Minerals Engineering 112 (2017) 103–113

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

The evolution of mineral processing in extraction of rare earth elements MARK

using solid-liquid extraction over liquid-liquid extraction: A review
⁎
Nur Nadiatul Hidayaha, Sumaiya Zainal Abidina,b,
a
Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia Pahang, 26300 Gambang, Pahang, Malaysia
b
Centre of Excellence for Advanced Research in Fluid Flow (CARIFF), Universiti Malaysia Pahang, 26300 Gambang, Pahang, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: This review paper summarises the fundamental in the production of rare earth elements (REE) specifically on the
Rare earth elements extraction of REE. Liquid-liquid extraction (LLE) is known to be the most common method employed in the
Solid liquid extraction extraction of REE. However, it possesses a few disadvantages by having poor contact area and the formation of
Liquid-liquid extraction third phase during the extraction process. Solid-liquid extraction (SLE) compensates most of the disadvantages in
Ionic liquid
LLE such as the formation of third phase and poor contact between extractant and desired elements. The focus of
Synergist
this paper is to review the evolution of REE extraction and discovers the potential of REE extraction through SLE.
Supporting materials
Extractants are available widely but when assisted by supporting material via immobilisation, theoretically it
elevates the contact area between extractant and desired REE and this concept is known as extractant im-
mobilised material (EIM). The graphical abstract illustrates the concept of EIM between extractant immobilised
supporting materials which increases the potential of REE being extracted from aqueous phase. The material is
not limited to polymeric resin, silica and membrane, but also microorganism, bio-derived and hybrid materials.
EIM is expected to enhance the contact surface area, avoid third phase formation, and reduce the use of che-
micals thus increasing the extraction and selectivity of REE. Also, EIM in SLE has the potential to surpass the
conventional method in LLE in terms of quantity and quality.

1. Fundamental in production of REE
The production of REE mainly starts with mining the mineral
bearing rare earth elements (REE). Minerals bearing REE are available
in mineral rocks mined from dry lands or placer deposit dug from
watery reserves (Jordens et al., 2013; Rezaee Ebrahim Saraee et al.,
2009; Sultan and Shazili, 2009). However, the concentration of REE in
most of rock forming minerals are not economically efficient for com-
mercial refining. The properties of minerals formed in different loca-
tions are varied in terms of its compositions. Apart from REE, other
elements with similar properties are found in the same minerals as REE
(Li and Yang, 2014).
Based on geological survey, monazite, bastnasite, and xenotime are
the three major minerals enriched with REE and feasible for commer-
cialisation. Mining and refining these minerals are practicable
considering cerium (Ce), lanthanum (La), and neodymium (Nd) are
enriched in batnasite and monazite. While, xenotime bears mostly yt-
trium (Y), dysprosium (Dy), erbium (Er), ytterbium (Yb), and holmium
(Ho) (Walters et al., 2011). Monazite is classified as phosphate minerals
with a mixture composition of Ce, La, praseodymium (Pr), and Nd. In
addition, monazite has a mix of radioactive elements such as thorium
(Th) and uranium (U) around 4–12% composition (Jordens et al.,
2013). Bastnasite is a fluorocarbonate mineral and xenotime is yttrium
phosphate mineral (YPO4). Apart from bastnasite, monazite, and xe-
notime, ion-adsorbed clays is another source of REE that normally en-
riched with 60% of rare earth oxides (REO) (Haque et al., 2014). These
mixed up elements in minerals require a long chain of process for high
purity production of REE.
The production of REE requires most practices in metallurgy.
Hydrometallurgy, pyrometallurgy, ionometallurgy, electrometallurgy,

Abbreviations: CHON, Carbon, hydrogen, oxygen, and nitrogen; CMPO, Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide; COOH, Carboxylic acid; Cr, Chromium; CREE,
Critical rare earth elements; D2EHPA, Di-(2-ethylhexyl)phosphoric acid; DHOA, N,N-di-n-hexyl octanamide; DODGAA, N,N-dioctyldiglycol amic acid; EDASiDGA, 3-(ethylenediamino)
propyl silica gel; EGDMA, Ethylene Glycol Dimethacrylate Copolymers; EIM, Extraction immobilised material; HFSLM, Hollow fibre supported liquid membrane; HLW, High level liquid
wastes; HRE, Heavy rare earth element; HTTA, Thenoyltrifluoro-acetone; IIL, Imprinted ionic liquid; IL, Ionic liquid; LAMP, Lynas Advanced Material Plant; LLE, Liquid-liquid extraction;
LRE, Light rare earth elements; MAH, Maleic anhydride; MRE, Medium rare earth; NPH, Normal paraffin hydrocarbon; P204, Bis(2-ethylhexyl) phosphate; REE, Rare earth elements; REO,
Rare earth oxides; RNO3, Resin nitrate; RPF6, Resin hexafluorophosphate; SE, Synergist extractant; SHLW, Simulated high-level waste; SIL, Supported ionic liquid; SIR, Solvent im-
mobilised resin; SLE, Solid liquid extraction; SLM, Supported liquid membrane; TBP, Tributyl phosphate; TEOS, Tetraethoxysilane; TODGA, N,N,N′,N′‐Tetraoctyl Diglycolamide
⁎
Corresponding author at: Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia Pahang, 26300 Gambang, Kuantan, Pahang, Malaysia (S.Z. Abidin).
E-mail address: sumaiya@ump.edu.my (S.Z. Abidin).

http://dx.doi.org/10.1016/j.mineng.2017.07.014
Received 6 March 2017; Received in revised form 21 July 2017; Accepted 24 July 2017
Available online 30 July 2017
0892-6875/ © 2017 Elsevier Ltd. All rights reserved.
N.N. Hidayah, S.Z. Abidin
Fig. 1. Example of simplified process flow based on REE plant.
and beneficiation are examples of standard practices in production and
purification of metals. Even though the characteristics and applications
of REE are slightly different from other metals, these practices are
feasible for REE processing. Fig. 1 shows a simplified process flow of
common practice in REE industrial production. The examples of process
were adapted from Lynas Advanced Materials Plant (LAMP) process
flow (Walters et al., 2011; Earth and Processing, 2016; Chu, 2011;
Lynas, 2016). Lynas is a corporation from Australia that mining rare
earth bearing minerals from Mt Weld, Western Australia and then
shipped to LAMP for refining and concentration operation. The first
phase is physical beneficiation to concentrate the monazite and fol-
lowed by chemical beneficiation via cracking and roasting which pro-
duces leachate. The leachate will undergone the separation and ex-
traction phase to segregate the desired elements before going through
the final phase of REE product recovery. Each of the phase has a se-
quences of other subsidiary processes such as solvent extraction,
leaching, precipitation, floatation, and wet processing. Most of the
processes were combined for a complete production of REE which re-
sulted into thousands of stages (Jordens et al., 2013; Haque et al., 2014;
Abbott and Frisch, 2013; Gupta, 1981; Krishnamurthy and Gupta,
2004).
1.1. Physical and chemical beneficiations
Beneficiation is a process commonly applied in metallurgy sector
and it is divided into physical and chemical beneficiations. The main
purpose of beneficiation is to remove gangue minerals from raw ores to
ensure high concentration of REE output solution. The route flow in
beneficiation processes varies corresponding to the type of input of
REE. The input can be from raw rock minerals, placer deposits, recycle
materials, or heavy metal waste that expected to be rich in REE.
Physical beneficiation is a treatment conducted on excavated hard
rocks minerals by breaking down the solid into fine powder (Walters
et al., 2011). On the other hand, chemical beneficiation or also known
as pyrometallurgy is a process that breaks down the chemical bonding
between REE and other gangue elements to form highly concentrated
REE mixtures (Lynas, 2016; Gupta, 1981; Krishnamurthy and Gupta,
2004).
Physical beneficiation is applied according to the type of ores.
Normally, the dried mined ores are crushed and ground to produce
solids with high particle surface area and further processed in the next
subsequent phase (Lee Yee et al., 2011). However, mineral ores from
placer deposits have different physical treatment considering the wa-
tery feed. Placer deposit is collected from watery reserves such as river,
stream, and marine environment (Rezaee Ebrahim Saraee et al., 2009;
Sultan and Shazili, 2009). Gravitational separation and flotation are the
additional processes for watery feed to separate water from ores before
the drying process. Magnetic separation, electrostatic separation, and
screening are usually the supporting practices used in the physical
beneficiation (Gupta, 1981). However, no all ores require physical
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Minerals Engineering 112 (2017) 103–113
treatment. Feeds such as recycled materials and ion adsorbed clays are
going straight to the chemical processing since these kind of feeds do
not require physical beneficiation treatment.
Chemical beneficiation produces highly concentrated REE leachate
mixture in a composition that compromise with water phase which
increase the separation and extraction of minerals in organic phase.
(Lynas, 2016; Gupta, 1981; Krishnamurthy and Gupta, 2004). First,
chemical beneficiation uses high temperature to break down the bond
between REE and gangue elements. The temperature must be at least
between 300 and 1000 °C and processed in 60-m long gas fired kilns
(Haque et al., 2014; Krishnamurthy and Gupta, 2004). This high tem-
perature process is also known as roasting or cracking, with the purpose
to ease water introduction to the rare earth ores (Lynas, 2016; Lee Yee
et al., 2011; Xie et al., 2014). Then, high concentrations of chemicals
such as hydrochloric, sulphuric, and nitric acids are introduced into the
roasted or cracked rare earth ores. Lastly, ore slurry is produced from
the chemical beneficiation phase.
Approximately 30–35% of ore slurry is produced that is then treated
with froth flotation and pressed to get high concentrated leachate
(Walters et al., 2011) and followed by treatment process known as
leaching. Leaching is a process that separates ore slurry into leachate
that contains valuable REE metals and undesired compounds for dis-
posal. Leachate consists of at least 60% of REO mixture and 40% im-
purities (Walters et al., 2011). This leachate will be an input for the next
process which is separation and extraction to slim down the elements
into desired metal compositions.
High operating temperature, high chemical concentration, and large
quantity of chemicals consumed produces a severe toxic waste that
harms the environment (Liao et al., 2013). Environmental activists are
really against the production of REE mainly due to physical and che-
mical beneficiation phases. Apart from having to deal with the ex-
istence of radioactive elements during the process, the waste from the
production of REE is also difficult to manage and dispose. Though,
studies have been conducted to find alternatives to REE production and
introduce greener methods.
1.2. Separation and extraction
Separation and extraction is the most important phase to ensure
high purity REE is obtained. Separation in REE industry is defined as
classification process of desired compounds (REE) and undesired com-
pounds in a mixture of leachate. Meanwhile, extraction is a selective
action taken on desired elements (REE) from aqueous phase (leachate).
For example, a high level liquid wastes (HLW) is separated from a
mixture of minor actinides (MA) and lanthanides. Then, La is extracted
from MA using N,N,N',N'-tetrakis(4-propenyloxy-2-pyridylmethyl)
ethylene-diamine (TPEN) that acts as an extraction solvent (Takeshita,
2010; Takeshita et al., 2008).
Separation and extraction phase is complex and sensitive. It is
crucial to ensure a high efficiency of individual REE separation and able
N.N. Hidayah, S.Z. Abidin
to be recovered at the end of the process. Many approaches have been
conducted to attain viable extraction method of REE by understanding
the extraction behaviours, selectivity, capacity, solubility, mass
transfer, phase separation, and economic feasibility. Liquid-liquid ex-
traction (LLE) and solid liquid extraction (SLE) are two general con-
cepts applied to separate and extract REE. LLE employs two different
immiscible liquids (i.e., aqueous and organic solvents) to separate
compounds. Extraction occurs when the desired element from one side
of liquid phase is attracted towards another liquid phase. Meanwhile,
SLE is an extraction process of desired element from liquid phase that
attracted towards reactive solid phase (Meloan, 1999). The product
from separation and extraction phase is then extended to the next phase
of product recovery.
1.3. Product recovery
In product recovery phase, the output from separation and extrac-
tion phase is processed for final purification. A scrubbing circuit is
engaged at the end of the separation and extraction phase to wash
impurities from organic phase before going through the final purifica-
tion stage (Krishnamurthy and Gupta, 2004). It is important to ensure
the concentration of desired REE is at optimum and free from impurities
to achieve the highest REE purity during product recovery. Individual
or a group of REE is recovered after thorough processes such as strip-
ping, precipitation (Li and Wang, 2009); electrometallurgy (Gao et al.,
2009; Egorov et al., 2010), and ion exchange. The final products of REE
are available in solid form of rare earth carbonates (RECO3), rare earth
oxalates (REO), rare earth nitrate hexahydrate (RE(NO3)3·6H2O), or
simply pure REE. The quality and quantity of final products are de-
pendent on the operation of beneficiations, separation, and extraction
of REE (Gupta, 1981; Krishnamurthy and Gupta, 2004).
2. Liquid-Liquid Extraction (LLE) of REE
Separation and extraction are the most vital phases in the produc-
tion of REE and commonly conducted via LLE. However, to conduct
separation and extraction, it is important to understand the composi-
tion of feeds that affects the entire separation and extraction processes.
The ores are composed of mixed elements that have strong bonds be-
tween each element. Chemical and physical properties between Sc, Y,
lanthanides series (REE), and actinides series (radioactive elements
such Th, U, and Am) are almost identical in perspective of metal be-
haviour. The similarity of these metals are influenced by the geological
formation effects on the reserve location where REE are found (Singh,
2007; Xu and Peng, 2009).
LLE performance is evaluated based on the extraction and se-
lectivity efficiency of REE (Sun et al., 2010). Apart from different kind
of extraction methods, the extractants used in the process also give a big
impact on the extraction and selectivity efficiency. For example, the
selectivity of Y is anomalous depending on the type of extractant (Xie
et al., 2014). Lack of understanding on the behaviour of REE will lead to
misperception on the best method or solution to be implemented.
Composition of gangue elements, concentration of individual REE,
oxidation state, and separation factor of extractant are issues that must
be reflected in the arrangement of processes in separation and extrac-
tion of REE.
Hydrometallurgy is a chemical metallurgy method that conducts
separation and extraction of metals based on reaction in aqueous
medium. Leaching, ion exchange, solvent extraction, and precipitation
are examples of hydrometallurgy processes. Solvent extraction is a well-
known process and commonly used in the extraction and separation of
REE (Gupta, 1981) due to its capability to handle large volumes of
dilute pregnant liquor of aqueous solution (Xie et al., 2014). However,
solvent extraction process consumes a large amount of conventional
extractants that releases volatile organic compounds (VOC), toxic, and
flammable wastes.
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Minerals Engineering 112 (2017) 103–113
The evolution in solvent extraction is observed by the type of sol-
vent extractants and innovative methods used in various literatures.
Solvent extraction is divided into four components, which are ex-
tractant, diluent, modifier, and synergist. Conventional extractants such
as TBP, D2EHPA and Cyanex 272 (Xie et al., 2014; Flett, 2005) had
replaced the use of traditional solvents such as benzene, heptane, and
kerosene (Atanassova et al., 2015; Liu et al., 2012). The threat from
traditional solvent extractants towards the environment such as highly
flammable and air pollution had led to the use of ionic liquid (IL). IL has
the potential to extract metals but mainly ends up as diluents to main
extractants (Larsson and Binnemans, 2014). The diluent must be
homogeneous with extractant but immiscible with aqueous phase to
avoid contamination (Atanassova et al., 2015; Sun et al., 2012). The
example of diluent functions are to reduce viscosity of extractant thus
improving the hydrodynamic properties of the system (Gupta, 1981).
Modifier is an additional solution used to avoid the formation of
third phase or emulsion during the extraction stage (Gupta, 1981).
Emulsion normally occurs when two immiscible solvents are mixed and
commonly shaken (Sun et al., 2012; Pospiech and Kujawski, 2015). In
continuous operation, emulsion is caused by poor flow rate and poor
viscosity control. NaNO3, an example of modifier, is added into aqueous
solution to destabilise the third phase formation (Rout and Binnemans,
2014). Long chain alkyl alcohols like isodecanol, 2-ethylhexanol, non-
yphenol, and tributyl phosphate (neutral extractant) are another ex-
amples of modifiers (Gupta, 1981).
Recently, synergist extractant (SE) has become common to increase
separation (Suna et al., 2015), selectivity (Yang et al., 2012), and avoid
emulsion (Gupta, 1981; Ciceri et al., 2014). Synergist is a combination
of two solvents or more to form a new dynamic solvent (Gupta, 1981).
SE is also known as bi-functional solvent which found to give better
extraction and selectivity efficiency compared to individual perfor-
mance of extractant. CA-12-Cyanex272 (Sun et al., 2005), HEHEHP-
D2EHPA (Zhang et al., 2014), Cyanex 272-D2EHPA, and Cyanex 302-
D2EHPA (Darvishi et al., 2005) are examples of synergist used in REE
extraction. Synergists also can be a combination of solvent extractant,
modifier, and diluent (Gupta, 1981).
SE has the advantage of having less consumption of primary ex-
tractant, able to achieve high separation efficiency, and ability to re-
generate the extractant. Nevertheless, SE may not be as effective in
extraction of REE due to disadvantages of LLE such as poor contact area
between two phases and formation of third phase (Xie et al., 2014).
Although LLE was commonly used in industrial scale, the extraction
efficiency is always questionable. Problems such as low extraction ef-
ficiency, impurities in final product, loss of extractant into aqueous
phase, and low purity still occur in large scale processes
(Krishnamurthy and Gupta, 2004). SLE offers the advantages of having
large surface area and better contact between extractant and REE in
aqueous phase. Extraction immobilised material (EIM) has been con-
sidered recently to counter the drawbacks found in solvent extraction
process. EIM was found to increase the extraction efficiency, selectivity,
quality, contact area, and reduce chemical consumption in the se-
paration and extraction of REE (Xiaoqi et al., 2009; Zhu et al., 2012).
3. Solid-Liquid Extraction (SLE) of REE using Extractant
Immobilised Material (EIM)
Recently, the extraction of REE using solid-liquid extraction (SLE) is
highly considered when the concept of solvent impregnated resin (SIR)
and supported ionic liquid (SIL) are widely disclosed in literatures (Zhu
et al., 2012; Kabay et al., 2010). SIR is a concept that selects the most
effective extractant to recover REE and infuses the solvent onto the
selected material. N,N-dimethylformamide (DMF), TODGA, Cyanex-
923, and P-204 are examples of solvent extractants impregnated onto
selected materials such as silica and resin (Xiaoqi et al., 2009; Neagu
et al., 2010; Zhu and Chen, 2011). SIL is similar to SIR except that
instead of solvent extractant, IL is employed. Cyphos IL-104, [Cnmim]
N.N. Hidayah, S.Z. Abidin
[PF6] and N-methylimidazole are examples of IL infused onto sup-
porting materials (Zhu et al., 2012; Kubota et al., 2010). Either con-
ventional extractant or IL, both complex ligands apply the similar
concept where selected solvent is infused onto the supported material.
After infusion, the material is denoted as extractant immobilised ma-
terial (EIM).
EIM can be manipulated using ion exchange or adsorption tech-
nique in REE recovery. These two techniques have the capability to
recover desired metal at high efficiency especially at low concentration
of REE in the solution (Liu et al., 2012). In fact, SLE using ion exchange
and adsorption have been used in REE extraction long before solvent
extraction ever been commercialised. In 1893, Y and Gd were the first
elements separated using ion exchange technique with activated carbon
(AC) supports, but the extraction yield was very poor (Krishnamurthy
and Gupta, 2004). The characterisation analysis on the AC discovered
that the plain surface of the adsorbent was the main reason of having
poor extraction of REE. In 1947, Boyd and team had conducted mod-
ification on the surface area of the adsorbent material using citric acid
and gained positive results in the extraction of REE (Boyd and Ketelle,
1947). Apparently, pH of aqueous has a significant influence on the
recovery of REE in the adsorption process. The research was then
continued by Powell and team on the behaviour of REE in the ad-
sorption and desorption cycles (Powell et al., 1957; Powell and
Spedding, 1967; Spedding and Adolf, 1949). Gradually by 1960, high
quality of REE were produced through ion exchange method using
various materials of adsorbent followed by leaching and precipitation.
However, during that period, SLE is produced in a small scale pro-
duction. Thus, around that year, most of the manufacturers in me-
tallurgy industry have already implemented solvent extraction process
(Krishnamurthy and Gupta, 2004).
The main advantage of solvent extraction is its capacity to handle
large scale of separation but the separation efficiency and purity level of
REE are deficient. Multiple contacts between aqueous and organic so-
lution may increase the extraction efficiency of REE but the organic
extractant has high tendency to loss into the aqueous phase after a long
contact of aqueous and organic phases (Krishnamurthy and Gupta,
2004; Zhu et al., 2009). In addition, there is high potential for the
solvent to produce emulsions during the process due to poor control of
flow rate and mass transfer (Regel-Rosocka and Alguacil, 2013; Sun
et al., 2013). Though, the advantages of LLE can be applied in SLE by
the immobilisation of material with the most effective extractant
identified using EIM concept. Theoretically, this idea should increase
the contact area between organic and aqueous solution. Thus, the im-
mobilisation should reduce the amount of IL used, increase the interface
area, reduce the diffusion distance, and speed up the transportation rate
(Zhu et al., 2012).
EIM is developed to achieve high recovery and selectivity of REE by
increasing the surface area of extractant and the diffusion rate of REE
into extractant. Fig. 2 illustrates the concept of EIM in the extraction of
REE using extractant immobilised onto supporting material. This con-
cept is conducted by a few researchers that practise SLE system to ex-
tract metal ions. Table 1 lists the functionalised materials in the se-
paration of REE. Most of EIM studies used the most recognised
extractants in extraction of REE in LLE such as Aliquat 336, CA-100,
D2EHPA, DODGAA, Cyanex-923, [Cnmim][PF6], [Cnmim][NTf2], and
Cyphos IL-101. These extractants are proven to be an attractive solvent
towards REE. In some studies, the selected material is modified to attain
good chemistry between extractant and material to enhance adsorption
and desorption cycle and increase its durability for a series of cycles.
The supporting materials can be developed from different materials
such as polymer, membrane, silica, microorganism, hybrid, and bio-
derived materials. Most of the adsorbent materials are modified or
immobilised so EIM can be designed with strong bonding and robust
specifically for the extraction of REE.
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Minerals Engineering 112 (2017) 103–113
Fig. 2. Illustration of EIM in extraction of REE.
3.1. Types of adsorbent materials
Adsorbents are available in various material forms such as natural
and synthetic of organic, inorganic, or a composite. Natural materials
such as zeolites and clays have limitation in adsorption, so modification
is made on the materials to enhance the capabilities through additional
physical and chemical properties. The modified material is known as
synthetic material. Synthetic material is more stable compared to nat-
ural material (Ullah et al., 2012). The adsorbent materials are cate-
gorised into polymer, silica, membrane, microorganism, hybrid, and
bio-derived materials. Theoretically, materials such as polymer and
silica consist a good framework to carry positive and negative electric
charges, high stability, convenient preparation method, and good in-
teraction with positive-negative charges.
3.1.1. Polymer
Polymer resin is known to be low in cost, abundantly available,
mechanically robust, chemically inert, thermal and chemically stable,
tuneable, consist a good framework to carry positive and negative
electric charges, and widely applied (Atanassova et al., 2014). Most
polymer resins came from polystyrene-based resin with the pendant
chloromethyl groups (Zhu et al., 2012). It is available in either gel or
macroporous structure which can be activated as ion exchange mate-
rials. Activated polymer or ion exchange resin can be tuned into acid
cation exchange resin and base anion exchange resin (Masram, 2013).
Cation exchange resin is divided into strong and weak acid ex-
change resins. Strong acid cation exchange resin is normally associated
with sulfonic group (SO3-), acting similarly to strong acid and active in
any pH level. On the other hand, weak acid cation exchange resin be-
haves the opposite of strong acid exchanger and simply releases H+ due
to its weak dissociation. This behaviour makes weak acid cation ex-
change resin is favoured in metal ions extraction and has higher ion
exchange capacity than the strong acid exchanger. Weak acid cation
exchanger is generally associated with carboxylic group (COOH) and
passive in the pH range of 4–6 (Masram, 2013). D113-III is an example
of weak acid cation exchanger and was experimented on Nd(III) and Er
(III) (Xiong et al., 2009, 2011). This type of EIM is functionalised by
carboxylic resin and independent from any additional immobilised
solvent. The pH values of 6.04 and 6.9 are the optimal adsorption
conditions for Er(III) and Nd(III), respectively, and the adsorption ef-
ficiency declined at pH 6. Adsorption capacity has slight deviation with
temperature changes but it is negligible. The optimum pH value is
consistent with Masram’s theory on weak acid cation exchanger
(Masram, 2013).
 Table 1
Compilation of functionalised materials in REE separation.

Matrix Functionalised/impregnation of solvents Metal ions Results Reference

N.N. Hidayah, S.Z. Abidin

D113-III resin (COOH) Not available Er(III)Nd(III) Optimal adsorption condition for Er(III) and Nd(III) were at pH 6.04 and 6.9, Xiong et al. (2009); Xiong et al.
respectively, with adsorption efficiency of 74% (2011)
Merrifield Resin (RNO3) N-dimethylformamide (DMF), N-methylimidazole, Sodium Ce(IV) Ce(IV) is adsorbed onto RNO3 resin and adsorption equilibrium of 0.54 mmol/g was Zhu and Chen (2011)
Nitrate achieved within 180 min for approximately 23% of Ce(IV) reduction
Merrifield resin (RPF6) N-dimethylformamide, N-methylimidazole, Sc(III) 60% extraction of Sc(III) was achieved using RPF6 resin impregnated with [C8mim] Zhu et al. (2011)
Hexafluorophosphoric acid, [C8mim][PF6] and Cyanex-923 [PF6] and Cyanex-923
PS-DVB N-dimethylformamide, N-methylimidazole Cr(IV) Adsorption of Cr(IV) from plating wastewater using functionalised resin was at Neagu et al. (2010); Zhu et al.
optimum in pH range of 2–5 with 99% recovery of heavy metals but adsorption (2009); Deng et al. (2012)
decreased from pH 5.0 to 10.0
Diglycol amic acid group resin Not available Sc(III) Adsorption took more than 48 h to reach equilibrium and adsorption efficiency was Van Nguyen et al. (2015); Van
less than 50% in chloride aqueous medium Nguyen et al. (2016)
Amberlite XAD-7 [A336][CA-100] Sc(III) The final extraction efficiency of [A336][CA-100] was approximately 79% with time Zhu et al. (2012)
to reach equilibrium was less than 30 min
Amberlite XAD-7 D2EHPA Sc(III) Extraction can still be done even under big ratio of 200:1 between aqueous solution Lee et al. (2009)
and resin containing D2EHPA compared to resin impregnated with PC88A or Cyanex
923 that can only handle extraction at ratios of 5:1 and 50:1
Amberlite XAD-7 Cyanex923 and [C8mim][PF6] Y(III) The optimum extraction efficiency was achieved at 80% and equilibrium time was Sun et al. (2008)
shorten to 20 min. However, the application of EDTA as complexing agent reduced
the extraction efficiency from 99.95 to 2.6%
TEOS Cyphos IL-104 and [Cnmim][PF6] (n = 4,8) Y(III) Combination of [C4mim][PF6] and Cyphos IL-104 resulted in more than 50% of Liu et al. (2009)
extraction efficiency than [C8mim][PF6] and Cyphos IL-104
TEOS Cyanex 923 and [C8mim][PF6] Y(III) Y(III) was 91% extracted at pH 5.6 in 60 min Liu et al. (2007)

107
EDASiDGA diglycolic anhydride Dy(III) Adsorption ratio of using diglycol amic acid functionalised silica increased with Ogata et al. (2014); Ogata et al.
higher amount of diglycolic anhydride at pH 2 (2015)
Porous silica particles TPPEN, NIPA, DMF Am(III) High selectivity to Am(III) from solution containing Am(III) and Eu(III) at a Takeshita et al. (2008)
separation factor value of 3.7
EGDMA 4-Vinylpyridine Gd(III) The selectivity on Gd(III) increased from separation factor value of 7 to 20 but Garcia et al. (2002)
declined extraction efficiency from 60 to 22%
Magnetic GMZ bentonite P-204 Eu(III) The adsorption efficiency reached 98% at the optimum pH of 3.04 Chen et al. (2012)
TEOS MAH Gd(III) Adsorption of Gd(III) by mesoporous silica nanoparticles using MAH reached Zheng et al. (2015)
equilibrium within 100 min at 60% efficiency
Alginate-silica Not available Nd(III) Wet alginate-silica adsorbed better than dry alginate silica due to microsphere Roosen et al. (2015)
shrinking under drying condition which ultimately reduced porosity of silica at pH
5–6
Salmon milt Not available Yb(III) Lu(III) High selectivity towards Yb(III) and Lu(III) compared to other REE at pH 4 Takahashi et al. (2014)
Hollow fibre membrane TODGA, DHOA. NPH Am(III) Very high extraction efficiency of 99.9% by hollow fibre supported liquid membrane Ansari et al. (2008)
Polyvinylidene fluoride film DODGAA and [Cnmim][PF6] (n = 4,8,12) Y(III) Eu(III) Extraction of Y(III) and Eu(III) using membrane immobilised with DODGAA and Kubota et al. (2010)
[Cnmim][PF6] were completed under initial pH of 0.5–1.5 compared to
immobilisation using n-dodecane. [C8mim][PF6] and [C12mim][PF6] were more
stable in the membrane pores and more hydrophobic than [C4mim][PF6]
Stainless steel microfiltration Not available La(III) The optimum condition of 95% extraction was achieved via dispersion of extractant Hou et al. (2013)
membrane into aqueous solution with bulk flow rate of 160 mL/min
Bacillus subtilis Not available Tm(III), Yb Adsorption reached equilibrium within 10 min of agitation at pH 4 with 0.39 g/L of Takahashi et al. (2005)
(III) Lu(III) Bacillus subtilis concentration
Bacillus subtilis Not available La(III), Eu(III), Adsorption percentage of La(III), Eu(III), and Tm(III) were 78, 89, and 96%, Moriwaki et al. (2013)
Tm(III) respectively, at pH 3 using 20 mg of WT Bacillus subtilis
Minerals Engineering 112 (2017) 103–113
N.N. Hidayah, S.Z. Abidin
Strong base anion exchanger resin uses quaternary amine (NR3+),
while tertiary (NR2), secondary (NRH), and primary (NH2) amine will
produce weak base anion exchanger resin. Strong base anion resin
works at all levels of pH, but weak base anion mostly active at very low
pH level (Masram, 2013). Lili Zhu et al. (2009) polymerised N-methy-
limidazolium functionalised with strong basic anion exchange resin
(MIm-AER) using Merrifield resin (Zhu et al., 2009). Mim-AER using
Merrifield resin was found to be more stable than Amberlite IRA-400
during the stability test using hydrogen peroxide H2O2 (Neagu et al.,
2010). The performance of Mim-AER is reflected on the ionic surface
that can be manipulated. Deng et al. (2012) applied the same Mim-AER
synthesis method as Lili Zhu et al. (2009, 2011) but used different kind
of resin. Instead of Merrifield resin, PS-DVB resin was used to adsorb Cr
(VI) from electroplating wastewater. PS-DVB polymer was found to be
able to withstand five adsorption cycles. The adsorption capacities of
PS-DVB polymer is 125 mg/g and it is better than Merrifield resin. This
may be caused by high concentration of DVB in the PS-DVB resin
compared to Merrifield resin. DVB is commonly known as a good
crosslinker. Amberlite XAD-7 is well known for its uniform pore size
distribution and high surface area. The attachment of arcrylic ester
group (-RCOO) in the middle polarity offers a good attraction of hy-
drophobic affects (Xiaoqi et al., 2009; Lee et al., 2009; Sun et al., 2008).
Cyanex923 and [C8mim][PF6] were impregnated on Amberlite XAD-7
and reached equilibrium time of 20 min with 50% more efficient
compared to LLE system that engaged the same extractants (Sun et al.,
2008). This proved that SLE system ameliorates the disadvantages in
LLE by enhancing the mass transfer rate and increasing the contact area
between extractant and metal ions.
Overall, polymer based EIM is found to be feasible to extract REE
ions with the right type of polymer, size porosity, crosslinking, and
suitable extractants. Though, resin is prone to swell or shrink under
long time operation.
3.1.2. Silica
Silica based material has a good porous structure, good quality of
mechanical properties, good physical and chemical stability, con-
venient preparation, high thermal stability, and has negligible swelling
or shrinking silica (Atanassova et al., 2014). Synthesised silica is con-
sidered to be a good adsorbent for heavy metal ions as various func-
tional groups can be immobilised on silica based material. The chemical
synthesis of silica was also found to be simpler compared to polymer
resins (Zhu et al., 2012). Liu et al. (2009) investigated the effectiveness
of Cyphos IL-104 combined with [Cnmim][PF6] (n = 4,8) and further
impregnated onto tetraethoxysilane (TEOS), creating EIM with a
covalent bonding. At pH 5.6, the extraction efficiency was at optimum
when Cyphos IL-104 paired with [C4mim][PF6] instead of [C8mim]
[PF6] (Liu et al., 2009). Thus, the extraction of Y using Cyphos IL-104
and [C8mim][PF6] was found to reach 92% compared to 46% efficiency
of Cyanex 923 and [C8mim][PF6]. Both cases applied the same silica
type (Liu et al., 2007). Apparently, higher viscosity of IL contributed to
a slight interference in extraction efficiency with 9% differences be-
tween [C4mim][PF6] and [C8mim][PF6] (Liu et al., 2009).
EDASiDGA is another example of silica that emerged with extractant
that is in the same group as DODGAA. Ogata et al. (2014) stated that
the performance of EDASiDGA is affected by the concentration of HCl
where the adsorption decreased with increasing HCl concentration. In
addition, EDASiDGA exhibited inclination towards HRE with selectivity
sequence of Dy followed by Nd, Fe, Cu, and Zn under the same op-
eration condition (Ogata et al., 2014). Ogata et al. (2015) continued the
research on EDASiDGA using a continuous packed adsorption column.
It was found that REE extraction using EDASiDGA was highly inclined
towards MRE and HRE (Ogata et al., 2015). EDASiDGA was also found
to have high potential to be commercialised. The optimum operation
condition for both adsorption and desorption are very acidic where no
additional base required.
Overall, silica based EIM is much simpler to synthesise and combine
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Minerals Engineering 112 (2017) 103–113
with other extractant compared to polymer resin. In addition, silica is
found to be very efficient in the extraction of heavy metals. Silica is
stable at high acidic condition, however it degrades easily at high pH
value and difficult to be separated from water under continuous in-
dustrial operation (Zhu et al., 2012).
3.1.3. Membrane
Membrane is a common supporting material in SLE. The extraction
process using membrane is known to consume low energy, has high
selectivity on REE, low cost operation, and simple to manage.
Polytetrafluoroethylene, polyviylidene fluoride, polyamide, and
ceramic membranes are the examples of membrane supports (Zhu et al.,
2012; Kubota et al., 2010) used in REE extraction. Ansari et al. (2008)
studied the extraction of Am(III) using hollow fibre supported liquid
membrane (HFSLM) soaked with TODGA, N,N-di-n-hexyl octanamide
(DHOA) and normal paraffin hydrocarbon (NPH). The impregnated
membrane was used as a separation media for the extraction of acti-
nides and lanthanides from aqueous media (Ansari et al., 2008). HFSLM
gave a complete separation containing pure 99.9% of Am(III) within
20 min at 200 ml/min of flow rate at 25 °C. Then, the study on HFSLM
was extended on mixed solution of Am(III) and Nd(III) and it took
40 min to extract Am(III) completely. HFSLM was proven to be able to
extract 98% of LRE from simulated high-level waste (SHLW) that con-
tained assorted metal ions within 45 min and disregarded metal ions
outside actinides and lanthanides group (Ansari et al., 2008). Basically,
TODGA in HFSLM is designed to have high selectivity for elements such
as Am(III), Cr(III), and La(III) (Sasaki et al., 2015; Sengupta et al.,
2014).
Kubota et al. (2010) studied the effects of polyvinylidene fluoride
film after being immersed in DODGAA and [Cnmim][PF6] (n = 4, 8,
and 12) to create a new type of supported liquid membrane (SLM) of
EIM. This SLM is claimed to be more durable for long operation even
after 120 h of operation. In this study, SLM was found to extract Y(III)
and Eu(III) successfully at a very low pH range of 0.5–1.5. This SLM is
more effective compared to polyvinylidene fluoride film impregnated in
n-dodecane (Kubota et al., 2010). Furthermore, [Cnmim][PF6] with
longer alkyl chain exhibited better membrane properties such as high
hydrophobicity and it is more stable within the membrane structure.
The IL was found difficult to loss into aqueous phase making the SLM is
durable for a long time of operation (Kubota et al., 2010).
Hou et al. (2013) used the concept of membrane to extract La(III)
without any extractant impregnation. Instead, the membrane function
is improved by creating micro-dispersion extractant using stainless steel
microfiltration membrane. EHEHPA is dispersed using the microfiltra-
tion membrane to enhance the contact between aqueous phase and
EHEHPA. The long capillary tube that mixes the dispersed organic and
aqueous phases increases the interaction time for proper extraction of
La(III) from aqueous phase. Approximately 95% of extraction was
achieved using this method at the optimum flow rate of 160 mL/min
(Hou et al., 2013). This process is considered as the LLE process using
membrane to increase the contact between the two liquid phases.
3.1.4. Microorganism materials
Microorganism as sorbent material is found to be quite efficient and
more environmentally friendly in the extraction of metal ions
(Gavrilescu, 2004). It reduces the usage of expensive and toxic reagents.
The most common microorganisms used in cell-sorption of REE are
Bacillus subtilis, Escherichia coli, Pseudomonas fluorescens, Paracoccus
denitrificans, Schwanella putrefaciens, and Alcaligenes faecalis (Das and
Das, 2013; Moriwaki and Yamamoto, 2013). Based on Moriwaki and
Yamamoto (2013), there are four types of sorption mechanism involve
in the interaction of metal ions with microorganisms, which are surface
adsorption, adsorption on extracellular biopolymer, biologic absorp-
tion, and adsorption on extracellular bio-mineral (Moriwaki and
Yamamoto, 2013).
Surface adsorption is found to be more effective in the extraction of
N.N. Hidayah, S.Z. Abidin
REE. Surface adsorption using microbial cells is highly preferred due to
its ability to produce extracellular polymeric substances (EPS). EPS
from microbial cell allows the adsorption on the cell wall, leaving the
inner part of the cell unharmed, avoids abrupt degradation of the cell
adsorbent, and can be regenerated for a few cycles of adsorption and
desorption (Moriwaki et al., 2013). There are two types of bacteria used
in metal extraction which are gram-positive and gra-negative bacteria.
Most of the REE has high affinity towards the gram-positive bacteria. It
has been reported that each bacteria cell surface consists of two binding
group sites, which are carboxylate and phosphate (Takahashi et al.,
2005; Emmanuel et al., 2011; Park et al., 2016). REE is prone to be
attached on these two binding functional groups.
Bacillus subtilis is an example of a gram-positive bacterium
(Takahashi et al., 2005; Moriwaki et al., 2013) and Escherichia coli is an
example of a gram-negative bacterium (Emmanuel et al., 2011). Bacillus
subtilis is inclined to separate HREE especially Tm, Yb, and Lu
(Takahashi et al., 2005; Moriwaki et al., 2013). Based on Takahashi
et al. (2005), the extraction of REE reached an equilibrium in 10 min at
pH 4 with 0.39 g/L concentration of strain. An increase in the con-
centration of Bacillus subtilis had increased the enrichment of REE on
Bacillus subtilis. At pH 5.8, REE adsorption efficiency reduced with the
increase of agitation time (Takahashi et al., 2005; Moriwaki et al.,
2013). It can be assumed that Bacillus subtilis degraded at high pH and
agitation process was found to accelerate the degradation process.
Gram-positive bacterium has four sections on the cell wall, which
are cell membrane, peptidoglycan, lipoteichoic acid (LTA), and wall
teichoic acid (WTA) as shown in Fig. 3 (Moriwaki and Yamamoto,
2013). Hiroshi Moriwaki studied the effect of wild type (WT) and li-
poteichoic acid (LTA) defective strains of Bacillus subtilis in extracting
La(III), Eu(III), and Tm(III). WT exhibited better removal performance
compared to LTA since metal ions adsorbed on the WTA located on cell
wall instead of LTA that localised inside the cell wall. However, ex-
traction of REE using WT powder must be followed with filtration as it
failed to coagulate and settled down like LTA powder (Moriwaki et al.,
2013). Similar to the optimum condition studied by Takahashi et al.
(2005), the overall optimum Bacillus subtilis performance was at low pH
and the adsorption reached an equilibrium at a very short time of
agitation.
Microorganisms have a very high potential in extracting REE and
being eco-friendly is a bonus. The major drawbacks of microorganisms
sorbent based materials are the large requirement of microorganisms to
produce dry powder adsorbent, large area to cultivate the micro-
organisms, difficulty to maintain the right condition to nurture the
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Minerals Engineering 112 (2017) 103–113
microorganisms, and high energy is required to separate the strains
from water (Mansa et al., 2012). Plus, microorganisms have a poor
elution and uneconomical for industrial scale of REE (Gavrilescu, 2004;
Das and Das, 2013).
3.1.5. Hybrid and Bio-derived materials
The revolution in materials for EIM has emerged into a new class via
hybrid of natural and synthetic materials (Ullah et al., 2012). The
motivation that leads to hybrid material is mainly caused by certain
limitation in materials like polymer, silica, and microorganism. Hybrid
material can be developed through merging the natural and synthetic
materials together either using biological, chemical, or physical forces
to elevate the material capacity and durability. With regards on green
separation, most hybrid materials are bio-renewable materials (Dodson
et al., 2015). Magnetic clay adsorbent, chitosan silica, salmon milt,
algae silica, and imprinted adsorbent are the examples of hybrid and
bio-derived materials that had been experimented on adsorption of
REE.
Bentonite is an inexpensive natural clay mineral and an efficient
adsorbent with drawback issue on separation and recycling bentonite
from aqueous solution. Chen et al. (2012) studied the effects of mag-
netised bentonite using iron oxide instead of using extractant to im-
mobilise the bentonite. The purpose of magnetised bentonite is to solve
problem on separation as it uses the magnetic force to extract bentonite
from aqueous solution. Iron oxide was found to be strongly intact on
bentonite at the pH range of 3–11. However, iron oxide on bentonite
gave poor extraction of Eu(III). The magnetised bentonite was im-
mobilised with P204 and resulted in 98% extraction efficiency of Eu(III)
at pH 3.04. However, it was difficult to strip Eu(III) completely from
immobilised magnetised bentonite where the adsorption efficiency
decreased dramatically to 65% just after three cycles (Chen et al.,
2012). This is possibly due to slipping of P204 into aqueous solution
after every adsorption and desorption cycle.
Chitosan is derived from chitin, which is exploited from crustacean
shell of shrimp and crab. Chitosan is a bio-polymer classified under the
group of amino with high affinity reputation towards metal ions (Dutta
et al., 2004). Gandhi and Meenakshi (2013) studied the hybrid mate-
rials between chitosan and silica gel. Chitosan was fused with silica gel,
with the aim to create a strong adsorbent that able to increase REE
extraction known as silica-chitosan composite (SiCS) (Gandhi and
Meenakshi, 2013). In recent development, Zheng et al. (2015) studied
the immobilisation of SiCS with maleic anhydride (MAH) extractant
and found that this hybrid material could dramatically increase the
Fig. 3. Schematic structure of the cell wall of gram-positive bacteria
(Moriwaki and Yamamoto, 2013).
N.N. Hidayah, S.Z. Abidin
adsorption of metal ions. The adsorption of REE using immobilised SiCS
was lenient towards MRE especially Eu(III) and Gs(III) with an ad-
sorption equilibrium rate recorded in 100 min. In addition, the per-
formance of immobilised SiCS was maintained at high chemical stabi-
lity even after five cycles. However, the adsorption ability was reduced
in every cycle (Zheng et al., 2015). High chemical stability of SiCS was
unable to maintain MAH from losing into the aqueous phase after few
regeneration cycles.
Algae is another type of bio-derived material and alginate is syn-
thesised out of algae. Alginate is an anionic polysaccharide on the cell
wall of brown family of algae. Roosen et al. (2015) designed alginate to
be bio-derived using silica Sikron M600. The alginate-silica was created
as microspheres absorbent using vibrating-nozzle technology and was
tested on Nd(III). It was discovered that wet alginate-silica adsorbed
better than dry alginate. The drying process of the alginate-silica re-
sulted in shrinkage of the microsphere and ultimately reduced the
porosity of the adsorbent. The optimum pH for Nd(III) extraction was 5
and limited to pH 6 due to the precipitation of Nd(III). A complete
elution of Nd(III) was highly effective at pH 0.56. This adsorbent went
through seven adsorption-desorption cycles and maintained adsorption
ability over 80% in the final adsorption cycle (Roosen et al., 2015). This
bio-derived material was excellent in maintaining the adsorption ability
for seven cycles and theoretically could be enhanced with the supports
of extractant.
Takahashi et al. (2014) made an interesting study using salmon milt
as a new bio-derived adsorbent and has potential as REE adsorbent. The
salmon milt was cleaned with high purity water, chopped into smaller
pieces, freeze-dried, and lastly powdered using an agar mortar. This
adsorbent had high selectivity towards Yb(III) and Lu(III) compared to
other REE at pH 4. Through this study, salmon milt powder and WT
powder of Bacillus subtilis were compared. Both bio-derived adsorbents
had similar adsorption pattern in the extraction of REE. However,
salmon milt powder was observed to be more efficient at recovering
REE at pH 4 while WT powder gave the optimum adsorption at pH 3
(Takahashi et al., 2014).
Hybrid and bio-derived materials have stretched the capability of
ion exchange and adsorption into a new level and still manage to
maintain green separation. There is no limit in type of materials applied
as adsorbent as long the process could achieve optimum extraction at
an economical operation. Alginate silica has a big potential and further
research on this material is recommended by immobilising the material
with solvent extractants.
3.2. The modification and immobilisation of supporting materials
Polymeric resin, silica, membrane, microorganism, and salmon milt
are the examples of materials that have been used in the extraction of
REE as supported materials. Some of these materials had been tested as
EIM with potentials to adsorb and desorb REE. Improvement on these
materials can be made by immobilisation and modification in certain
ways. The purpose of modification is to enhance adsorption and fixated
material ionic surface specifically for the desired elements (Ullah et al.,
2012; Masram, 2013). Thus, the solid is altered to improve the surface
area, increase the mass transfer efficiency, tune the ionic surface, and
hinder the loss of IL and extractant during the process (Xiong et al.,
2009). The attachment of extractant on the material is preferred in the
form of covalent bond so the matrix and extractant are able to with-
stand EIM adsorption and desorption cycles.
The techniques for chemical and physical modifications are varied
with different side effects on the stability and capability of EIM.
Usually, physical immobilisation methods such as simple impregnation,
sol gel, doped material, and encapsulation create a layer of extractant
shield on the solid support. Chemical immobilisation or modification
methods enhance the adsorption ability of a material by manipulating
the chemical bonding, ionic surface, or physical formation of ad-
sorbent’s material using chemicals. Chemical modification is highly
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Minerals Engineering 112 (2017) 103–113
preferred due to the formation of covalent bonding between solvent’s
moieties and materials (Zhu et al., 2012). The modification effects are
observed on the pore size, porosity capacity, stability of material,
crosslinking degree, composition of aqueous phase after adsorption
process, re-adsorption ability, and recovery of REE after regeneration.
3.2.1. Functionalised material
Functionalised material can be modified using carboxylic acids,
organophosphorous acids, and glycol amide acids. Immobilisation of
the selected group onto the solid creates a matrix of functionalised
material based on the group of reagent involved (Ogata et al., 2015).
For example, D113-III is functionalised on macroporous resin with an
active surface area of carboxylic acid (eCOOH). This active sites are
designed by mixing acrylic acid together with polymeric resin before
polymerisation (Xiong et al., 2009). Resin containing diglycol amic acid
is an example of weak cation acid exchanger. The modification method
of this resin is patented under Japanese Registered Patent and Trade-
mark Attorney (Van Nguyen et al., 2016). Van Nguyen et al. (2016)
studied the behaviour of this resin and discovered that the adsorption
efficiency of this resin was poor with less than 45% efficiency. The
optimum desorption of this resin was 60% after elution with 2 M of HCl
at 25 °C in batch test. The desorption increased up to 95% when the
temperature was increased to 80 °C (Van Nguyen et al., 2016).
The problem with this resin is that the pore size is small (8.9 nm) to
adsorb or release Sc(III) at room temperature. On the other hand, high
temperature condition facilitates the movement of Sc(III) to be com-
pletely eluted from the resin. Regardless, the selectivity of this resin is
high on Sc(III) and hardly affected by other REE since the pore size can
only accept the size radius of Sc(III). In addition, the adsorption effi-
ciency of both D113-III and resin containing diglycol amic acid reduced
slowly in every consecutive cycle. The solvent impregnated in these
resins was discovered to be slowly leached into aqueous phase as the
presence of additional functional groups (C]O and -OH) was detected
in the solution after adsorption process (Xiong et al., 2009; Xiong et al.,
2011; Van Nguyen et al., 2015; Van Nguyen et al., 2016).
3.2.2. The tune of material ionic surface
Polymer and silica have flexible ionic surface and it is tuneable by
simply mixing it with chemicals that produce the same polarity of ca-
tion or anion (Zhu and Chen, 2011). The ionic surface attracts the op-
posite charge of desired metal ions onto the solid. Cation acid ex-
changer has negative charge on the ionic solid surface and attracts
positive charge from aqueous phase. The attraction power of cation acid
exchanger depends on the strength of the acid and vice versa for the
anion base exchanger (Masram, 2013).
Lili Zhu et al. (2009, 2011) investigated the performance of Mim-
AER in the extraction of metal ions by manipulating the ionic solid
surface of Mim-AER between Cl−, SO42−, and NO3−. Mim-AER is de-
rived from methylimidazole and DMF solution where the mixture is
immobilised onto Merrifield resin by stirring the resin and chemicals
together at 80 °C. The initial ionic surface of Mim-AER is Cl− and
manipulated by mixing Mim-AER with nitric acid or sodium sulphate to
create resins with ionic surface of SO42− or NO3− (Neagu et al., 2010;
Zhu et al., 2009; Deng et al., 2012). The main advantage discovered was
nearly no loss in adsorption and desorption capacity of Cr(IV) after four
cycles of Mim-AER’s Merrifield resin using a mixed solution of 0.3 mol/
L of 1:1 ratio of NaOH and NaCl (Zhu et al., 2009).
Immobilisation of Mim-AER with synergist extractant of Cyanex-
923 and [C8mim][PF6] are futile due to the hydrophilic characteristic of
RCl−. The hydrophilic characteristic of Cl− ions on Mim-AER are in-
capable of incorporating the immobilisation of Cyanex-923 and
[C8mim][PF6] on the resin. Therefore, the ionic surface of the resin is
tuned to PF6− ions. Lili Zhu et al. (2011) had tuned the ionic surface of
RCl− resin with PF6- ions and the modification is shown in Fig. 4. Resin
RPF6- was found to have better chemical and physical stability, very low
hydrophilic characteristic, and cooperates better with other extractants
N.N. Hidayah, S.Z. Abidin Minerals Engineering 112 (2017) 103–113

Fig. 4. Tuning surface characteristic of resin (Zhu et al., 2011).

(Zhu and Chen, 2011; Zhu et al., 2011). Complex ionic surface such as functionalised with phosphate or carboxylate group, with high affinity
PF6− ions on the resin is more effective than simple ions such as Cl− towards REE (Das and Das, 2013; Moriwaki and Yamamoto, 2013).
and NO3− to capture REE metal ions. Normally, selected microorganism material is inoculated with the pre-
cultures strain under suitable medium and cultivated until it reaches
the exponential growth phase (Mansa et al., 2012). Then, the micro-
3.2.3. The effect of solvent on supporting materials
organism is harvested for drying process, either by freezing or heat
Extractant plays a significant role in maintaining high extraction
drying (Takahashi et al., 2005; Moriwaki et al., 2013). Additional re-
efficiency of REE. Synergist extractant boosts the potential of in-
agents are added into harvested strains to enhance the electrostatic
dependent extractant to be highly efficient, reduces the extractant
interaction, surface complexion, and active functional groups, whereas
consumption, and increases the stability of extractant. The same con-
the dried cell diameter size can be manipulated through grinding
cept is applied by immobilising the advanced extractant onto selected
(Moriwaki et al., 2013; Das and Das, 2013).
solid for better contact and mass transfer of metal ions.
Another additional modifications are made on adsorbent to increase
Apart from being hydrophobic, IL such as [C8mim][PF6] contributes
the selectivity of REE such as IIL on polymer (Garcia et al., 2002) and
to stronger structure of silica, increases in the size of pores, and in-
REE binding tag on cell surface (Park et al., 2016). Garcia et al. (2002)
creases availability of surface area. Normal extractants like Cyanex 923
produced IIL on polymer resin by first designing the IL imprinted with
and Cyphos IL-104 hardly have any impact on the surface of materials
Gd(III). Subsequently, the IIL is immobilised on the polymer resin.
(Liu et al., 2009, 2007). Liu et al. (2009) had conducted four times
Then, cation contained Gd(III) is removed from the IIL to provide an
regeneration using silica immobilised with SE of Cyanex 923-[C8mim]
empty cation space specifically for Gd(III) that is extracted from aqu-
[PF6]. Declination was discovered in extraction from 94 to 76% of Y(III)
eous solution. When adsorption takes place, Gd(III) is adsorbed im-
using SE of Cyanex 923-[C8mim][PF6] with loss of C8mim+ in aqueous
mediately on the surface of immobilised IIL polymer resin with less
solution (Liu et al., 2007). However, the same type of silica, under the
competition with other REE (Garcia et al., 2002). This material mod-
same operating condition and same number of cycles, silica im-
ification gives very high selectivity but the adsorption capacity is
mobilised with Cyphos IL 104-[C4mim][PF6] showed a slight reduction
considered low compared to other adsorption materials. In addition, the
with 93% Y(III) extracted (Liu et al., 2009). This may be related to
synthesis process for IIL is complex. Cell surface binding tag implies the
Cyphos IL-104 being better extractant than Cyanex 923 and high visc-
same idea and has been tested on La(III) (Park et al., 2016).
osity of [C8mim][PF6] reduced the efficiency of the REE extraction.
Sun et al. (2008) compared the immobilisation methods between
immersing the resin in SE of hexane-Cyanex 923 and direct immersing
4. Summary
of resin in SE of IL-Cyanex 923. Hexane as diluent is less effective in
retaining Cyanex 923 compared to IL with 42% loss of Cyanex 923
The separation and extraction of REE has been realised in various
using hexane into aqueous while using IL, the loss rate was smaller with
methods and chemicals. Solvent extraction is the most common method
only 30% loss of Cyanex 923 (Sun et al., 2008). This concludes that IL is
but lack in extraction and selectivity efficiency. Researchers have been
benefited by restraining extractant from losing into aqueous solution. In
trying to improve the properties of extractant to diminish the efficiency
2009, Xiaoqi changed the SE immobilised on Amberlite 7 with Aliquat
problems in extraction of REE. This situation leads to discovery of a
336 and CA-100 ([A336][CA-100]). [A336][CA-100] immobilised on
wide range of extractants, either independent solvent extractants (i.e.,
Amberlite XAD-7 was found to be more effective in extracting Sc(III)
D2EHPA, TBP, and DODGAA) or SE (i.e., HL-HTTA and CMPO-[C4mim]
compared to XAD-7 immobilised with [A336][NO3] and the extraction
[NTf2]).
reached an equilibrium in less than 30 min (Xiaoqi et al., 2009). In
Regardless of the type of extractant, the extraction efficiency of REE
other case study, the same resin exhibited a different adsorption be-
is still poor due to technical drawbacks in LLE such as formation of third
haviour using different immobilisation of extractants such as Cyanex
phase and poor contact between organic and aqueous phases.
923, D2EHPA, and PC88 A. D2EHPA on XAD-7 obviously adsorbed La
Therefore, SLE is implemented to counter the drawbacks in LLE using
(III) better than Cyanex 923 and PC88A even under the big ratio of
supporting materials. SIR and SIL started to influence the conventional
aqueous to resin of 200:1. Thus, D2EHPA has high selectivity on Sc(III)
process in the extraction of REE through the development of various
over La, Ce, Pr, and Nd (Lee et al., 2009). This concludes that extractant
types of supporting materials. Basically, SIR and SIL are employing the
infused into polymer matrix plays a significant role in increasing the
concept of EIM in SLE.
extraction degree of REE, apart from morphology of the matrix.
The materials used for EIM can be selected from polymeric resin,
silica, and microorganism. These materials are modified accordingly to
3.2.4. Other modification methods enhance the physical and chemical properties. Some of the materials
Materials modified from microorganism are yet to be immobilised are immobilised with selected extractant to enhance the selectivity of
with any extractants in any literatures. Most cell are naturally REE during SLE process. The use of EIM can be the new trend in the

111
N.N. Hidayah, S.Z. Abidin
extraction of REE. Based on literatures, most EIM have better extraction
and selectivity efficiency compared to extraction using conventional
method of LLE. Thus, EIM is capable of increasing the surface area of
organic phase, reducing the formation of third phase, reducing the loss
of extractant into aqueous phase, and reducing the consumption of
extractant.
Acknowledgement
This research was supported by the Ministry of High Education
Malaysia [grant number: RDU150115].
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