Fluid Phase Equilibria 493 (2019) 137e143

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Salt effect on liquideliquid equilibria of tetrahydrofuran/water/5-

hydroxymethylfurfural systems
Yujiao Xie, Fangyong Yu*, Yong Wang, Xianglei He, Shengren Zhou, Hongyou Cui**
School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo, 255049, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Salts strongly affect the phase equilibria of aqueous systems in biotechnological processes. In this work,
Received 13 December 2018 the influence of salt on the performance of extracting 5-hydroxymethylfurfural (HMF) from aqueous
Received in revised form media using tetrahydrofuran (THF) was investigated. The liquideliquid equilibria (LLE) of ternary (THF/
11 April 2019
water/MCl, M ¼ Li, Na or K) and quaternary (THF/water/HMF/MCl) systems were determined at 303.15 K
Accepted 16 April 2019
and atmospheric pressure. The salting-out effects of LiCl, NaCl, and KCl were studied at different con-
Available online 18 April 2019
centrations within their solubility limits. From the experimental LLE of the THF/water/MCl, it was found
that THF was salted out from the aqueous phase upon addition of salt. Based on the LLE of THF/water/
Keywords:
Liquideliquid equilibrium
HMF/MCl, the partition coefficient of HMF and selectivity were determined. Finally, the experimental
Salt effect equilibrium data of the quaternary systems were correlated via the nonrandom two-liquid (NRTL) model,
Tetrahydrofuran and the calculation results showed good agreement with the experimental data.
5-Hydroxymethylfurfural © 2019 Elsevier B.V. All rights reserved.
NRTL

1. Introduction Tetrahydrofuran (THF) has been proposed as a suitable organic

Biofuels and biochemicals have been developed as promising
renewable and sustainable alternatives due to growing concerns
regarding environmental protection [1e3]. 5-
hydroxymethylfurfural (HMF), which can be produced by dehy-
dration/hydrolysis of sugar, oligosaccharide, starch, and cellulose, is
an important biomass platform chemical and feedstock for many
liquid fuels, polymers, and chemical intermediates, such as 2,5-
furandicarboxylic acid, 2,5-dimethylfuran, 2,5-bis(hydroxymethyl)
furan, and levulinic acid [4e9]. In the production and separation of
HMF, numerous technologies have been used to improve the HMF
yield. The biphasic reaction system demonstrates many merits in
efforts to enhance the yield of HMF and is viewed as the most
promising technology for HMF production because the in situ
liquideliquid extraction using an organic solvent is integrated with
the production process. With the aid of extraction, HMF can be
extracted instantly into the organic phase from the aqueous solu-
tion where the reaction to form HMF is taking place, and the kind of
solvent is an important factor to influence the HMF production
yield [10e13].
* Corresponding author.
** Corresponding author.
E-mail addresses: yfy316@sdut.edu.cn (F. Yu), cuihy@sdut.edu.cn (H. Cui).
solvent for the production of HMF. Salt is added to enhance the
phase separation and partitioning of HMF into the organic phase.
Atanda et al. observed that HMF yields increase from 23.6% to 71%
after addition of 20 wt% NaCl to the water/THF system [14]. Li et al.
found that the yield of HMF by glucose dehydration reaches 63.1%
in biphasic water/THF systems with NaCl [9]. In our previous work,
conversion of glucose into HMF was investigated, and addition of
NaCl was observed to enhance the HMF extraction capacity in the
biphasic water/THF system [15].
Addition of salt could facilitate the partitioning of HMF between
the organic and aqueous phases and increase production yields. To
better understand the effect of salt on the partition coefficient of
HMF, knowledge of the liquideliquid equilibria (LLE) of systems
with different salts is required. Mohammad and Held et al. studied
the LLE of the water/MIBK/salt [16,17] and water/1-butanol/salt [18]
and determined the salt effect on the partitioning of HMF in these
systems. Results showed that salt increases the partitioning of HMF
in the organic phase and the salting-out behavior depends on the
type of salt applied. The phase equilibria of systems containing THF/
water and the influence of salt on the thermo-physical properties of
THF/water have already been reported [19e23]. For example, Li
et al. investigated the equilibrium of ternary systems of THF/water/
Na2SO4 and THF/water/MgSO4 and the quaternary system of THF/
water/Na2SO4/MgSO4 [19]. Roy et al. determined the influence of
three alkali metal chlorides on the apparent molar volumes and

https://doi.org/10.1016/j.fluid.2019.04.018
0378-3812/© 2019 Elsevier B.V. All rights reserved.
138 Y. Xie et al. / Fluid Phase Equilibria 493 (2019) 137e143
viscosities of THF/water mixtures [23]. However, to the best of our
knowledge, the LLE of THF/water/HMF/salt systems and the salt
effect on the partitioning of HMF have not been reported.
The thermodynamic model used to correlate the experimental
phase equilibrium data is a useful tool for the development of in-
dustrial extraction processes. Several correlation models have been
used for the phase equilibrium data of systems with salt. Lintomen
et al. adjusted binary interaction parameters with salt for the NRTL
and universal quasichemical (UNIQUAC) models in water/citric
acid/2-butanol/NaCl [24]. Chen et al. correlated the LLE of saturated
aqueous solutions of glycerol/1-butanol/water/NaCl with the NRTL
model [25]. Wang et al. modeled the LLE of the dichloromethane/
water/N,N-dimethylacetamide/NaCl system by using the NRTL and
UNIQUAC models, and the calculation results showed good agree-
ment with the experimental data [26].
In the present work, the LLE of the THF/water/MCl and THF/
water/HMF/MCl systems were measured experimentally at
303.15 K and atmospheric pressure. The influence of salts, including
LiCl, NaCl, and KCl, on the experimental LLE data, the partition
coefficient of HMF between the aqueous and organic phases, and
the selectivity were investigated. Finally, the NRTL model was used
to correlate the experimental LLE data, and the binary interaction
parameters were obtained.
2. Experimental
2.1. Materials
The materials used in the experiments are listed in Table 1. THF,
HMF, and 1-methoxy-2-propanol were purchased from Aladdin
Industrial Corporation and had purities of 99.5%, >99.0%, and
99.5%, respectively. These chemicals were used without further
purification. All salts, including LiCl (97.0%), NaCl (99.8%), and
KCl (99.8%), were purchased from Sinopharm Chemical Reagent
Co., Ltd. and used without further treatment. Deionized and
redistilled water was used throughout all experiments.
2.2. LLE measurement
The LLE of the ternary systems of THF/water/MCl and the qua-
ternary systems of THF/water/HMF/MCl were measured in a 25 mL
Erlenmeyer flask, which was used as the equilibrium cell. Each cell
was equipped with a cap to avoid solvent losses caused by evapo-
ration. The equilibrium cell was placed in a circulating water bath
with mechanical agitation.
To begin the test, the desired salts were weighed and dissolved
in water before addition of THF or HMF. Equal volumes of water and
THF were used in each system. After weighing, the solution was
agitated vigorously for at least 1 h and then allowed to equilibrate
for at least 12 h to ensure complete phase separation. Preliminary
studies carried out for this work have verified that the selected
stirring speed and equilibration time are sufficient for phase mixing
and separation. Samples from the aqueous and organic phases were
collected with syringes after phase separation.
Table 1
Sample provenance table.
Compound IUPAC name
THF tetrahydrofuran
HMF 5-hydroxymethylfurfural
1-methoxy-2-propanol 1-methoxy-2-propanol
LiCl lithium chloride
NaCl sodium chloride
KCl potassium chloride
2.3. Analytical method
THF was analyzed by using a gas chromatograph (Varian CP
3800) equipped with a flame ionization detector and a capillary
column. Nitrogen flowing at a rate of 30 mL/min was used as the
carrier gas. The initial oven temperature was held at 333.15 K for
2 min and then increased to 423.15 K at a ramp rate of 10 K/min. The
detector and injector temperatures were held at 523.15 and
533.15 K, respectively. For quantitative analysis, THF contents were
determined by using the internal standard method; 1-methoxy-2-
propanol was used as the internal standard (0.1 g/mL for the
organic phase and 0.4 g/mL for the aqueous phase). Samples from
the aqueous and organic phases were diluted with the internal
standard solution and ethanol at a dilution factor of 1:10. Calibra-
tion was performed by measuring mixtures of the THF solutions
and the internal standard solution. All samples were analyzed at
least thrice, and the average of these measurements is reported as
the result.
The concentration of salt in the two phases was determined by
ion-exchange chromatography (ICS-2000, Thermo Fisher, Dionex)
with a Dionex IonPac AS11 column. Samples from the aqueous and
organic phases were diluted with water to the desired concentra-
tion before analysis. KOH elution buffer was used at a flow rate of
1.0 mL/min. The Cl of the samples was analyzed using an electrical
conductivity detector due to interactions with the column material.
HMF was measured by a high-performance liquid chromatog-
raphy (Waters e2695) equipped with a UV detector. Samples from
the organic and aqueous phases were diluted with water to the
desired concentration. Waters Xbridge C18 column was used with a
flow rate of 0.8 mL/min of the elution, a mixture of methanol and
water with a volume ratio of 95:5 v/v.
The amounts of water in the organic and aqueous phase were
determined by Karl Fischer moisture analysis. Samples were ob-
tained from each of the two phases and analyzed at least twice; the
average value of these two measurements is reported as the result.
2.4. Data calibration
The LLE of the methyl isobutyl ketone (MIBK)/water/HMF was
measured to calibrate the accuracy of the equipment. The experi-
mental equilibrium weight fractions in MIBK/water/HMF are listed
in Table S1 in the supplementary material and compared with the
data reported by Mohammad et al. [17]. As shown in Figure S1 in
the supplementary material, the data in this work are in good
agreement with those reported in the literature [17].
3. Results and discussion
3.1. LLE of the ternary system THF/water/MCl
In this work, different salts, including LiCl, NaCl, and KCl, were
added to the THF/water system to study the influence of salt on LLE.
The experimental LLE of the THF/water/MCl system were measured
at 303.15 K and atmospheric pressure. The equilibrium weight
Purity, mass based Supplier
99.5% Aladdin
>99.0% Aladdin
99.5% Aladdin
97.0% Sinopharm
99.8% Sinopharm
99.8% Sinopharm
 Y. Xie et al. / Fluid Phase Equilibria 493 (2019) 137e143 139

Table 2
Experimental equilibrium weight fractions in the THF/water/MCl systems at 303.15 K and atmospheric pressure.a

Aqueous phase Organic phase

LiCl
wTHF wwater wLiCl wTHF wwater wLiCl
0.2251 0.7429 0.0320 0.7818 0.2181 0.0000
0.2050 0.7263 0.0687 0.8694 0.1305 0.0000
0.2016 0.7121 0.0864 0.9026 0.0973 0.0001
0.1755 0.7098 0.1148 0.9274 0.0725 0.0001
0.1731 0.7000 0.1269 0.9432 0.0567 0.0001
NaCl
wTHF wwater wNaCl wTHF wwater wNaCl
0.3732 0.6055 0.0213 0.7234 0.2765 0.0001
0.2313 0.7182 0.0505 0.8916 0.1084 0.0001
0.1174 0.8058 0.0768 0.9026 0.0973 0.0001
0.0646 0.8329 0.1024 0.9244 0.0755 0.0001
0.0697 0.8134 0.1169 0.9531 0.0468 0.0001
KCl
wTHF wwater wKCl wTHF wwater wKCl
0.4081 0.5727 0.0192 0.7297 0.2696 0.0007
0.2259 0.7324 0.0418 0.8279 0.1712 0.0009
0.1659 0.7621 0.0719 0.8263 0.1729 0.0008
0.1018 0.8162 0.0820 0.8987 0.1004 0.0009
0.0758 0.8272 0.0970 0.9282 0.0708 0.0010
a
Standard uncertainties u for atmospheric pressure, temperature and weight fractions are u(P) ¼ 1.0 kPa; u(T) ¼ 0.05 K; In the aqueous phase u(wTHF) ¼ 0.0014, u(wwa-
ter) ¼ 0.0055, u(wMCl) ¼ 0.0018; In the organic phase u(wTHF) ¼ 0.0023, u(wwater) ¼ 0.0015, u(wMCl) ¼ 0.0012.

fractions of all components in the aqueous and organic phases were
determined according to the experimental section. Table 2 lists the
experimental LLE of the THF/water/MCl systems. The amount of salt
dissolved in the aqueous phase is much larger than that present in
the organic phase in all investigated systems. Moreover, the weight
fraction of THF decreases in the aqueous phase with increasing salt
addition. Hence, THF was salted out from the aqueous phase upon
addition of salt.
To investigate the strength of the salting-out effect of THF from
different salts, the weight fraction of THF in the aqueous phase
versus the weight fraction of salt in the aqueous phase is illustrated
in Fig. 1. For systems with NaCl and KCl, the equilibrium weight
fraction of THF in the aqueous phase decreases dramatically with
increasing weight fraction of the salt. In comparison with the
strength of the salting-out effects of THF from the aqueous phase by
NaCl or KCl, that of LiCl is weak at low LiCl concentration, and the
influence of LiCl concentration on the weight fractions of THF in the
aqueous phase is less pronounced. As described by Mohammad
et al. [17], the formation of ion pairs strongly contributes to the
salting-out phenomenon. In this study, Liþ is strongly hydrated in
the aqueous phase at high LiCl weight fractions, which increases
the weight fractions of THF in the aqueous phase.
3.2. LLE of the quaternary system THF/water/HMF/MCl
The LLE of the quaternary system of THF/water/HMF/MCl were
determined at 303.15 K and atmospheric pressure; the examined
salts are LiCl, NaCl, and KCl at concentrations of 0.10 and 0.25 g MCl/
mL H2O, both of which are within the saturation limit at 303.15 K.
The LLE data were measured at a constant salt concentration with
varying HMF concentration and at a constant HMF concentration
with varying salt concentrations.
Tables 3 and 4 list the equilibrium weight fractions of the
various components of the quaternary systems at different salt
concentrations. Salt strongly influences the LLE, especially at high
HMF weight fractions. Fig. 2 compares the experimental LLE data of
the THF/water/HMF/LiCl systems at two different LiCl concentra-
tions on a salt-free basis. The tie-line slope increases with
increasing LiCl content, which means HMF is salted-out from the
aqueous phase with increasing LiCl concentration. Similar phe-
nomena are observed for the systems with NaCl and KCl, as shown
in Figs. 3 and 4, respectively.
Based on the experimental LLE data, the partition coefficient (K)
and selectivity (S) could be calculated as follows:
org
wHMF
KHMF ¼ (1)
waq
HMF

KHMF
S¼ (2)
KWater

where KHMF refers to the partition coefficient of HMF in the THF/

Fig. 1. Weight fractions of THF in the aqueous phase versus salt weight fractions in the
aqueous phase of the THF/water/MCl systems at 303.15 K and atmospheric pressure.
org
water/HMF/MCl system, wHMF is the equilibrium weight fraction of
HMF in the organic phase, and waq HMF is the equilibrium weight
fraction of HMF in the aqueous phase. The K and S for the THF/
water/HMF/MCl systems at different salt concentrations are sum-
marized in Tables 3 and 4
Fig. 5 shows the changes in partition coefficient as a function of
HMF concentration in the THF/water/HMF/MCl system at two salt
140 Y. Xie et al. / Fluid Phase Equilibria 493 (2019) 137e143

Table 3
Experimental equilibrium weight fractions in the THF/water/HMF/MCl systems with 0.10 g MCl/mL
H2O at 303.15 K and atmospheric pressure.a

Aqueous phase Organic phase K S

LiCl
wTHF wwater wHMF wLiCl wTHF wwater wHMF wLiCl
0.2653 0.6745 0.0071 0.0532 0.8832 0.0963 0.0197 0.0008 2.8 20
0.2575 0.6730 0.0148 0.0547 0.8409 0.1205 0.0369 0.0016 2.5 14
0.2510 0.6703 0.0237 0.0551 0.8078 0.1349 0.0551 0.0023 2.3 12
0.2243 0.6864 0.0346 0.0547 0.7716 0.1451 0.0803 0.0029 2.3 11
0.2129 0.6861 0.0470 0.0540 0.7153 0.1736 0.1052 0.0060 2.2 8.9
NaCl
wTHF wwater wHMF wNaCl wTHF wwater wHMF wNaCl
0.1982 0.7510 0.0054 0.0454 0.8601 0.1173 0.0219 0.0007 4.0 26
0.2256 0.7128 0.0107 0.0509 0.8285 0.1246 0.0463 0.0007 3.9 22
0.2117 0.7196 0.0157 0.0530 0.7994 0.1383 0.0616 0.0007 3.9 20
0.2053 0.7192 0.0207 0.0548 0.7678 0.1486 0.0825 0.0010 3.9 19
0.2228 0.6962 0.0261 0.0550 0.7465 0.1514 0.1004 0.0017 3.8 18
KCl
wTHF wwater wHMF wKCl wTHF wwater wHMF wKCl
0.2225 0.7299 0.0067 0.0408 0.8475 0.1283 0.0233 0.0009 3.5 20
0.2007 0.7416 0.0140 0.0437 0.8026 0.1488 0.0473 0.0013 3.4 17
0.2329 0.7031 0.0211 0.0428 0.7581 0.1723 0.0680 0.0016 3.2 13
0.2166 0.7091 0.0280 0.0463 0.7298 0.1797 0.0884 0.0021 3.1 12
0.2351 0.6832 0.0353 0.0464 0.7142 0.1870 0.0963 0.0025 2.7 10
a
Standard uncertainties u for atmospheric pressure, temperature and weight fractions are u(P) ¼ 1.0 kPa; u(T) ¼ 0.05 K; In the aqueous phase u(wTHF) ¼ 0.0014, u(wwa-
ter) ¼ 0.0055, u(wHMF) ¼ 0.0025, u(wMCl) ¼ 0.0018; In the organic phase u(wTHF) ¼ 0.0023, u(wwater) ¼ 0.0015, u(wHMF) ¼ 0.0018, u(wMCl) ¼ 0.0012.

Table 4
Experimental equilibrium weight fractions in the THF/water/HMF/MCl systems with 0.25 g MCl/mL H2O at 303.15 K and atmospheric pressure.a

Aqueous phase Organic phase K S

LiCl
wTHF wwater wHMF wLiCl wTHF wwater wHMF wLiCl
0.0672 0.7647 0.0057 0.1624 0.7136 0.2491 0.0347 0.0026 6.1 18
0.0750 0.7515 0.0120 0.1615 0.6467 0.2814 0.0688 0.0031 5.8 15
0.0740 0.7491 0.0163 0.1606 0.5898 0.3156 0.0914 0.0032 5.6 13
0.0757 0.7423 0.0230 0.1590 0.5234 0.3463 0.1268 0.0036 5.5 12
0.0792 0.7245 0.0346 0.1618 0.4810 0.3647 0.1508 0.0035 4.4 8.7
NaCl
wTHF wwater wHMF wNaCl wTHF wwater wHMF wNaCl
0.0401 0.8217 0.0040 0.1342 0.6179 0.3496 0.0310 0.0016 7.8 18
0.0403 0.8140 0.0083 0.1375 0.5118 0.4248 0.0614 0.0019 7.4 14
0.0337 0.8167 0.0114 0.1383 0.4684 0.4486 0.0809 0.0021 7.1 13
0.0334 0.8156 0.0136 0.1374 0.4407 0.4622 0.0949 0.0022 7.0 12
0.0329 0.8096 0.0176 0.1400 0.3972 0.4825 0.1180 0.0023 6.7 11
KCl
wTHF wwater wHMF wKCl wTHF wwater wHMF wKCl
0.0465 0.8411 0.0048 0.1075 0.5532 0.4237 0.0225 0.0006 4.6 9.2
0.0493 0.8298 0.0096 0.1113 0.5109 0.4464 0.0421 0.0005 4.4 8.2
0.0514 0.8127 0.0145 0.1214 0.4960 0.4414 0.0620 0.0005 4.3 7.9
0.0494 0.8066 0.0176 0.1264 0.4623 0.4635 0.0736 0.0005 4.2 7.3
0.0499 0.7911 0.0237 0.1353 0.3503 0.5518 0.0973 0.0006 4.1 5.9
a
Standard uncertainties u for atmospheric pressure, temperature and weight fractions are u(P) ¼ 1.0 kPa; u(T) ¼ 0.05 K; In the aqueous phase u(wTHF) ¼ 0.0014, u(wwa-
ter) ¼ 0.0055, u(wHMF) ¼ 0.0025, u(wMCl) ¼ 0.0018; In the organic phase u(wTHF) ¼ 0.0023, u(wwater) ¼ 0.0015, u(wHMF) ¼ 0.0018, u(wMCl) ¼ 0.0012.

concentrations. Here, KHMF decreases with increasing HMF con-
centration. Comparison of the K values at the two salt concentra-
tions shows that K increases with increasing salt concentration,
which means salt enhances the salting-out effect. NaCl causes a
stronger salting-out effect than KCl at both 0.10 and 0.25 g MCl/mL
H2O, which is in accordance with the results of Mohammad et al.
[18]. The salting-out of HMF from the aqueous phase by the salts
shows the order NaCl > KCl > LiCl at 0.10 g MCl/mL H2O concen-
tration; at 0.25 g MCl/mL H2O, the salting-out effect shows the or-
der NaCl > LiCl > KCl. The strength of the interaction between the
cation and anion corresponds to the strength of the salting-out
effect on HMF partitioning. The influence of LiCl on the salting
out of HMF depends strongly on the LiCl concentration because of
the dissociation and hydration of this salt in the aqueous phase.
Fig. 6 shows changes in S as a function of HMF concentration in
the THF/water/HMF/MCl system at two salt concentrations. Results
show that S decreases with increasing HMF concentration. Sepa-
ration is enhanced with decreasing NaCl and KCl concentrations; by
comparison, LiCl concentrations have a limited influence on S.
Among those of the systems studied, the S values of systems with
0.10 g NaCl/mL H2O are largest, which means that NaCl is the most
effective salt for separation.
3.3. Data correlation
The NRTL model was employed to correlate the experimental
LLE data. Water, THF, HMF and salt were considered as single
component, and the phenomena of total and partial dissociation
were not considered in the adjustment. The binary interaction
parameters were calculated using the following equation:
 Y. Xie et al. / Fluid Phase Equilibria 493 (2019) 137e143 141

Fig. 2. Phase diagram of the THF/water/HMF/LiCl system at 303.15 K on a salt-free Fig. 5. Partition coefficients as a function of HMF concentration in the THF/water/HMF/
basis. Symbols connected by tie-lines represent the compositions of the coexisting MCl systems.
phases.

Pn
GE X j¼1 tji Gji xj
n
¼ xi Pn (3)
RT i¼1 k¼1 Gki xk

g g Dg g g Dg
where tij ¼ ijRT jj ¼ RTij , tji ¼ jiRT ii ¼ RTji , Gij ¼ expð  aij tij Þ, and
Gji ¼ expð  aji tji Þ.
Here, gij and gji are energy parameters characterizing the
interaction of species i and j, and aij and aji are non-randomness
factors that could be derived from the local composition assump-
tion. In this case, the non-randomness parameter was set to a
constant value (aij ¼ 0.3). Dgij and Dgji are binary interaction pa-
rameters correlated from the experimental data.
The Dgij and Dgji were obtained by minimizing the objective
function (OF), as given in the following equation:
2 !2 !2 3
Xn X 4
xEij  xCij xEij  xCij
OF ¼ 4 þ 5 (4)
i¼1 j¼1
xEij xEij
org aq
Fig. 3. Phase diagram of the THF/water/HMF/NaCl system at 303.15 K on a salt-free
basis. Symbols connected by tie-lines represent the compositions of the coexisting where xEij represents the mole fraction based on the experiments,
phases. xCij represents the mole fraction based on the calculations, and n
represents the point number of the data.

Fig. 4. Phase diagram of the THF/water/HMF/KCl system at 303.15 K on a salt-free

basis. Symbols connected by tie-lines represent the compositions of the coexisting Fig. 6. Selectivity as a function of HMF concentration in the THF/water/HMF/MCl
phases. systems.
142 Y. Xie et al. / Fluid Phase Equilibria 493 (2019) 137e143

Table 5
Binary parameters of NRTL model for the THF(1)/water(2)/HMF(3)/MCl(4) systems.

i-j LiCl NaCl KCl

Dgija Dgjia RMSD Dgija Dgjia RMSD Dgija Dgjia RMSD

0.10 g MCl 1e2 0.138 0.631 0.0046 0.248 0.613 0.0039 0.195 0.641 0.0033
/mL H2O 1-3 0.296 0.186 0.910 0.475 0.754 0.555
1-4 0.598 0.357 2.220 1.118 2.289 1.129
2-3 0.193 0.965 1.809 0.539 1.438 0.563
2-4 0.0584 0.497 2.712 0.700 2.859 0.718
3-4 0.036 1.218 0.585 0.962 0.665 0.953
0.25 g MCl 1e2 0.247 0.823 0.0040 0.223 1.255 0.0038 0.150 1.148 0.0023
/mL H2O 1-3 0.896 0.467 0.534 0.350 0.809 0.416
1-4 1.120 1.173 1.752 1.184 2.146 1.150
2-3 1.758 0.629 1.306 0.378 1.837 0.751
2-4 1.929 0.727 1.938 0.694 2.414 0.678
3-4 0.384 0.928 0.722 0.819 0.747 0.984
a
The unit of parameters is 104 J/mol.

The equilibrium mole fractions of the THF/water/HMF/MCl
systems at 303.15 K and atmospheric pressure are listed in Table S1
(0.10 g MCl/mL H2O) and Table S2 (0.25 g MCl/mL H2O) in the
supplementary material. The NRTL model was used to correlate the
equilibrium mole fractions, the calculated Dgij and Dgji are shown in
Table 5. Comparisons between the experimental and calculated
data were performed by calculating the root-mean-square devia-
tion (RMSD). The RMSD values in Table 5 are satisfactory.
4. Conclusions
In this work, salt effects on the LLE of THF/water/HMF systems
were investigated. The phase diagrams of the ternary system of
THF/water/MCl and quaternary system of THF/water/HMF/MCl
were determined at 303.15 K and atmospheric pressure; LiCl, NaCl,
and KCl were the investigated salts. The experimental LLE of the
THF/water/HMF/MCl systems were also correlated with the NRTL
model.
In the THF/water/MCl systems, most of the salts were present in
the aqueous phase, and only a very small amount of salt was found
in the organic phase. THF was salted out from the aqueous phase
upon addition of salt. In the quaternary THF/water/HMF/MCl sys-
tems, the strength of the salting-out effect was enhanced by
increasing the salt concentration. Considering the influences of the
investigated salts on the partitioning of HMF in the quaternary
systems, NaCl produced the strongest salting-out effect. For
modeling, the binary interaction parameters were obtained, and
the NRTL model was able to describe experimental data well.
Acknowledgements
The authors are grateful for the support from Natural Science
Foundation of Shandong Province (ZR2018BB062), Key Research
and Development Program of Shandong Province
(2018GGX107003) and National Natural Science Foundation of
China (21476132).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.fluid.2019.04.018.
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