017). The effects of
pH value, temperature, and anion types of ILs on the non-
oxidative leaching of chalcopyrite were investigated. It finds
that [Bmim]HSO4 solution showed the best leaching perfor­
mance. It is considered that the oxide layer formed in some
ionic liquids may be the reason for the reduction of leaching
capacity. CS2 and CO2 are produced in the leaching process of
all systems. CS2 produced in the leaching process may help to
reduce the sulfur layer on the surface of chalcopyrite samples,
rather than the oxide layer, to improve the leaching efficiency.
A series of different ILs with simple structure was screened
by machine learning platform, and the behavior of copper
leaching from chalcopyrite by these ILs was studied (Al-
Zubeidi, Godfrey, and Albrecht 2018). It was found that ILs
with more polar cations (NH4+, K+, [Hmim]+) showed the
better effect than ILs with less polar cations ([Emim]+, [Bmim]
+). The leaching process of all systems can be divided into three
stages: the leaching of iron rich/copper poor layer, the leaching
of large chalcopyrite, and the passivation of chalcopyrite. The
leaching rate enhances with increasing the stirring speed, indi­
cating that the leaching process is controlled by mass transfer
to a certain extent. It is found that the leaching performance of
[Emim]HSO4 and [Bmim]HSO4 is relatively poor.
The direct recovery of high-purity copper from the leaching
solution of sulfide minerals of copper such as copper blue (CuS),
chalcopyrite (Cu2S) and chalcopyrite (CuFeS2) in the choline
chloride/urea and choline chloride/glycol DESs were studied
(Anggara et al. 2019). It is found that the three sulfide ore in
14 G. TIAN AND H. LIU
Figure 9. The type of ILs (a) and H2O2 concentration (b) on copper extraction in ILs. [Reprinted (Hu et al. 2017) with permission from Elsevier].
the DESs can recover high-purity copper by electrochemical
dissolution and electrodeposition. The main copper species exist­
ing after the dissolution of copper blue and chalcocite is CuCl42-,
while chalcopyrite forms a mixture of Cu(I) and Cu(II) species.
Copper has mixed chloride, oxygen, or nitrogen donor coordina­
tion in choline chloride/urea. But it did not produce sulfides, SO2
or H2S in minerals are oxidized to sulfate. The optimal copper
recovery of 99% was achieved by using a mixed DESs of 80 wt%
choline chloride/glycol and 20 wt% choline chloride oxalic acid.
It is found that the copper selectivity in the electro-winning stage
can be improved by changing the solute morphology and redox
properties.
González, Ayala, and Escobar (2020) injected oxygen into the
chlorination medium to study pure chalcopyrite dissolution in
[Bmim]HSO4. At the same time, it is compared with the leaching
system without oxygen. The results show that the O2 injection
will lead to the increase in oxygen dissolved in the system and
the passivation of chalcopyrite. When the temperature is 80 ℃,
the [Bmim]HSO4 concentration of 20% (v/v), and added a small
amount of chloride, the best extraction rate of copper is 65.53%.

Figure 10. Effect of cations (A), anions(b) and K2Cr2O7 concentration (C) on copper extraction in ILs. [Reprinted (Hu, Zi, and Tian 2021) with permission from Elsevier].
Rodríguez et al. (2020a) investigated pure chalcopyrite dis­
solution in [Bmim]HSO4 with bromine like complexing agents.
The results were compared with those of acid leaching in
a sulfate medium with bromine and chloride ions. It was
found that the ILs and bromine ions can improve the leaching
performance of chalcopyrite. The best leaching conditions are
ILs concentration of 20%, temperature of 90°C, and bromine
concentration of 100 g/L. Then they used pure pyrite and
chloride as complexing agents to study the leaching chalcopyr­
ite in [Bmim]HSO4 aqueous solution (Rodríguez et al. 2020b).
The results demonstrate that when the ratio of chalcopyrite/
pyrite is 4/1, there will be no current effect. At 80 ℃, when the
concentration of H2SO4 is 0.5 M, the concentration of lithium
ion is 20% and there is no pyrite, the extraction rate of copper is
the highest, which is 73.83%.
Li et al. (2020b) studied copper extraction from sulfide ore
minerals (bornite, chalcopyrite, and chalcocite) in FeCl3/ethy­
lene glycol (FeCl3/EG) solution. At the same time, the extrac­
tion of copper from FeCl3/ethanol, CuCl2/EG, and FeCl3
/propylene glycol system was investigated. Some results are
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 15
shown in Figure 11. It is found that all systems can extract
copper, but FeCl3/EG system has the best leaching effect. The
leaching products of chalcopyrite in FeCl3/EG system are
CuCl, FeCl2, and solid elemental sulfur, and the leaching pro­
cess is determined by the chemical reaction on the surface.
After the leaching, solution was filtered, copper was electro­
deposited, and it was found that uniform cubic crystal pure
copper deposits were formed.
Carlesi et al. (2022) studied the chalcopyrite dissolution in
choline chloride/ethylene glycol (ChCl/EG) (1:2) DESs at ambient
pressure and medium temperature. Iron and copper dissolve
without changing the solvent pH and their oxidation state, form­
ing a stable chloride complex, and the system has no signs of
passivation. At 50°C, about 2900 ppm of copper dissolved from
chalcopyrite in the system after 4 h. It is found that the rate control
step of the dissolution process is the diffusion of species in the
solvent, and copper and iron can be recovered separately from
solution.
Sahlabad, Javanshir, and Honarmand (2022) synthesized
a new aliphatic ILs 1,2-ethane diammonium bisulfate
16 G. TIAN AND H. LIU
Figure 11. Effect of types of ores (a) and solvent and oxidizing agent (b) on the copper and iron leaching from chalcopyrite. [Reprinted (Li et al. 2020b) with permission
from RSC under CC BY-NC 3.0 license].
([EDA]HSO4), which was used in the dissolution of chal­
copyrite together with the oxidant H2O2. This ILs is more
environmentally friendly and more efficient than previously
reported ILs. The effects of oxidant and ionic liquid con­
centration, leaching time, and temperature on [EDA]HSO4
leaching chalcopyrite were studied by response surface
methodology (RSM). The results demonstrate that the
higher the concentration of oxidant, the more obvious the
influence of temperature on the process. Therefore, using
25% (w/w) H2O2 at 57 ℃, pulp density of 10 g/L, 100% (v/
v) [EDA]HSO4, the leaching efficiency can reach more than
91% after 2 h of leaching.
Leaching of silver and gold ores
The hydrometallurgy of gold and silver ores mainly includes
cyanidation, chlorination, thiourea, high-pressure acid leach­
ing, thiosulfate method, bacterial leaching, and other methods,
which have the problems of large reagent consumption, toxi­
city, high-energy consumption, low efficiency, serious environ­
mental pollution, and so on (Bai . 2008; He, Tong, Cui 2004).
Therefore, if a new leaching system can be found to overcome
the shortcomings of the traditional acidic thiourea silver leach­
ing system, it will be a major breakthrough in thiourea silver
leaching technology. ILs and DESs is a new type of green
solvent, which has incomparable excellent performance

compared with traditional reagents. For example, for different
raw materials, different anions and anions can be chosen to
adjust their solubility, to achieve the purpose of selective dis­
solution. By simplifying the extraction process of metal in the
leaching solution, the production process can be shortened.
The energy consumption and operation complexity can be
reduced, and the ILs and DESs can be recycled. Therefore,
the application of ILs and DESs in metal extraction from silver
and gold mineral is expected to develop a new green hydro­
metallurgy technology, and can solve serious environmental
pollution problems existing in the current metal extraction and
separation.
Whitehead, Lawrance, and McCluskey (2004)) used
[Emim]HSO4 as the leaching medium and added Fe2(SO4)3
and thiourea to leach gold and silver from the associated gold
ores of pyrite, chalcopyrite, magnetite, and sphalerite. It was
found that the leaching rate of low valence metals (Cu, Zn, Pb,
and Fe) is very low, with the extraction rate of gold higher than
85% and that of silver higher than 60%, as shown in Figure 12.
The research shows that the ILs and DESs leaching medium
has high selectivity for silver and gold, the extraction rate of
gold is similar to that in Fe2(SO4)3/H2SO4/thiourea system, and
the extraction rate of silver are significantly higher than that in
sulfuric acid aqueous solution. Further research shows that the
ILs after leaching can be recycled for at least four times after
being treated with activated carbon, which will not lead to the
degradation of ILs and the reduction of leaching rate of Au
and Ag.
Whitehead et al. (2007) leached gold and silver in
[Bmim]HSO4 aqueous solution by using Fe2(SO4)3 oxidant.
At 20–50℃, gold and silver in artificial oxidized ore and
natural sulfide ore were leached. The effects of thiourea and
[Bmim]HSO4 concentration on gold extraction from synthetic
gold ore were studied. It was found that thiourea concentration
had no observable effect on the extraction rate of gold. When
the concentration of [Bmim]HSO4 is 0–50%, the gold extrac­
tion rate does not change significantly. It is found that the rate
of Au leaching is greater than 85%, and the leaching rate of Ag
in natural sulfide ore is greater than 60%, which is greater than
that of acidic aqueous solution (<10%). The effects of different
cations, anions, particle sizes, sulfur-containing extractants
and ionic liquids on the gold extraction rate were investigated.
Some results are presented in Figure 13. The extraction rate of
hair cash basically decreases with the growth of a carbon chain.
After comparing different leaching media, it is found that
[Bmim]HSO4 has the best selectivity for gold and silver, fol­
lowed by [Bmim]CH3SO3 (1-butyl-3-methylimidazolium
methylsulfonate). [Bmim]HSO4 is the most effective ILs for
silver and gold extraction. There is a poorly difference in the
extraction rate of gold between ILs solution and acidic aqueous
solution, while the extraction rate of silver in ILs solution is
much greater than that in acidic solution. The smaller the
particle, the higher the extraction rate of silver and gold.
Except for thiourea, only mercaptothiazoline can be used as
a leaching agent for the oxidative leaching of silver and gold.
Silver, gold, and base metals were leached from gold sulfide
ore in [Bmim]HSO4 and [Bmim]Cl (1-butyl-3-methylimidazo­
lium chloride) and saturated K2SO4 aqueous solutions with
bromide, thiourea, chloride or iodide extractants, iron (III),
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 17
Figure 12. Comparative leaching of silver and gold in [Bmim]HSO4 or H2SO4
aqueous with thiourea and Fe2(SO4)3. [Reprinted (Whitehead et al. 2004) with
permission from RSC].
and peroxymonosulfate (HSO5−) as oxidants (Whitehead et al.
2009). In the presence of HSO5-/thiourea, the silver and gold
recoveries in the two ILs are more than 85% at 25–50 ℃. The
recovery of sulfate is much higher than that of silver. In
[Bmim]HSO4, the leaching efficiency of oxidant HSO5- is
similar to that of iron (III), and HSO5− is much higher in
[Bmim]Cl system. The recovery rate of base metal in the
ionic liquid medium used can be ignored, so the system studied
has high selectivity for gold and silver.
Fang et al. (2014a) studied on leaching silver concentrate with
[Bmim]HSO4 and thiourea. The effects of grinding fineness,
[Bmim]HSO4 concentration, thiourea concentration, Fe3+ con­
centration, liquid–solid ratio, and leaching times on silver leach­
ing rates were studied. The results show that under the optimal
conditions of grinding fineness of −0.043 mm accounting for
80%, thiourea concentration of 0.18 mol/L, [Bmim]HSO4 con­
centration of 0.3 mol/L, Fe3+ concentration of 7.5 mmol/L, a L/S
ratio of 3:1, and leaching 18 h, the silver leaching rate can reach
73.96%. In [Bmim]HSO4/thiourea, H2SO4/thiourea, and cyani­
dation system, not only the silver leaching rate is the highest, but
also the leaching time is the shortest. Then, they used Fe2(SO4)3
as an oxidant to leach silver from silver sulfide and pure silver
powder in [Bmim]HSO4 ionic liquid and thiourea system (Fang
et al. 2014b). The effects of pH value, leaching time, thiourea
concentration, oxidant dosage, temperature, stirring speed and
other factors on the leaching rate of silver was examined. It was
showed that [Bmim]HSO4 can strengthen the silver leaching
with thiourea. At the conditions of the thiourea concentration
of 0.16 mol.L−1, Fe3+ concentration of 1.25 × 10−3 mol.L−1, stir­
ring speed of 250 r.min−1, [Bmim]HSO4 concentration of 0.30
mol. L−1, and leaching temperatures of 298 K, the leaching rate
of silver can reach 78.85% after 24 h. The leaching rate of silver
in H2SO4 system with pH = 1 is just 51.10%. [Bmim]HSO4 in
silver leaching cannot only adjust the pH value, but also reduce
the decomposition of thiourea, and decrease the secondary pre­
cipitation of silver sulfide.
Zhang et al. (2016) studied leaching behavior of flotation
silver concentrates with copper content of 4.87% and 880 g/t of
silver in [Bmim]HSO4/thiourea and H2SO4/thiourea system.
Silver minerals in flotation silver concentrate mainly exist in
the form of silver sulfide and natural silver. The effects of pulp
18 G. TIAN AND H. LIU
Figure 13. Extraction results of gold and silver (a), and base metals (b) in ILs aqueous solution. [Reprinted (Whitehead et al. 2007) with permission from Elsevier].
pH value, Fe3+ concentration, thiourea concentration, leaching
time and other process parameters on leaching are examined. It
was showed that [Bmim]HSO4 can enhance the leaching selec­
tivity and leaching rate of silver under the conditions of weak
acid pulp, less Fe3+ dosage, and low thiourea concentration.
The leaching rate of silver in [Bmim]HSO4/thiourea system is
80.60%, while that in a sulfuric acid thiourea system is only
70.80%
Jenkin et al. (2016) studied the dissolution of silver and gold,
chalcopyrite, galena, pyrite, and bismuth telluride (Bi2Te3) in
choline chloride/ethylene glycol (1:2) DESs with iodine (0.1
mol.dm−1) as oxidant and the recovery of metals. It is found
that the gold, galena, chalcopyrite, and bismuth telluride (Bi2
Te3) can be oxidatively dissolved in DESs at 45–50 ℃, while
pyrite is insoluble. The dissolution rate of silver gold ore is the
fastest and chalcopyrite is the slowest. Compare to the current
cyanide industrial process, the dissolution rate of silver is very
favorable. This makes it possible to separate silver and gold
from the solution by electrodeposition. It is also found that
refractory phases (such as calamine and pyrite) can be also
dissolved in the DESs by electrolysis.
Other metal sulfides
Davris et al. (2014) used [Bmim]HSO4 for the leaching of
industrial brass ash to obtain zinc and copper. When
[Bmim]HSO4 aqueous solution (50% v/v) was applied to
leach at 70℃, the dissolution of zinc and copper reached
about 99% and 25%, respectively. In addition, in the presence
of H2O2 oxidant, the recovery of copper can be increased
to 82%.
The acetylcholine/ethylene glycol DESs was used to study
the electrochemical oxidation and reduction dissolution of
pyrite (Abbott et al. 2017). The paste made of mineral powder
in DESs was electrochemically oxidized or reduced and dis­
solved. It was found that pyrite in the system could be electro­
chemically dissolved, and the results showed that H2S or SO2
was not formed. Soluble species including arsenic and other
elements can also be recovered by electrochemical methods.
Hartley et al. (2020) studied the speciation and dissolution of
five different arsenide and iron sulfide minerals in DESs. It was
found that iron formed Fe(III)-O donor complex in DESs med­
ium after electrochemical dissolution, while cationic As(V)-O
donor complex is formed for arsenic. The EG component in
DESs can coordinate well with these species. It is found that the
dissolution behavior of these minerals is strongly affected by
sulfide or arsenide, and the dissolution rate of arsenide and
sulfur arsenide minerals is slower than that of pure iron sulfide.
The dissolution rate is also related to the band gap. The smaller
the band gap is, the faster the dissolution rate is.
Tian et al. (2022) selected four imidazole-based ILs of
[Bmim]I (1-butyl-3-methylimidazolium iodide), [Emim]BF4
(1-methyl-3-methylimidazolium tetrafluoroborate),
[Bmim]NO3 (1-butyl-3-methylimidazolium nitrate) and
[Bmim]BF4 to reveal the inhibition performance of ILs on
spontaneous combustion. It was showed that the main pro­
ducts are SO2 and Fe2O3 produced in the process of oxidative
spontaneous combustion. ILs have a significant inhibitory

effect on the spontaneous combustion of sulfide ores, which
can reduce the spontaneous combustion of sulfide ores, and
[Bmim]NO3 has the strongest effect.
From the above research works, it can be seen that using ILs
and DESs or its aqueous to leach chalcopyrite and other miner­
als can obtain high leaching rates of metals such as Cu and Zn
in a relatively short time, especially for precious metals such as
silver and gold. Because the low vapor pressure of ILs and
DESs, it will hardly volatilize and can be recycled, so the
method of leaching minerals with ILs and DESs is expected
to develop a new green metallurgical technology with zero
emissions. ILs and DESs are new kinds of green solvent. At
present, its cost is more expensive than other commonly used
industrial systems, and its high viscosity had a certain impact
on leaching. The research of ILs and DESs in mineral leaching
is still in its infancy. Although some progress has been made, it
has not been widely used. The basic problems such as the
interaction between ionic liquids and minerals, the existing
forms of species in the leaching solution, the dissolution
mechanism, the separation and purification mechanism of
valuable elements/impurity elements, and its impact on the
subsequent electrodeposition process are still unclear, and
need to be further solved. In addition, ILs and DESs have
combinatorial variability (designability), and different combi­
nations of anions and Cations can form ILs and DESs with
different properties. Theoretically, more than 1018 kinds of ILs
and DESs can be obtained from the known combinations of
anions and anions. Therefore, how to screen and design cheap
ionic liquids with excellent solubility and high selectivity will
be an important research direction in the future.
Interaction between ILs and soil minerals
Ionic liquids, as a kind of environment-friendly ‘green’ solvent,
have been widely concerned and applied in many aspects. ILs
are difficult to volatilize, so it will not pollute the air during use.
However, if the waste liquid containing ILs are not treated
reasonably and effectively in time, ILs may be discharged into
the environment with the waste liquid. With the increasing use
of ionic liquids, ILs entering the environment will gradually
accumulate in the soil, and its risk of entering the soil, surface
water and groundwater environment will inevitably increase.
Because ILs have certain eco-toxicity, it is very important to
study the migration behavior of ILs in the soil environment
(Azevedo et al. 2017; Haerens et al. 2009; Markiewicz,
Jungnickel, and Arp 2013a). The adsorption/desorption beha­
vior of ILs will affect their migration process in the environ­
mental medium, and the ILs properties themselves, soil
properties (such as the content of organic matter and clay
minerals), and exogenous coexisting with organic matter
(such as dissolved organic matter) will affect the migration
characteristics of ILs in the soil environment (Berg et al.
2001; Engel and Chefetz 2016; Fu et al. 2016; Mrozik et al.
2012). Therefore, studying the adsorption/desorption behavior
of ILs in the soil is helpful to understand their environmental
fate, and provides an important scientific basis for the ecolo­
gical assessment of ILs.
Gorman-Lewis and Fein (2004) measured the [Bmim]Cl
adsorption on the surfaces of gibbsite, quartz, and sodium
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 19
montmorillonite.The effects of S/L ratio, time, ionic strength,
pH value were investigated. It was showed that [Bmim]Cl is
unstable in water with pH lower than 6 and larger than 10, and
shows ionic strength and pH independent related adsorption
on Na montmorillonite containing 0.4, 0.8, 1.0, 1.2, and 2.0 g/L
clay. At pH 6–10, [Bmim]Cl will not adsorb on gibbsite or
quartz. The distribution coefficient of [Bmim]Cl on Na mon­
tmorillonite changes with the change in ionic strength.
Mrozik et al. (2008) studied in detail the interaction and
adsorption mechanism of [Bmim]Cl, [Emim]Cl, [Hmim]Cl,
[MBPy]Cl (1-methyl-4-butylpyridinium chloride), and
[Omim]Cl (1-octyl-3-methylimidazolium chloride) with kao­
linite clay minerals. The results demonstrate that ILs has multi­
layer adsorption on the mineral surface, and the partition
coefficient of long alkyl-chain molecules is the highest. It is
found that the adsorption mechanism is the result of physical
adsorption and electrostatic interaction. Ion exchange and van
der Waals interaction are dominant during initial adsorption,
and dispersion interaction is dominant when ionic liquid con­
centration is high.
Beaulieu, Tank, and Kopacz (2008) conducted adsorption
experiments on four alkyl methylimino-based ionic liquids of
[Hmim]Cl, [Emim]Cl, [Omim]Cl, [Bmim]Cl and with four
aquatic sediments to evaluate the ability of these sediments to
remove chemicals from the water column. It was showed that
the concentration isotherm is nonlinear, and the distribution
coefficient decreases with increasing the concentration. The
apparent partition coefficient is positively correlated with the
content of sediment organic matter (SOM). It is shown that the
adsorption of ILs on the tested sediment is not strong.
Increasing the alkyl-chain length will not result in the increase
of adsorption, which indicates that hydrophobic interaction is
not the most important adsorption mechanism. Aquatic sedi­
ment has limited adsorption capacity for alkyl methylimidazole
ionic liquids, the sediment will not strongly weaken the migra­
tion of these pollutants in the aquatic system. Studzińska,
Sprynskyy, and Buszewski (2008) measured the adsorption
kinetics of [Bmim]Cl, [Emim]Cl, and [Hmim]Cl in five soil
with different total organic carbon (TOC) contents under static
conditions. It was showed that the adsorption capacity
increases with the increase of TOC content and cationic hydro­
phobicity of ILs. The kinetic adsorption parameters and dis­
tribution coefficient obtained can be used to assess the
adsorption characteristics of soil types on ILs. The adsorption
of the cations of ILs on the soil can usually be regarded as
physical adsorption with exothermic effect. However, when the
TOC content in soil is very high (45%). The adsorption of
cations is chemical adsorption. ILs is adsorbed by electrostatic,
hydrogen bond, and π * π interaction with clay mineral and soil
organic matter.
Matzke et al. (2009) studied the influence of two different
clay minerals montmorillonite and kaolinite, as well as organic
matter in German standard soil Lufa 2.2 on the cation adsorp­
tion, desorption behavior, and interaction of three imidazole-
based ILs [Bmim]BF4, [Bmim]Ntf2 (1-butyl-
3-methylImidazolium bis(trifluoromethylsulfonyl)-imide) and
[Omim]BF4. It is found that montmorillonite has an obvious
effect on the adsorption capacity of all three ILs, indicating that
ion interaction plays a key role in the adsorption and
20 G. TIAN AND H. LIU
desorption of ionic liquids in soil. When the clay content is 10
wt% or 15 wt%, the adsorption of [Bmim]BF4 and [Bmim]Ntf2
in the soil containing kaolinite is the same. The adsorption rate
of kaolinite with a mass fraction of 15% is even lower than that
with a mass fraction of 10%. The desorption sequence is
[Bmim]Ntf2 > [Bmim]BF4 > [Omim]BF4. Compared with kao­
linite and organic matter, montmorillonite has the greatest
effect on desorption. The desorption kinetic of [Bmim]Ntf2 is
more concentration dependent than that of [Bmim]BF4.
Mrozik et al. (2012) evaluated the interaction and adsorp­
tion of nine imidazole and pyridine chloride ionic liquids in 11
different soil environments through chemo-metrics. It was
shown that compounds with long alkyl side chains are easy to
be adsorbed than compounds with weak lipophilicity. In addi­
tion, salt containing short derivatives and/or hydroxyl deriva­
tives is more mobile in soil/sediment, which may cause the risk
of surface water or groundwater pollution. According to the
interaction with the soil surface, ionic liquids form two main
clusters. One is compounds with short hydroxyalkyl side
chains, and the other is compounds with other compounds.
The main soil parameter responsible for adsorption is cation
exchange capacity, which has a low adsorption potential at
a low pH value.
Reinert et al. (2012) studied the interaction and adsorption
of five ILs of [Bmim]Cl, [Omim]Cl, [Amim]Cl (1-Allyl-
3-methylimidazolium chloride), [Bpy]Br (N-methyl pyridine
bromide) and [Opy]Br (N-octylpyridine bromide) with Na
montmorillonite. It is found that five ILs can be inserted into
the Na montmorillonite layered structure through the disper­
sion in its aqueous solution. The intercalation of all ionic
liquids expands the spacing of silicate layers. RTIL is mostly
adsorbed by cation exchange mechanism. The maximum
adsorption capacity is closely related to the properties of
organic cations and the alkyl-chain length, and the order is
[Bpy]Br > [Opy]Br≈[Bmim]Cl ≈[Amim]Cl > [Omim]Cl.
Markiewicz et al. (2013b) studied the interaction between
the imidazole ionic liquids [Omim]Cl, [Hmim]Cl, [Bmim]Br
and mineral components of kaolinite and quartz. The adsorp­
tion of kaolinite and quartz was studied from the aspects of
adsorption isotherms, zeta potential changes, and partition
coefficients in clay modified by the aggregates of ILs. It was
found that the adsorption was monolayer adsorption, and the
alkyl chains in imidazole molecules were adsorbed on the sur­
face in parallel to minimize the contact with water. The chain
length of alkyl in imidazolium will affect the charge and char­
acteristics stability of minerals.
Chen et al. (2022) studied the adsorption performance of
ciprofloxacin (CIP) on iron hydride and montmorillonite by
five imidazole based ILs ([Emim]Cl, [Omim]Cl, [Bmim]Cl,
and anti-anion soluble ILs (1-butyl-3-methylimidazoliumtosy­
late ([Bmim]TOS) and [Bmim]PF6) with different chain
lengths of alkyl. It was showed that ILs can inhibit the adsorp­
tion of CIP on the two minerals due to the competition of
adsorption sites between CIP molecules and cations, the steric
hindrance caused by the long alkyl chain of ILs, and the
electrostatic interaction. With the extension of the alkyl
chain, the adsorption inhibition of ionic liquid of iron hydride
has almost no change. The order of influence of ILs on CIP
adsorption on montmorillonite is [Hmim]Cl > [Bmim]Cl >
[Emim]Cl The inhibition of adsorption mainly depends on the
anti-anion PF6- > TOS- > Cl-, which is primarily due to the
difference of anion in ion size and binding affinity with miner­
als. In addition, as the pH value of the solution increases from
5.0 to 9.0, the degree of inhibition of [Bmim]TOS on CIP
adsorption on iron hydride decreases with increasing the solu­
tion pH, and for montmorillonite, the degree of inhibition
increases with the increase of the pH value.
As seen from above, the published research works have
mainly focused on the interaction between imidazole and pyr­
idine-based ILs and different types of soils and minerals. The
results show that ILs interact with the mineral surface through
chemical adsorption or physical adsorption, and both cationic
and anionic parts of IL play an important role. If soil or
minerals contain organic carbon, its alkyl chain can also be
effectively adsorbed. However, the effects of chain length of
alkyl in imidazole-based ILs, soil composition and inorganic
cations coexisting in the environment on their adsorption/
desorption in soil are not obvious. The influence mechanism
of the structural properties (polar functional groups and aro­
matic structures) of dissolved organic matter in the soil on the
adsorption/desorption of imidazole bases ILs in soil need to be
further clarified.
Conclusion and outlook
ILs and DESs, as new type materials, have the advantages of
organic solvents and high-temperature molten salts at the same
time, and become very promising low-temperature ‘green’
solvents. Because of their wide liquid temperature range, low
melting point, good thermal and chemical stability, low vapor
pressure and nonvolatile, good solubility, and adjustable prop­
erties and functions, they have the great potential applications
in mineral processing. In recent years, with the deepening of
research and the continuous emergence of creative achieve­
ments, the application of ILs and DESs in mineral flotation,
leaching and other mineral processing fields has made gratify­
ing achievements.
ILs and DESs have been successfully used to high-efficient
float some minerals that are difficult to float, such as rare-earth
minerals, quartz, quartz and quartz hematite, as well as carbo­
nate asphalt. Compared with the traditional flotation reagents
for these minerals, the amount of ILs and DESs used is
obviously smaller, and the selectivity and effect of flotation
are better than that of the traditional system. ILs collector has
better quartz collection effect, and foaming agent is not
required in flotation. The length in the alkyl chain in ILs
plays a key role in floatability. Compared with the interaction
between ILs and quartz surface, the length of the alkyl chain is
more important. In addition, ILs and DESs have almost no
vapor pressure, will not evaporate and leak during application,
and are not difficult to regenerate and recycle. Therefore, it has
been potential for further industrial application. Using ILs or
ILs aqueous solution to leach sulfide ores (such as chalcopyrite,
pyrite, etc.) and other minerals, can obtain higher leaching rate
and efficiency in a relatively short time, especially for precious
metals such as silver and gold. Most-used ILs are imidazolium
hydrogen sulfate. It is found that single pure ILs has limited
leaching effect on minerals, especially sulfide ore. In the

presence of ILs aqueous solution and oxidant, the leaching rate
can be greatly improved, and the leaching time can be shor­
tened. Because ionic liquids have obvious selectivity, they can
achieve selective leaching and extraction of valuable metals. In
addition, compared with the traditional leaching, the amount
of ILs is less. It can selectively leach metals, and its vapor
pressure are low. It will hardly volatilize, and it can be recycled.
Therefore, the method of leaching minerals with ILs and DESs
are expected to develop a new zero-emission green mineral
processing technology. The research on the effects of ILs on soil
minerals and groundwater mainly focuses on the imidazole,
and pyridine based ILs. It is found that ILs interact with
mineral surfaces through chemical adsorption or physical
adsorption, and both cations and anions can play a role. The
alkyl-chain length, soil composition, and coexisting with inor­
ganic cations in the environment of imidazole-based ionic
liquids have no obvious effect on their adsorption/desorption
in soil.
Hundreds of millions of ILs and DESs can be formed by
different cations and anions or HBDs and HBAs. Therefore,
there is no an universal method to select them to meet specific
needs. After analyzing from the reported literature, it is found
that ILs used for flotation of oxide ore such as rare earth,
quartz, quartz hematite, etc, are mainly composed of cation
and anion with long alkyl branch chain and containing nitro­
gen, phosphorus, and oxygen elements. Such as long-chain
ammonium halide, long-chain substituted imidazole halide,
aminoalkyl-substituted imidazole, betainium, multi-chain
long alkyl substituted ammonium/phosphine ILs were used.
DESs used for flotation is mainly formed by hydrogen bond
donors containing N, P, oxygen and thiourea. ILs used for
leaching sulfide ores and precious metals are mainly composed
of sulfur, nitrogen, phosphorus, and oxygen elements and
longer alkyl chains, such as imidazole hydrogen sulfate or
halide salts, and oxidants have to be added. Commonly used
DESs for leaching mainly include nitrogen, sulfur, phosphorus,
and chlorine containing HBA, and the HBD such as urea,
thiourea, and ethylene glycol (EG)Mostly used DESs are
[Bmim]HSO4/thiourea, choline chloride/EG, betainium/EG,
betainium/thiourea, 1, 2-ethane diammonium hydrogen sul­
fate ([EDA]HSO4), FeCl3/EG.
It can be seen from the published works that ILs and DESs
have obvious effects in mineral flotation and leaching compared
with traditional reagents. The related research has made many
progress, which is expected to further develop into a new green
mineral processing technology based on green chemistry and
engineering. However, as new green solvents, ILs and DESs still
have many unknown aspects, such as their properties, solution
chemistry, ion existence formation, interaction, migration, and
diffusion. Their dissociative adsorption/desorption mechanism
on the mineral surface, flotation, or leaching reaction mechan­
ism need further research. The following directions should be
strengthened. (1) Quantitative structure–activity relationship of
structure and properties of ILs and DESs need to be established
for the design and selection of ILs and DESs to for flotation and
leaching. In combination with the best solution chemical envir­
onment for the interaction of flotation agent, leaching agent,
and mineral, it is an important work in the future to select new
high-efficiency ionic liquid and deep eutectic solvent flotation
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 21
agent and leaching agent, design interface assembly and green
synthesis. (2) Mineral separation mechanism based on particle
behavior and interface regulation in ILs and DESs, the chemical
reaction mechanism of flotation agent/mineral/interface in ILs
and DESs, and the mechanism of mineral particle surface force
and aggregation and dispersion behavior should be revealed. (3)
The influence of mineral dissolved components in ILs and DESs
on mineral surface electrical properties and flotation, the chem­
istry of flotation leaching solution, and the thermodynamics and
kinetics in the process of separation enhancement in ILs and
DESs need to be studied to realize the performance regulation of
valuable minerals, strengthen the separation difference between
valuable minerals, gangue minerals and impurity elements, and
provide a theoretical basis for reasonable screening and selec­
tion of ILs and DESs and their dosage. (4) Large-scale synthesis
and system integration of ILs and DESs, recycling and large-
scale industrial applications. At present, the large-scale synthesis
of ILs and DESs has not been established, and the cost is
relatively high. Exploring large-scale integrated systems with
mild conditions and simple technical routes, reducing costs is
the bottleneck problem they face in large-scale industrial appli­
cations in mineral separation and extraction. It is believed that
with the deepening of research, ILs and DESs will play an
increasingly important role in the field of comprehensive and
efficient utilization of mineral resources and truly form an
emerging field.
Disclosure statement
No potential conflict of interest was reported by the author(s).
Funding
This work was supported by the National Natural Science Foundation of
China under Grant No. 51774158 and 51264021; Department of Science
and Technology of Yunnan Province under Grant 2011CI013.
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