Journal of Membrane Science 585 (2019) 218–229

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Silver-based ionic liquid as separation media: Supported liquid membrane T

for facilitated methyl linolenate transport
Xianghong Lu∗, Qianxia Chen, Dehua Zhao, Jiajian Zhu, Jianbing Ji
Zhejiang Province Key Laboratory of Biofuel, Biodiesel Laboratory of China Petroleum and Chemical Industry Federation, College of Chemical Engineering, Zhejiang
University of Technology, Hangzhou, 310014, PR China

ARTICLE INFO ABSTRACT

Keywords: Methyl linolenate (C18-3) is a type of unsaturated fatty acid methyl ester with high biological activity.
Supported ionic liquid membrane Membrane separation of C18-3 from tallow seed oil methyl ester by supported ionic liquids membranes (SILM)
Methyl linolenate containing carrier Ag+ was successfully achieved in this study. The interaction between Ag+ and C18-3 was
Complexation explored by density functional theory (DFT). High selectivity to C18-3 was mainly due to the π/inverse π
DFT
complexation interactions between Ag+ and C=C bonds. The effects of ionic liquid structure, carrier Ag+
AgBF4
concentration, adjacent phase flow rates and membrane pore size on permeability and selectivity to C18-3 were
examined. The existence of 1-hexene in the stripping phase and carrier Ag+ can facilitate C18-3 transport. Good
separation performance was achieved by the 0.45 μm nylon membrane impregnated with ionic liquid [BMIm]
BF4 containing AgBF4. C18-3 was enriched from 16.7% in the feed phase to higher than 75% in the product.
Moreover, adding a hydrophobic PVDF protective membrane to form a composite membrane was an effective
method to increase the SILM stability and membrane lifetime by about twice compared with a single nylon
membrane.

1. Introduction
Linolenic acid, an omega-3 polyunsaturated fatty acid, is nu-
tritionally important to form cell membranes and biological enzymes. It
has functions of lowering the level of blood pressure, maintaining li-
poprotein balance and regulating cholesterol metabolism.
Unfortunately, humans can't biosynthesize omega-3 fatty acids which
must be taken from the outside [1–3]. Linolenic acid (in the form of
glyceride) presents in plants such as linseed oil, perilla seed oil, and
eucalyptus oil with oleic acid, linoleic acid and palmitic acid together.
Due to the similarity of molecular size, polarity and structure, separa-
tion of linolenic acid from unsaturated analogues remains challenging.
Several methods were proposed to separate polyunsaturated fatty acids
(esters), including freezing crystallization [4], molecular distillation
[5], urea complexation [6], supercritical fluid extraction [7] and silver
ion complexation [8].
Silver ion complexation extraction is a separation method based on
the complexation between Ag+ and C=C bonds. Compared with other
methods, the silver ion complexation extraction has advantages of high
selectivity, mild separation conditions and low reaction energy, which
has been widely used to separate unsaturated fatty acids (esters) by
liquid-liquid extraction [9]. Li et al. [10] reported that silver salt/ionic
liquid (IL) was an excellent extraction solution to separate and enrich
polyunsaturated fatty acid methyl esters. C20-5 (EPA) and C22-6 (DHA)
were largely enriched from 18.0% in the original cod liver oil to 74.2%
with [HMIm]PF6 containing AgBF4 as the extractant.
However, liquid-liquid extraction consumes large quantities of ex-
pensive silver salts and needs multi-step operations to fully separate
target product. To reduce the consumption of silver salts and simplify
manipulations, liquid membrane separation technology is a promising
alternative. The liquid membrane separation technology combines two
processes of extraction and stripping in a single operation simulta-
neously, with target product directly obtained from stripping solvent.
Besides, small quantities of membrane solvent and carrier could achieve
efficient separation. It also has advantages of larger specific surface
area for extraction, one-step mass transfer operation, better energy ef-
ficiency, lower consumption of organic solvents and much lower en-
vironmental impact, which has been suggested for many industrial
fields [11]. In general, there are different types of liquid membranes
such as supported liquid membranes (SLM), bulk liquid membranes
(BLM), and emulsion liquid membranes (ELM) [12]. Emulsion liquid
membrane, known as emulsion surfactant liquid membrane, usually has

∗
Corresponding author.
E-mail addresses: luxh@zjut.edu.cn (X. Lu), 535852494@qq.com (Q. Chen), 1542108788@qq.com (D. Zhao), 514019880@qq.com (J. Zhu),
jjb@zjut.edu.cn (J. Ji).

https://doi.org/10.1016/j.memsci.2019.05.027
Received 31 January 2019; Received in revised form 10 May 2019; Accepted 10 May 2019
Available online 17 May 2019
0376-7388/ © 2019 Elsevier B.V. All rights reserved.
X. Lu, et al.
stability issues. In addition, making and breaking emulsion is a difficult
and costly process [13]. As to the BLM, Zhang et al. [14] selected
methanol-AgNO3 aqueous solution as BLM to separate methyl linole-
nate from tallow seed oil methyl ester. Under the optimal conditions,
methyl linolenate with purity of 94.1% could be extracted from the
tallow seed oil methyl ester, and the yield was approximately two times
higher than that of fraction extraction. Baylan et al. [15] used imida-
zolium-based ionic liquids as a bulk liquid membrane, tributyl phos-
phate as a carrier in the membrane to remove levulinic acid. However,
the extreme thickness of the membrane phase (thickness ≥ 0.1 cm)
results in large mass transfer resistance and low mass transfer rate of
BLM in the separation process. Therefore, BLM is difficult to upgrade
from lab scale to pilot/commercial scale. SLM is a liquid membrane
prepared by impregnating porous supports in the membrane solvent
with dissolved carriers by capillary forces [16]. Compared with BLM,
the thickness of SLM is extremely minimal, therefore, the mass transfer
rate could be effectively increased and the consumption of membrane
solvents and carriers would be greatly reduced. The main drawbacks of
SLM are low stability and short lifetime resulting from leakage or
evaporation of membrane phase, which limit the scale up of the SLM
technique [17]. An effective approach to enhance the stability of SLM is
to appropriately increase the viscosity of membrane phase. Relatively
high viscous ILs with negligible vapor pressure is a promising mem-
brane solvent. Furthermore, ILs have excellent solvent properties
[18,19]. In previous studies, supported ionic liquid membrane (SILM)
was used to separate light organic compounds such as alcohols, organic
acids, and aromatic hydrocarbons [17,20,21], mixed gases [22,23] and
metal ions [24,25]. However, to our best knowledge, no studies on the
separation of unsaturated fatty acid methyl esters (UFAMEs) by SILM
were reported.
In this work, SILM containing carrier Ag+ was designed for methyl
linolenate (C18-3) extraction from tallow seed oil methyl ester mix-
tures. The effects of different ILs and operating variables (Ag+ con-
centration, adjacent phase flow rates and pore size of supported
membrane) on the separation process were investigated. DFT calcula-
tion was conducted to explore the action mechanism between Ag+ and
UFAMEs at the molecular level. In addition, a 24 h long-term operation
verified the stability of SILM and then an effective procedure was
proposed to increase the membrane lifetime.
2. Materials and methods
2.1. Materials
In this paper, the feed phase was fatty acid methyl esters (FAMEs)
petroleum ether solution. The stripping phase was 1-hexene petroleum
ether solution. Nylon membrane with different pore size of 0.22 μm and
0.45 μm was used as supported membrane. PVDF membrane with pore
size of 0.45 μm was used as protected membrane. Nylon membrane and
PVDF membrane were purchased from Tianjin Bo Jin Technology Co.,
Ltd.
The FAMEs mixture was prepared with tallow seed oil by transes-
terification. The composition of FAME mixture was determined by GC-
FID, as listed in Table 1.
Table 1
The composition and content of tallow seed oil methyl ester.
FAME Formula Content
Methyl-2,4-decandienoate CH3CH=CHCH=CH(CH2)4COOCH3 1.4%
(C10-2)
Methyl Palmitate (C16-0) CH3(CH2)14COOCH3 15.3%
Methyl Stearate (C18-0) CH3(CH2)16COOCH3 4.5%
Methyl Oleate (C18-1) CH3(CH2)7CH = CH(CH2)7COOCH3 30.2%
Methyl Linoleate (C18-2) CH3(CH2)3(CH2CH=CH)2(CH2)7COOCH3 31.9%
Methyl Linolenate (C18-3) CH3(CH2CH=CH)3(CH2)7COOCH3 16.7%
219
Journal of Membrane Science 585 (2019) 218–229
ILs with the purity of 99% were purchased from Lanzhou Green
Chemistry and Catalysis, LICP, CAS(China). The molecular structures
and physical properties of ILs used in this work were listed in Table 2.
AgBF4 (≥99%, purity) was obtained from Adamas Reagent Co. Ltd.
1-hexene (≥95%, purity) was obtained from Tokyo Chemistry Industry
Co. Ltd. All the materials were used without further purification.
2.2. Methods
2.2.1. Preparation of SILMs
All SILMs were prepared at room temperature by impregnating the
porous membrane with ILs. Due to the complexation of Ag+ with 1-
hexene, the addition of 1-hexene as cosolvent could effectively promote
the dissolution of AgBF4 in IL. First, a certain amount of AgBF4, 0.6 mL
1-hexene and 0.5 mL ionic liquid were added into a 2 mL centrifuge
tube which was shaken for 10 min. Then the mixture was centrifuged at
12000 rpm for 10 min in darkness to ensure the complete stratification
of two phases, and the lower liquid was applied to the surface of the
support. After the membrane was wetted thoroughly, excess of liquid
was removed from the membrane surface using a tissue [26]. To de-
termine the amount of membrane solvent immobilized in the support
membrane, all the membranes were weighed before and after impreg-
nation.
2.2.2. Liquid membrane extraction configuration
The schematic of experimental setup used in this study was shown
in Fig. 1. Membrane contactor consisted of two identical PTFE modules
(100 mm × 100 mm × 8 mm), and each module had a cylindrical
cavity with a diameter of 47 mm and a height of 2 mm. In the upper
PTFE module there were two ports which corresponded with the
stripping solvent inlet and outlet. Similarly, in the lower PTFE module
there were also two connections which were the feed solution inlet and
outlet. The SILM was clamped in the two PTFE modules and sealed by
fluoro rubber gaskets hermetically to avoid the leakage of liquid. The
stripping solvent and the feed solution were placed in 50 mL sealed
centrifugal tubes and delivered by peristaltic pumps (Baoding Longer
Precision Pump Co., Ltd.).
2.2.3. Liquid membrane extraction operation
The prepared supported ionic liquid membrane was placed into the
membrane contactor, and screws were tightened firmly to keep the
membrane from moving. FAMEs petroleum ether solution (50 mg/mL)
was used as feed solution. 10 wt% 1-hexene petroleum ether solution
was used as stripping solvent. Feed solution (20 mL) and stripping
solvent (20 mL) were placed in 50 mL centrifugal tubes apart. The
stripping solvent and the feed solution were circulated through upper
and lower sides of the membrane respectively in a cross flow way. The
flow rates were adjusted by peristaltic pumps, and calibrated by mea-
suring the volume of liquid with a graduated cylinder and a stopwatch.
Samples (1 mL) were taken from the stripping solvent tube and the
feed solution tube respectively per hour, and then analyzed by GC to
determine the content of FAMEs. The concentration of FAMEs over time
in the stripping solvent and the permeability of FAMEs were used to
describe the mass transfer rate of SILM. The separation factor and the
purity of C18-3 in the product were used to characterize the separation
performance of SILM. The separation factor was calculated by Eq. (1).
( i / j ) stripping phase
Separation factor Sij =
( i / j ) feed phase (1)
where Sij stands for the degree of separation between component i and
component j; ωi and ωj are the mass fraction of components i and j.
The permeability coefficient (P) was calculated by the following
method. The C18-3 mass flux J = P (Cf - Cs), where P is the permeability
of SILM, Cf and Cs are C18-3 concentrations in the feed phase and the
stripping phase respectively. The mass flux was also expressed
X. Lu, et al. Journal of Membrane Science 585 (2019) 218–229

Table 2
Molecular structures and physical properties of ILs.
′ Cation Anion Viscosity (cP, 20 °C) density（g/cm3） MW

[EMIm]BF4 45 1.21 197.97

[BMIm]BF4 140 1.26 226.02

[HMIm]BF4 266 1.15 254.08

[OMIm]BF4 415 1.09 282.13

[BMIm]PF6 366 1.37 284.18

[BMIm]NTf2 69 1.44 419.36

[BMIm]CF3SO3 93 1.29 288.29

V dC
as J = Ss dts according to the mass balance, where Vs, S and ε are the gas chromatograph (GC) equipped with an auto injector (Model
volume of stripping phase, the membrane area and the membrane 7683B), a flame ionization detector (FID) and a J&W DB-WAX column
porosity respectively. Cf = Cf0 - Cs when the feed phase and the strip- (30 m×32 μm×0.25 μm). The temperatures of injector port and FID
ping phase have the same volume. Then, ln 1
2Cs
= 2 V Pt could be
S were held at 280 °C and 300 °C respectively. The oven temperature was
C f0 s initially held constant at 150 °C for 2 min, and increased at 10 °C/min
Vs dCs
obtained from the integration ofP (Cf Cs ) = S dt
, and P can be de- to 200 °C and kept at 200 °C for 4 min, followed by being increased at
40 °C/min to 230 °C, and finally held at 230 °C for 9 min. The injector
termined from the slope of ln 1 over time.
2Cs
C f0 volume was 1 μL and the split ratio was 15:1 [27].
The absolute correction factor of methyl palmitate, methyl stearate,
2.2.4. GC analysis methyl linoleate and methyl linolenate was regarded as the same
The concentration of FAMEs was determined by an Agilent 7890A

Fig. 1. Schematic of membrane module device.

220
X. Lu, et al.
Table 3
Electron configuration of silver ion.
UFAME Functional group
3+
[C18-2·3Ag] C=C
C=O
[C18-3·4Ag]4+ C=C
C=O
because of their highly similar molecular structure and physicochem-
ical properties [28,29]. Methyl palmitate with purity of 98% was
chosen to obtain the absolute correction factor. Then the concentration
of fatty acid methyl ester was calculated using Eq. (2):
Ci = f Ai (2)
−3
where f is the absolute correction factor (f = 1.98 × 10 ); Ci stands
for the concentration of component i; Ai is the peak area of component
i.
2.2.5. X-ray diffraction (XRD)
XRD analysis of blank nylon membrane and the support ionic liquid
membrane was carried out on an X'Pert Pro Advance diffractometer
with Cu-Kα radiation source (λ = 1.5406 Å) at 40 KV and 30 mA. The
diffraction patterns were collected in the range of 2θ from 10° to 80° by
step of 0.05°.
2.2.6. Computational details
The structure optimization of C18–3 and C18-2 was performed at
B3LYP/6-31G (d, p) level of theoretical method using SMD model in
Gaussian program. The electronic properties of these two compounds,
such as HOMO, LUMO and NLUMO, were also recognized by DFT ap-
proach.
The structures of the two complexes of C18-3·Ag+ and C18-2·Ag+
were optimized at the level of B3LYP/6-311 + G (d, p) +LANL2DZ.
The atoms of C, H and O have been described with 6–311 + G (d, p)
basis sets, and Ag+ with LANL2DZ basis sets. Vibrational analyses were
performed at the same level to confirm the stationary of the optimized
geometries. The results showed that the optimized structures corre-
sponded to a minimum of potential energy surface with no imaginary
frequency. Natural bond orbital (NBO) analysis was also carried out for
the evaluation of the orbital contribution of all possible donor atoms of
ligands to Ag+ for C18-3·Ag+ and C18-2·Ag+, and the bonding and
anti-bonding charge transfer was clarified quantitatively using second
order perturbation energy.
3. Result and discussion
3.1. Interaction between carrier Ag+ and UFAMEs
Silver ions (or other transition metal ions such as cuprous) could
form reversible π-bond complexation with C=C bonds [30], which
could effectively improve the extraction efficiency and selectivity to
unsaturated materials [31,32]. Li et al. [10] illustrated the extraction of
UFAMEs predominantly resulted from the coordinative interaction be-
tween silver ions and UFAMEs, and the distribution ratios of C18–3 and
C18-2 reached 42.0 and 18.4, respectively, at AgBF4 concentration of
0.042 mmol/mL. Dou et al. [33] used SILMs with carrier Ag+ to carry
out efficient ethylene/ethane separation, and ethylene permeability
and ethylene/ethane selectivity were significantly elevated. These
works showed that Ag+ is an effective carrier to promote the separation
of saturated/unsaturated compounds. However, although the
221
Journal of Membrane Science 585 (2019) 218–229
Ag+ electronic configuration
Before complexation After complexation
[core]5s(0.00)4d(10.00) [core]5s(0.11)4d(9.94)5p(0.03)
[core]5s(0.09)4d(9.94)5p(0.01)
[core]5s(0.07)4d(9.98)5p(0.02)
[core]5s(0.00)4d(10.00) [core]5s(0.09)4d(9.94)5p(0.01)
[core]5s(0.08)4d(9.94)5p 0.01)
[core]5s(0.09)4d(9.94)5p(0.01)
[core]5s(0.07)4d(9.98)5p(0.02)
interaction between Ag+ and double bonds has already been experi-
mentally investigated (UV–visible spectroscopy and FT-IR analysis)
[31], few researchers theoretically studied it at the molecular level. In
addition, in our work, both carbonyl group and C=C bonds in the
molecule of C18-3 possess large negative electrostatic potentials [27],
and thus both structures can interact with Ag+, which was not con-
ducive to improving the selectivity to C18-3. Thus, we investigated the
action mechanism by DFT and made a deeper insight into the re-
lationship between Ag+ and UFAMEs. In addition, the performance of
carrier Ag+ and the effect of Ag+ concentration on separation of C18-3
were studied.
3.1.1. The action mechanism between Ag+ and UFAMEs
NBO analysis could be used to investigate the electron transfer and
orbital action in the molecule, which is beneficial to the analysis of the
action mechanism between molecules. To explore the interaction site
between Ag+ and UFAMEs, Ag+ electronic configurations before and
after complexation were obtained by NBO calculation. The calculation
was performed using the NBO 3.0 program as implemented in the
Gaussian 09 package at 311 + G (2d, p) +LANL2DZ level while silver
ions were placed near the carbon-carbon double bonds and carbonyl
groups of unsaturated fatty acid methyl ester molecules. Three silver
ions coordinated respectively with two C=C bonds and a carbonyl
group of C18-2, while four silver ions respectively coordinated with
three C=C bonds and a carbonyl group of C18-3. The electron con-
figurations of silver ions were shown in Table 3.
Before complexation, the 5s orbit of Ag+ was empty, while 4d orbit
was full. In Table 3, regardless of Ag+ interacted with a carbonyl group
or C=C bonds, the electron quantity of the 5s and 4d orbitals increased
and decreased, respectively, which indicated the UFAMEs provided
electrons to form σ coordination bond with the 5s orbital of Ag+, while
Ag+ provided 4d electrons to UFAMEs and formed π back bonding
coordination. Compared with the complexation between C=C bonds
and sliver ions, the number of electrons increased in the 5s and de-
creased in the 4d was fewer than silver ions coordinated with carbonyl
group. It showed that the interaction between Ag+ and C=C bond was
stronger than that between Ag+ and carbonyl group, in other words,
Ag+ preferentially coordinated with the C=C bonds.
Zhu et al. [27] calculated the molecular electrostatic potential of
C18-3 molecule at the level of DFT/B3LYP/6-311G (d, p) using the SMD
solvent model of Gaussian view. The results showed that the negative
electrostatic potential of the carbonyl group was higher than the C=C
bond, but the stability of the functional groups was not investigated.
Since both the molecular electrostatic potential and stability of func-
tional group affected its donating electrons ability, the stability of Ag+
interacted with these two functional groups was further investigated in
this work based on frontier molecular orbital analysis. The molecular
orbitals and the energy levels of C18–2 and C18-3 molecules were
displayed in Fig. 2 by single-point calculation using the SMD solvent
model at the level of B3LYP/6-311 + G (2d, p) +LANL2DZ of Gaussian
view.
HOMO is the highest occupied molecular orbital with the donating
X. Lu, et al.
Fig. 2. Frontier orbitals of methyl linoleate and methyl linolenate molecule.
electrons ability, LUMO is the lowest unoccupied molecular orbital with
the accept electrons ability, and NLUMO is the next lowest unoccupied
molecular orbital with the accept electrons ability just below LUMO.
According to the frontier molecular orbital calculation, it could be seen
that HOMO and NLUMO charge density almost covered the C=C bond,
and the LUMO density was scattered only over C=O bond.
Since HOMO had the strongest electron-donating ability, silver ions
preferentially formed π orbitals with C=C bonds. Although the LUMO
orbit had the strongest electron accepting ability, the inverse π com-
plexation of Ag+ with the carbonyl group was unstable because the
HOMO was far apart from the LUMO located at C= O bond. Through
further orbital calculations, the energy level of NLUMO orbital was
almost the same as that of LUMO (Table 4), particularly for the C18-3
molecule, indicating that NLUMO had the same ability to accept elec-
trons. Furthermore, NLOMO and HOMO charge density both covered
the C=C bond, which indicated that Ag+ could form stable com-
plexation and anti-collaboration on the C=C bond. Thus, based on the
NBO analysis and frontier molecular orbital analysis, Ag+ preferentially
combined with C=C bonds and the interaction force between them was
stronger.
3.1.2. Fundamentals of transport
The complexation between Ag+ and C18-3 shown in Eq. (3) is a
reversible reaction, and the reaction direction can be altered by C18-3
concentration swing. On the feed side, the higher C18-3 concentration
contributed to coordination between C18-3 and Ag+, and thus C18-
3·Ag+ was formed and diffused through the SILM to the stripping side.
On the stripping side, the reaction proceeded in the reverse direction as
C18-3 concentration fell down sharply, which resulted in the decom-
plexation of C18-3·Ag+ and regeneration of SILM. Ag + transported to
the feed side to coordinate with C18-3 again.
Ag + + C18 3 C18 3·Ag +
To further increase the permeation rate of C18-3, 1-hexene was
added into the stripping solvent. 1-hexene and C18-3 can compete for
Table 4
Energy of selected molecular orbitals of methyl linoleate and methyl linolenate
molecule.
Orbital Energy
Methyl linoleate Methyl Linolenate
NLUMO 0.0637 eV −0.1254 eV
LUMO −0.1929 eV −0.1331 eV
HOMO −6.6151 eV −6.5689 eV
Journal of Membrane Science 585 (2019) 218–229
the complexation with Ag+ by C=C bonds in their molecules. The
competition mechanism can be explained by Eq. (4). On the feed side,
the reaction proceeded in a positive direction due to stronger com-
plexation ability of C18-3. On the stripping side, the high concentration
of 1-hexene prompted the reaction to proceed in the opposite direction.
The C18-3·Ag+ was decomplexed and the 1-hexene·Ag+ was formed.
The formed 1-hexene·Ag+ transported to the feed side to carry C18-3
again. Thus, we chosen 10 wt% 1-hexene petroleum ether as stripping
solvent to increase the transport rate of C18-3.
1 hexene·Ag + + C18 3 C18 3·Ag+ + 1 hexene (4)
3.1.3. Ag+ concentration
According to the action mechanism between Ag+ and UFAMEs,
+
Ag preferentially interacted with the C=C bonds of UFAME.
However, if Ag+ concentration is too high, excess Ag+ may react with
the carbonyl group to reduce the selectivity of C18-3, and the interac-
tion between Ag+ and UFAME would be enhanced excessively, which is
not conducive to the decomplexation. Thus, the effect of Ag+ con-
centration on the C18-3 extraction should be investigated. In this work,
membrane solvent with a concentration of 0–0.5 g/mL AgBF4 was se-
lected to coat on the supported nylon membrane. The concentration of
C18-3 over time in the stripping solvent was shown in Fig. 3a. The
purity of C18-3 in the product and the separation factor of C18-3 to
C18-1 (SC18-3/C18-1) and C18-3 to C18-2 (SC18-3/C18-2) within 6 h were
shown in Fig. 3b. Table 5 listed the permeability of C18–1, C18–2 and
C18-3 through different SILMs.
Experimental conditions: the initial concentration of fatty acid
methyl esters in feed phase: 50 mg/mL, stripping phase: 10 wt% 1-
hexene petroleum ether, the pore size of nylon membrane: 0.45 μm, IL:
[BMIm]BF4, flow rate:40.1 mL∙min−1.
Ag+ could promote the mass transfer rate and increase the se-
(3)
lectivity to C18-3. Compared with the absence of AgBF4, the C18-3
permeability increased by 3.1 times (0.2 g/mL AgBF4), 6.6 times (0.4 g/
mL AgBF4) and 10.1 times (0.5 g/mL AgBF4), respectively. Ag+ had less
influence on C18–2 and C18-1 due to their less C=C bonds. The per-
meability of C18-2 increased slightly with the increase in Ag+ con-
centration, with that of C18-1 slightly decreased. No obvious change in
the interaction between Ag+ and carbonyl group was found in the
range of 0–0.5 g/mL AgBF4. The difference in the permeability of
C18–3, C18–2 and C18-1 resulted in the increase in C18-3 selectivity
and purity. SC18-3/C18-1 and SC18-3/C18-2 reached up to 12.53 and 8.73,
respectively using 0.5 g/mL AgBF4, with the purity of C18-3 reaching
75%.
In our work, a SILM with about 0.1 mL membrane solvent con-
taining 0.05 g AgBF4 was used to extract C18-3 from 50 mg/mL FAMEs
222
X. Lu, et al. Journal of Membrane Science 585 (2019) 218–229

Fig. 3. Effect of AgBF4 concentration on (a) C18-3 concentration in stripping phase, (b) separation factors and purity of C18-3 in the product.

Table 5 the increase in the alkyl side chain length of imidazole ring. The
Effect of AgBF4 concentration on the permeability of C18–1, C18–2 and C18-3. maximum C18-3 permeability was obtained when the substituent group
CAgBF4 (g/mL) Permeability ( × 10−9 m/s) was butyl. As to the separation performance, [BMIm]BF4 also showed
the highest selectivity to C18-3, with SC18-3/C18-1 and SC18-3/C18-2
C18-1 C18-2 C18-3 reaching up to 12.53 and 8.73, respectively. Moreover, the purity of
C18-3 increased to almost 75% [BMIm]BF4 was used, which was in-
0.0 1.78 1.72 1.56
0.1 1.76 1.74 1.79 creased by about 20% compared with other ILs.
0.2 1.62 1.95 4.82 Overall, the alkyl side chain of IL cation had a significant impact on
0.3 1.53 1.90 4.60 the extraction of C18-3, which would affect the mass transfer rate and
0.4 1.31 2.31 10.33 the separation performance of SILM. Since UFAMEs could form hy-
0.5 1.15 2.69 15.77
drogen bonds with the H atoms on the imidazole ring, UFAMEs could be
separated from the saturated ones [27]. The alkyl side chain on the
mixture (16.7 wt% C18-3) in 20 mL feed solution, with the molar ratio imidazole ring affected the van der Waals force and hydrogen bond
of silver ions to C=C bonds of 0.16:1. As reported by Li et al. [9], AgBF4 interaction between cations and anions, which influenced the funda-
(5.5 mg) dissolved in [BMIm]BF4 (1 mL) as extraction phase was se- mental characteristics of IL such as polarity, hydrogen bond acidity and
lected to extract C18-3 (2 mg) dissolved in hexane (1 mL), with the basicity, viscosity, density and melting point. Therefore, the interaction
molar ratio of silver ions to C=C bonds of 1.37:1. The results showed between ILs and UFAMEs varied for different alky side chains. The IL
that the amount of Ag+ in membrane extraction was much lower than polarity, hydrogen bond acidity and basicity were usually described by
that in liquid-liquid extraction, which demonstrated that the amount of the empirical scales of Reichard's dye ET(30) and Kamlet-Taft using
Ag+ needed in the SILM extraction was minimal, and Ag+ as a carrier solvatochromic chemical probes [35–38]. The Kamlet-Taft method has
could facilitate transport repeatedly. three parameters: hydrogen-bond acidity (α), hydrogen-bond basicity
(β) and dipolarity/polarizabilty (π*). Considering these parameters, the
extraction ability of different SILMs for UFAMEs could be further ex-
3.2. The structure of ILs
plained.
The mass transfer rate of SILM was mainly affected by the polarity,
Imidazolium ionic liquid is a low-melting salt composed of an imi-
viscosity and steric hindrance of IL. The polarity of ILs followed the
dazolium ring and an organic or inorganic anion. The difference in IL
order: [OMIm]BF4＜[BMIm]BF4＜[HMIm]BF4≈[EMIm]BF4 (Table 7).
molecular structure leads to different physicochemical properties [34],
C18-3 was a low polarity material, which was easier to be dissolved into
e.g., viscosity, dissolving capacity for AgBF4, interaction with UFAMEs,
[OMIm]BF4 and [BMIm]BF4. Besides, due to higher viscosity, [OMIm]
which would have influence on SILM stability, permeability and se-
BF4 had huger resistance against mass transfer than other ILs. The steric
lectivity. In our study, imidazolium ionic liquids with different carbon
hindrance also increased with increasing alkyl chain length, which was
chain lengths and anions were selected as membrane solvents, and the
unbeneficial to the formation of hydrogen bonds between UFAMEs and
separation performance of Ag+ in different ILs was investigated.
imidazole rings [27]. Therefore, [OMIm]BF4 and [HMIm]BF4 as mem-
brane solvents had lower permeability than that of [BMIm]BF4 al-
3.2.1. The alkyl side chain of IL cation though they possessed higher C18-3 solubility. The selectivity to C18-3
Four ionic liquids with the same anion of [BF4]- were selected to was mainly affected by the hydrogen bond interaction between ILs and
investigate the effect of the length of the alkyl side chain at position 3 UFAMEs. With the increase in alkyl chain length, α/π* decreased and β
on the imidazole ring on the extraction separation of C18-3. The per- increased. Because higher hydrogen-bond acidity (α) could provide
meability and separation ability of different SILMs were shown in Fig. 4 more protons to form hydrogen bonds with UFAMEs, [BMIm]BF4 had
and Table 6. the higher interaction with C18-3 compared with [OMIm]BF4 and
Experimental conditions: the initial concentration of fatty acid [HMIm]BF4. In summary, when the alkyl side chain of imidazole ring
methyl esters in feed phase: 50 mg/mL, stripping phase: 10 wt% 1- was the butyl group, SILM showed the highest mass transfer rate and
hexene petroleum ether, AgBF4 concentration in membrane solvent: best separation performance.
0.5 g/mL, the pore size of nylon membrane: 0.45 μm, flow rate:
40.1 mL∙min−1.
It could be seen that both the concentration of C18-3 in the stripping 3.2.2. IL anion
solvent and C18-3 permeability first increased and then decreased with Zhu et al. [27] selected eight kinds of ionic liquids with the same

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Fig. 4. Effect of the alkyl side chain length of ILs on (a) C18-3 concentration in stripping phase, (b) separation factors and purity of C18-3 in the product.

Table 6 side) and decomplexation (on the stripping side), and the hydrogen-
Effect of the structure of ILs on the permeability of C18-3. bond basicity (β) had different effects on them. When β was low, the
ILs P × 10−9 (m/s) electron donating ability of ILs was relatively poor, and the interaction
between carrier Ag+ and IL decreased, which was more favorable for
[EMIm]BF4 7.26 the complexation of Ag+ with UFAMEs but not conducive to decom-
[BMIm]BF4 15.77
plexation. A suitable β value facilitated the complexation/decom-
[HMIm]BF4 6.92
[OMIm]BF4 6.28
plexation between Ag+ and UFAMEs. The results showed [BMIm]BF4
[BMIm]NTf2 5.22 had the highest mass transfer rate and best separation performance,
[BMIm]PF6 0.65 which indicated that the IL with β value of about 0.39 would be an
[BMIm]CF3SO3 5.77 appropriate membrane solvent.

3.3. Adjacent phase flow rates

Table 7
Reichard's dye and Kamlet-Taft parameters of imidazolium ionic liquids.
The transport process of the FAMEs from the feed phase to the
Ionic liquid Reichard's dye Kamlet-Taft Reference stripping phase involves five consecutives steps [19]: (1) forced con-
vection from the bulk of the feed solution to the feed–membrane in-
ET(30) π* α β
terface, (2) partition of the FAMEs between the feed phase and SILM,
[EMIm]BF4 53.7 – – – [37] (3) facilitated transport and molecular diffusion though the SILM to the
[BMIm]BF4 52.5 1.05 0.627 0.376 [37] membrane-stripping interface, (4) partition of the FAMEs between the
[HMIm]BF4 53.7 0.96 0.44 0.6 [37]
SILM and the stripping phase, (5) forced convection from the mem-
[OMIm]BF4 51.8 0.93 0.45 0.63 [37]
[BMIm]NTf2 51.5 0.96 0.63 0.24 [37,38]
brane-stripping interface to the bulk of the stripping solvent. The steps
[BMIm]CF3SO3 52.3 1.01 0.62 0.47 [37,38] of (2), (3) and (4) were affected by the concentration of silver ions. An
[BMIm]PF6 52.3 1.03 0.65 0.22 [37,38] appropriate Ag+ concentration was beneficial to the increase in parti-
tion coefficient of step (2) and (4), as well as the increase in the rate of
UFAMEs passing through the pores of SILM via facilitated transport in
cation [EMIm]+ to investigate the effect of anions on the liquid-liquid step (3). The step (4) was also affected by the properties of stripping
extraction of C18-3. The results indicated that anions played important solution. Besides, increasing forced convection could enhance the mass
roles in extraction of C18-3 in terms of the distribution coefficient and transfer rate of step (1) and (5). The forced convection could be in-
selectivity. tensified with the increasing flow rates of the feed solution and strip-
In this work, to investigate the effect of anions on the membrane ping solvent. Thus, to investigate the effect of the adjacent phase flow
extraction, [BMIm]NTf2, [BMIm]CF3SO3, [BMIm]BF4 and [BMIm]PF6 rates on the membrane extraction, the flow rates of the feed phase and
were chosen as membrane solvents to separate C18-3 from FAMEs. stripping phase across the membrane were set to 20 rpm
According to Fig. 5, [BMIm]PF6 was not suitable for the separation (16.5 mL∙min−1), 40 rpm (26.6 mL∙min−1)，60 rpm (40.1 mL∙min−1),
of C18-3. [BMIm]BF4 as membrane solvent had the highest mass 70 rpm (49.8 mL∙min−1) and 90 rpm (59.3 mL∙min−1).To eliminate the
transfer rate, and C18-3 concentration reached 1.24 mg/mL at 6 h transmembrane pressure and prevent the membrane deformation, the
which was only 0.50 mg/mL for [BMIm]NTf2 and [BMIm]CF3SO3. flow rates of adjacent phases were set to the same value. The perme-
Meanwhile, the C18-3 permeability of [BMIm]BF4 membrane was sig- ability and separation ability under the different adjacent phase flow
nificantly larger than other IL membranes, as shown in Table 6. The rates were shown in Fig. 6 and Table 8.
selectivity of ILs followed the order: [BMIm]NTf2＜[BMIm]CF3SO3 ＜ Experimental conditions: the initial concentration of fatty acid
[BMIm]BF4. When the anion was BF4−, the purity of C18-3 in the methyl esters in feed phase: 50 mg/mL, stripping phase: 10 wt% 1-
product was increased by 10.66% and 29.48% compared with hexene petroleum ether, AgBF4 concentration in membrane solvent:
[BMIm]CF3SO3 and [BMIm]NTf2. 0.5 g/mL, the pore size of nylon membrane: 0.45 μm, IL: [BMIm]BF4.
The difference in viscosity and HB acidity(α) for [BMIm]NTf2, It could be observed that the concentration of C18-3 in the stripping
[BMIm]CF3SO3 and [BMIm]BF4 was slight. However, the difference in phase and C18-3 permeability first increased and then decreased with
hydrogen-bond basicity(β) resulted in the different extraction ability of the increasing flow rates, and C18-3 permeability achieved a maximum
the three ILs by affecting the interactions between Ag+ and UFAMEs. value of 15.77 × 10−9 m/s at 40.1 mL/min. The change trend of C18-2
The liquid membrane extraction contained complexation (on the feed permeability was similar to that of C18-3, while the C18-1 permeability

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Fig. 5. Effect of IL's anion on (a) C18-3 concentration in stripping phase, (b) separation factors and purity of C18-3 in stripping phase. Experimental conditions: the
initial concentration of fatty acid methyl esters in feed phase: 50
mg/mL, stripping phase: 10 wt% 1-hexene petroleum ether, AgBF4 concentration in membrane solvent: 0.5 g/mL, the pore size of nylon membrane: 0.45 μm, flow
rate:40.1 mL∙min−1.

Fig. 6. Effect of flow rate on (a) C18-3 concentration in stripping phase, (b) separation factors and purity of C18-3 in the product.

increased with the increase in flow rates. The separation factor and Table 8
purity of C18-3 in the product also first increased and then decreased, Effect of flow rate on the permeability of C18–1, C18–2 and C18-3.
as shown in Fig. 6. The maximum selectivity of C18-3 reached at Flow rate (mL/min) Permeability ( × 10−9 m/s)
40.1 mL/min. The purity of C18-3 in the product at various flow rates
was about 71.0% (16.5 mL/min), 75.0% (40.1 mL/min) and 64.8% C18-1 C18-2 C18-3
(59.3 mL/min). The effect of adjacent phase flow rates on the selectivity
16.5 0.46 0.83 4.01
was mainly due to the effect of flows rates on the mass transfer rate of 26.6 0.49 1.31 6.78
C18–1, C18–2 and C18-3. As could be seen in Table 8, the flow rates 40.1 0.79 2.67 15.77
had different effects on their mass transfer ability, and C18-3 perme- 49.8 0.84 2.28 9.41
ability was more sensitive to flow rates than C18–1 and C18-2. 59.3 1.24 1.80 5.06

Increasing adjacent phase flow rates significantly reduced external

diffusion resistance. As the flow rates increased to a certain value, the
external diffusion resistance was negligible, and the mass transfer re-
sistance in the membrane was dominant. Thus, the permeability of C18-
3 should be stable at relatively high flow rates because the resistance in
the membrane was not affected by the external diffusion resistance.
However, the C18-3 permeability decreased after the flow rates ex-
ceeded 40.1 mL/min, which was due to the change in the SILM at high
flow rates.
XRD is a powerful tool for detecting the change of membrane sol-
vents’ dosage, which was used to determine the crystalline nature of the
blank nylon membrane and the membrane coated with [BMIm]BF4 and
Ag+. As shown in Fig. 7a, the diffraction peaks for blank nylon
membrane (A membrane) existed at 2θ = 17.8, 20.4, 23.0, 24.0 and
26.1°. By comparison, the diffraction peaks of the nylon membrane
coated with [BMIm]BF4 and Ag+ (B membrane) shifted to lower wa-
venumbers, and the intensity of the peaks decreased significantly,
which indicated that incorporation of [BMIm]BF4 and Ag+ could
change crystallinity degree of the membrane and the intensity of the
diffraction peaks. This was consistent with the results reported by
Mahdavi et al. [39]. In addition, the SILMs after 6 h at 60 rpm (C
membrane) and 90 rpm (D membrane) operation were analyzed by
XRD. The diffraction peaks of C membrane were similar with B mem-
brane. As to the D membrane, the intensity increased and the position

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Fig. 7. (a) XRD patterns of (A) the blank nylon membrane, (B) initial SILM, (C) SILM after 60rpm operation and (D) SILM after 90 rpm operation. (b) XRD patterns of
the SILM after (C) 60 rpm operation, (D) SILM after 90 rpm operation and PDF card (No.04–0783).

of diffraction peaks moved toward to the higher wavenumbers, which
indicated that the D membrane solvent was obviously lost.
Moreover, the XRD patterns of the C membrane and D membrane in
the 2θ range from 30° to 80° were magnified and presented in Fig. 7b. A
diffraction peak at 2θ = 38° was observed on the XRD patterns of both
membranes. Based on the PDF card (No.04–0783), the diffraction peak
corresponds to metallic silver. Similar result was reported by Fallanza
et al. who proposed a partial reduction of the silver ions to metallic
silver under the light condition [23]. The dosage of metallic silver on
the membrane represented the residual amount of carrier Ag+, which
could be judged by the intensity of diffraction peak at 2θ = 38°. The
peak intensity for C membrane was larger than D membrane, indicating
that the solvent loss of C membrane was much lower than D membrane.
Thus, based on the XRD analysis, it can be concluded that the mem-
brane solvent and carrier Ag+ were easy to fall off when the flow rates
were higher than 59 mL/min, which would result in the reduction of
permeability and selectivity of SILM.
3.4. Pore size of supported membrane
The composition and structure of supported membrane have im-
portant influence on the separation performance and stability. In this
work, the effect of pore size of supported nylon membrane with 0.22 μm
and 0.45 μm was studied.
As shown in Fig. 8, the mass transfer rate and separation perfor-
mance of C18-3 for 0.45 μm nylon membrane were better than 0.22 μm
nylon membrane. Due to the larger pore area, 0.45 μm membrane could
impregnate more membrane solvent and load more carrier silver ions,
resulting in higher permeability and selectivity. The permeability of
C18-3 for the 0.45 μm membrane was 1.72 times that of 0.22 μm
membrane. C18-3 of higher purity in the product was also obtained
differed by about 7% under the different pore size membranes.
3.5. Stability of SILM
The stability of membrane is an important factor in practical ap-
plication. However, a major drawback for SILMs is the lack of stability
over time owing to the gradual solubilization of the membrane solvent
(carrier and organic solvent) in the adjacent phases [20].
In this work, to study the long-term stability of the 0.45 μm nylon
membrane coated with [BMIm]BF4 and Ag+, taking 6 h as a cycle, and
after the one cycle, the stripping solution and feed solution were re-
placed with fresh ones. Data were obtained from a 24 h continuous
operation, with the results illustrated in Fig. 9 and Table 9. It could be
observed that the permeability ability and selectivity of the SILM de-
clined gradually, and C18-3 basically unable to penetrate the mem-
brane pores after three cycles. As could be seen in Fig. 9b and c, the
SILM could maintain relatively high separation factors in the first two

Fig. 8. Effect of membrane pore size on (a) C18-3 concentration in stripping phase, (b) separation factors and purity of C18-3 in the product.
Experimental conditions: the initial concentration of fatty acid methyl esters in feed phase: 50
mg/mL, stripping phase: 10
wt% 1-hexene petroleum ether, AgBF4 concentration in membrane solvent: 0.5 g/mL, flow rate: 40.1 mL∙min−1, IL: [BMIm]BF4.

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Fig. 9. Comparison membrane stability of single and hydrophilic/hydrophobic composite supported membranes (a) concentration of C18-3 in stripping solvent, (b)
the separation factor of C18-3 to C18-1, (c) the separation factor of C18-3 to C18-2.
Experimental conditions: feed concentration: 50
mg/mL, stripping phase: 10
wt% 1-hexene petroleum ether, IL: [BMIm]BF4, AgBF4 concentration:0.5 g/mL, flow rate: 40.1 mL∙min−1.

cycles, and then the selectivity declined apparently. The SILM com-
pletely lost the selectivity after 24 h operation.
Compared with the aqueous solution of liquid supported membrane
[40], the stability of SILM was greatly improved due to the relatively
high viscosity of ILs, but the membrane lifetime was still short. Further
increasing the viscosity of the membrane solvent would be detrimental
to the permeability of C18-3. An alternative method is reducing the
shear force and solubility between SILM and flowing adjacent phases,
which could reduce the loss rate of membrane solvent and carrier Ag+.
A 0.45 μm hydrophobic PVDF membrane was selected as a protected
membrane to form hydrophilic/hydrophobic composite membrane.
According to Fig. 9a and Table 9, C18-3 concentration in the
stripping phase and the permeability decreased after one cycle, which
indicated that the permeation flux of both the single membrane and the
composite membrane was reduced after one cycle. But the concentra-
tion of C18-3 obtained in the stripping phase was greatly increased by
using the composite membrane. The permeability of single membrane
deceased by 68.57% after first cycle, while the composite membrane
only decreased by 35.80%. The permeability of the composite mem-
brane at the fourth cycle was comparable to that of the single mem-
brane at the second cycle. The results indicated that the PVDF mem-
brane can effectively protect the SILM by reducing the shear force and
solubility between SILM and flowing adjacent phases.
Moreover, the selectivity of the composite membrane was sig-
nificantly higher than that of the single membrane, as shown in Fig. 9b
and Fig. 9c. SC18-3/C18-1 and SC18-3/C18-2 for the composite membrane
after fourth cycles were 6.88 and 2.38 times that of the single mem-
brane, respectively. It was mainly due to the reduced loss of membrane

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Table 9
The permeability of C18-3 through the single membrane and composite membrane.
Permeability × 10−9 (m/s) First cycle (0∼6 h)
Single membrane 13.46
Composite membrane 23.66
solvent and carrier Ag+. As mentioned in 3.1.3, the permeability of
C18-3 increased sharply with the increase in Ag+ concentration in
SILM, but Ag+ concentration had less effect on the permeability of
C18–1 and C18-2. PVDF membrane effectively reduced the loss of the
membrane solvent and kept the permeability of C18-3 at a higher value,
while the permeability of C18–1 and C18-2 changed slightly, which
resulted in the significant improvement of SC18-3/C18-1 and SC18-3/C18-2.
Furthermore, the average SC18-3/C18-1 and SC18-3/C18-2 of the single
membrane were 6.90 and 6.88 in the second cycle, while those of the
composite membrane were 11.75 and 6.12 in the fourth cycle, respec-
tively. It illustrated the lifetime of the composite membrane was dou-
bled compared with the single membrane. Based on the change in
permeability and selectivity of the single and composite membrane
within 24 h, the composite membrane could effectively increase the
service life and stability.
4. Conclusion
Facilitated transport supported ionic liquid membrane containing
carrier Ag+ was used to separate C18-3 from tallow seed oil methyl
ester. The mass transfer rate and separation performance were related
to IL structure, Ag+ concentration, adjacent phase flow rates and the
pore size of supported membrane. [BMIm]BF4 showed the best per-
meability and selectivity due to the most appropriate viscosity, polarity
and hydrogen bond acidity/basicity. Ag+ preferentially coordinated
with C=C bond rather than carbonyl group because of the more stable
interaction with the C=C bond. The amount of Ag+ and IL in liquid
membrane extraction was much lower than traditional liquid-liquid
extraction to achieve satisfactory permeability and selectivity of C18-3.
The convection mass transfer between the flow phases and the mem-
brane surface could be intensified by higher flow rates, but part of the
membrane solvent and carrier Ag+ would fall off. The highest perme-
ability of 15.77 × 10−9 m/s, SC18-3/C18-1 of 12.53 and SC18-3/C18-2 of
8.73 were obtained at 40.1 mL/min. Larger pores not only reduced the
mass transfer resistance but also accommodated more IL and carrier
Ag+, which was beneficial to increasing the permeability and se-
lectivity. The proper pore size was 0.45μm for the extraction of C18-3.
The stability of membrane is an important factor in practical applica-
tion. The selectivity of SILM was lost after 24 h operation. Hydrophobic
PVDF membrane could be used as protected membrane to form hy-
drophilic/hydrophobic composite membrane to effectively increase the
service life and stability. The lifetime of the composite membrane was
doubled compared with the single membrane. For future study, it is
crucial to find more effective procedures to further avoid the change of
membrane and increase the membrane lifetime. The membrane se-
paration method proposed in this study could be applied to other fatty
acid methyl esters.
Acknowledgement
This research is supported by The National Natural Science
Foundation of China (863 Program 2014AA022103).
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