Article

Cite This: J. Chem. Eng. Data 2018, 63, 1316−1324 pubs.acs.org/jced

Solubility of 2,5-Furandicarboxylic Acid in Eight Pure Solvents and

Two Binary Solvent Systems at 313.15−363.15 K
Yongzhao Zhang,*,† Xia Guo,‡ Ping Tang,† and Jian Xu†
†
Hangzhou Vocational & Technical College, Hangzhou 310018, People’s Republic of China
‡
Zhejiang Zanyu Technology Co., Ltd., Hangzhou 310009, People’s Republic of China

ABSTRACT: 2,5-Furandicarboxylic acid (FDCA) serves as a monomer

in various polyesters and is often obtained through the oxidation of 5-
Downloaded via UNIV DO ESTADO DO RIO DE JANEIRO on March 31, 2023 at 19:31:07 (UTC).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

hydroxymethylfurfural. The solubility data of FDCA are of great value for

the reaction process analysis and separation technology. The
experimental solubility of FDCA in eight pure solvents (water, methanol,
acetonitrile, acetic acid, ethyl acetate, methyl isobutyl ketone (MIBK), 1-
butanol, and isobutanol) and two binary solvent systems (water +
acetonitrile and water + acetic acid) in the temperature range of 313.15−
363.15 K was determined. In pure solvents and binary mixtures, the
solubility of FDCA increased with the increasing temperature. The order
from largest to smallest solubility in pure solvents was as follows:
methanol, 1-butanol, isobutanol, acetic acid, water, MIBK, ethyl acetate,
and acetonitrile. The mole fraction of FDCA in binary mixtures increased
first and then decreased with the increasing mole fraction of water. The solubility data were correlated with the UNIQUAC
model, NRTL model, and WILSON model.

■ INTRODUCTION
At the current consumption rate, the proven crude oil reserves
are estimated to last less than four decades.1 The use of the
abundant biomass resources to replace petrochemicals has
gained more and more attention of researchers. 5-Hydrox-
ymethylfurfural (5-HMF), which is obtained by the dehy-
dration of carbohydrates in acid media, is a key biomass-derived
platform chemical.2 2,5-Furandicarboxylic acid (FDCA) is an
important product through the oxidation of 5-HMF. FDCA
serves as a monomer in various polyesters.3 The presence of
two carboxylic groups in FDCA makes it a potential polymer
building block which could be a substitute for petro-based
terephthalic (TPA), isophthalic, and adipic acid.4 FDCA was
identified as one of the top 12 value-added chemicals from
biomass by the U.S. Department of Energy.5
Many researchers had studied the oxidation reaction of 5-
HMF to FDCA. The oxidation process is shown in Figure 1.6
In the oxidation reaction, homogeneous or heterogeneous
catalysts are often used.
Mei et al. used a magnetic palladium catalyst to synthesize
FDCA, and water was used as the solvent. Under optimized
conditions, the conversion of 5-HMF was 98.2%, and the yield
of FDCA was 91.8%.7
In literature,8 aerobic oxidation of HMF catalyzed by the Co/
Mn/Br catalyst was conducted in an acetic acid solvent. The
yield of FDCA was 60%. The addition of zirconium could
promote the reaction process.
In literature,7 the heterogeneous catalyst was used. During
the reaction process, FDCA might crystallize from water. The
crystallized particles would block the catalyst channel, and the
catalyst was deactivated. So, an alkaline aqueous solution was
usually used to prevent the crystal precipitation. Hansen et al.
also reported the influence of the FDCA solubility on the
oxidation reaction of 5-HMF in different solvents (methanol,
acetonitrile, ethyl acetate, etc.). The oxidation of 5-HMF to
FDCA seemed significantly more difficult to achieve than the
oxidation to DFF for the low solubility of FDCA.9
5-HMF was usually synthesized in biphasic systems. An
aqueous solution was used as the reactive phase. The organic
layer (1-butanol, isobutanol, MIBK, etc.) of the biphasic
systems acted as an extracting phase for the continuous
accumulation of 5-HMF into the organic phase.10 The
oxidation of 5-HMF in organic solvents of biphasic systems
without the separation of 5-HMF from organic solvents might
be an economical technology.
In literature,8 the homogeneous catalyst was used. After the
reaction, the cooling crystallization method was often applied
to separate FDCA from the mixture.
From the above illustration, FDCA was usually synthesized
through the oxidation of 5-HMF, and water would be formed
during the reaction process. The solubility data of FDCA in
pure solvents and binary aqueous mixtures was of great value
for the catalyst deactivation analysis and product separation
technology. In this article, the solubility of FDCA was measured
in eight pure solvents (water, methanol, acetonitrile, acetic acid,
ethyl acetate, methyl isobutyl ketone (MIBK), 1-butanol, and
Received: October 27, 2017
Accepted: April 17, 2018
Published: April 23, 2018

© 2018 American Chemical Society 1316 DOI: 10.1021/acs.jced.7b00927

J. Chem. Eng. Data 2018, 63, 1316−1324
Journal of Chemical & Engineering Data Article

Figure 1. Oxidation process of 5-HMF.

Table 1. Specifications for the Chemicals Used

chemical name CAS number source purity (w)
2,5-furandicarboxylic acid 3238-40-2 Aladdin Reagent Co., Ltd. 0.95
isobutanol 78-83-1 Aladdin Reagent Co., Ltd. 0.99
methanol 67-56-1 Hangzhou Gaojing Fine Chemical Industry Co., Ltd. 0.99
1-butanol 71-36-3 0.99
acetic acid 64-19-7 0.99
ethyl acetate 141-78-6 0.99
acetonitrile 75-05-8 Spectrum Chemical Manufacturing Co., Ltd. 0.999
MIBK 108-10-1 Shanghai Macklin Biochemical Co., Ltd. 0.99
water 7732-18-5 Hangzhou Wahaha Co., Ltd. conductivity was less than 5 × 10−4 S·m−1
terephathalie acid 100-21-0 Aladdin Reagent Co., Ltd. 0.99

isobutanol) and two binary solvent systems (water + Table 2. Experimental Mole Fraction Solubilities xexp and
acetonitrile and water + acetic acid) at 313.15−363.15 K. Reported Solubility Data xref of TPA in Acetic Acid at
The solubility data was correlated with the WILSON model, Varying Temperatures T and Pressure p = 0.1 MPaa
NRTL model, and UNIQUAC model.

■
T (K) 105xexp 105xref δRD
315.15 5.532 5.495 0.00670
EXPERIMENTAL METHODS
325.15 7.998 8.026 0.00350
Chemicals. All chemicals were used without further 334.15 11.023 10.53 0.0468
purification. Deionized water was used throughout all of the 343.15 14.210 14.330 0.00840
experiments. The specifications for the chemicals that were 354.15 20.895 20.710 0.00890
used are shown in Table 1. In Table 1, w is the mass fraction. 363.15 28.010 27.000 0.0374
Apparatus and Procedure. Solubility was measured by a
Standard uncertainties, u, were u(T) = 0.05 K, ur(p) = 0.05, and
the static analytical method. Solvent (pure solvents or specified ur(xexp) = 0.1.
composition binary mixture, about 18 mL) and excessive solute
were placed in a sealed equilibrium cell (20 mL). The
temperature was controlled with a thermoelectric controlling
system. Because the equilibrium cell had a small volume, it was this article agreed well with that reported in literature, and the
difficult to measure the equilibrium temperature directly. In the experimental method used in this article was reliable.
preliminary experiments, we found that the difference between Analysis Method. The samples were weighed by an
the equilibrium temperature and the water bath temperature analytical balance (OHAUS CP214) with an accuracy of 0.1
was less than 0.1 K. The mixture temperature in the equilibrium mg. The samples were transferred to volumetric flasks by
cell was nearly equal to the water bath temperature, which was washing the syringe 5 times and were diluted with methanol.
measured with a thermometer (accuracy was 0.1 K). Pre- The diluted samples were analyzed with Shimadzu LC 2016A
experiments showed that the equilibrium state could be reached high-performance liquid chromatography to determine the
with 2 h of vigorous shaking (shaking speed was 200 rpm) and content of FDCA. A Diamonsil C18 (150 mm × 4.6 mm)
8 h of static standing. About 0.5 mL of supernatant was chromatographic column and UV detector (265 nm) were
sampled with a syringe. The syringe was washed with methanol used. The mobile phase consisted of two eluents (water (0.02
5 times to transfer all of the components to the flask. mol·L−1 aqueous ammonium acetate, PH = 4) + acetonitrile),
To confirm the accuracy of this experimental procedure, the and the volume fraction of water was 0.8. With the HPLC
solubility of terephthalic acid (TPA) in acetic acid was analysis results, the mole fraction of FDCA could be obtained
measured with the experimental method reported in this with eq 1. In eq 1, x is the mole fraction of FDCA. k and c are
article. The samples were analyzed with the method used in the parameters of the calibration equation (R2 = 0.998). A is the
literature.11 The experimental solubility data and the solubility analysis result of HPLC. V is the dilution ratio of the sample. ms
data reported in literature11 are shown in Table 2. In Table 2, T is the mass of the sample.
is the equilibrium temperature, xexp is solubility data measured (kA + c)V
in this article, and xref is the solubility reported in literature.11 x=
δRD is the relative deviation. The solubility data measured in ms (1)

1317 DOI: 10.1021/acs.jced.7b00927

J. Chem. Eng. Data 2018, 63, 1316−1324
Journal of Chemical & Engineering Data Article

Table 3. Experimental Mole Fraction Solubilities x of FDCA in Different Pure Solvents at Varying Temperatures T and Pressure
p = 0.1 MPaa
solvent T (K) 104x solvent T (K) 104x solvent T (K) 104x
water 313.15 2.027 methanol 313.15 42.816 acetonitrile 313.15 0.611
318.15 2.253 318.15 48.886 318.15 0.915
323.15 2.827 323.15 53.960 323.15 1.120
328.15 3.698 328.15 68.017 328.15 1.359
333.15 4.206 333.15 80.088 333.15 1.662
338.15 4.646 338.15 86.856 338.15 2.118
343.15 5.984 343.15 89.420 343.15 2.481
348.15 6.408 348.15 2.780
353.15 7.808 353.15 3.408
358.15 9.084 358.15 4.093
363.15 11.002 363.15 4.875
acetic acid 313.15 2.353 ethyl acetate 313.15 0.778 MIBK 313.15 1.363
318.15 2.724 318.15 1.133 318.15 1.843
323.15 3.305 323.15 1.64 323.15 2.530
328.15 4.040 328.15 2.379 328.15 2.960
333.15 4.775 333.15 2.846 333.15 3.383
338.15 5.546 338.15 3.768 338.15 4.291
343.15 7.166 343.15 4.64 343.15 5.356
348.15 8.202 348.15 5.493 348.15 6.314
353.15 9.652 353.15 6.195 353.15 6.659
358.15 11.454 358.15 6.586 358.15 7.209
363.15 13.369 363.15 7.207 363.15 8.626
1-butanol 313.15 26.633 isobutanol 313.15 16.834
318.15 30.206 318.15 19.840
323.15 34.631 323.15 22.975
328.15 40.763 328.15 26.959
333.15 46.876 333.15 32.271
338.15 52.407 338.15 37.176
343.15 57.177 343.15 41.219
348.15 66.311 348.15 48.187
353.15 74.077 353.15 54.801
358.15 81.953 358.15 60.689
363.15 91.623 363.15 68.216
a
Standard uncertainties, u, were u(T) = 0.05 K, ur(p) = 0.05, and ur(x) = 0.1.

Table 4. Experimental Mole Fraction Solubilities x of FDCA for Different Water Mole Fractions, xwater, in a (Water +
Acetonitrile) Binary Mixture at Varying Temperatures T and Pressure p = 0.1 MPaa
T (K) xwater 104x T (K) xwater 104x T (K) xwater 104x
313.15 0.077 3.214 323.15 0.078 5.205 333.15 0.078 6.567
0.148 8.548 0.146 11.747 0.147 13.503
0.207 14.361 0.209 20.650 0.211 22.780
0.267 18.293 0.266 23.988 0.266 26.460
0.319 23.372 0.316 28.627 0.317 35.723
0.368 25.890 0.366 32.499 0.367 40.977
0.589 38.386 0.594 43.898 0.610 56.878
0.772 24.399 0.767 28.461 0.751 42.961
0.900 8.575 0.900 10.538 0.903 15.348
343.15 0.078 7.363 353.15 0.077 8.228 363.15 0.078 11.292
0.147 17.423 0.148 21.221 0.146 22.778
0.211 29.061 0.206 31.049 0.209 35.993
0.266 39.424 0.266 44.849 0.266 51.908
0.317 47.164 0.318 55.678 0.315 61.559
0.366 52.684 0.367 60.739 0.364 72.737
0.587 76.627 0.594 86.550 0.607 102.483
0.770 54.317 0.765 60.184 0.748 83.462
0.899 23.290 0.899 22.883 0.901 34.925
a
Standard uncertainties, u, were u(T) = 0.05 K, ur(xwater) = 0.001, ur(p) = 0.05, and ur(x) = 0.1.

1318 DOI: 10.1021/acs.jced.7b00927

J. Chem. Eng. Data 2018, 63, 1316−1324
Journal of Chemical & Engineering Data Article

Table 5. Experimental Mole Fraction Solubilities x of FDCA for Different Water Mole Fractions, xwater, in a (Water + Acetic
Acid) Binary Mixture at Varying Temperatures T and Pressure p = 0.1 MPaa
T (K) xwater 104x T (K) xwater 104x T (K) xwater 104x
313.15 0.083 2.727 323.15 0.085 3.650 333.15 0.085 6.027
0.162 3.546 0.160 4.216 0.161 6.842
0.226 3.813 0.226 4.375 0.229 7.590
0.286 4.496 0.286 5.062 0.290 8.508
0.343 5.015 0.343 5.892 0.346 8.941
0.392 5.584 0.397 6.992 0.392 10.474
0.455 6.506 0.476 8.372 0.472 13.017
0.690 11.797 0.690 13.824 0.689 16.521
0.834 7.338 0.832 9.366 0.838 13.479
0.926 5.160 0.929 5.903 0.929 10.368
343.15 0.083 8.920 353.15 0.085 11.371 363.15 0.085 16.780
0.161 10.796 0.160 12.861 0.161 18.770
0.226 11.749 0.225 13.501 0.229 20.761
0.285 13.028 0.286 15.359 0.290 23.051
0.342 15.463 0.342 18.758 0.346 25.065
0.392 17.664 0.396 20.810 0.391 27.147
0.455 20.802 0.455 23.533 0.454 33.190
0.689 27.073 0.688 36.860 0.688 42.918
0.832 21.875 0.832 30.929 0.831 36.659
0.926 14.661 0.925 16.862 0.924 26.047
a
Standard uncertainties, u, were u(T) = 0.05 K, ur(xwater) = 0.001, ur(p) = 0.05, and ur(x) = 0.1.

Table 6. pH of the Saturated Aqueous Solution at 298.15 K

system xwater pH system xwater pH
water + acetic acid + FDCA 0.018 3.85 water + acetonitrile + FDCA 0.081 4.16
0.176 3.56 0.155 4.02
0.229 3.48 0.213 3.87
0.284 3.4 0.267 3.59
0.343 3.32 0.324 3.05
0.390 3.12 0.377 2.78
0.458 2.53 0.591 3.29
0.689 2.09 0.772 3.28
0.804 2.37 0.898 3.35
0.927 2.58

■ RESULTS AND DISCUSSION

The experimental solubility data of FDCA in pure solvents and
binary solvent systems are listed in Tables 3, 4, and 5. In these
tables, x is the mole fraction of FDCA. xwater is the mole fraction
of water in the ternary mixture.
In eight pure solvents, the mole fraction of FDCA increased
with the increasing temperature. At a certain temperature, the
order from the largest to smallest solubility was as follows:
methanol, 1-butanol, isobutanol, acetic acid, water, MIBK, ethyl
acetate, and acetonitrile. In the FDCA molecule, one
hydrophobic furan ring and two hydrophilic carboxyl groups
were present. FDCA had a low polarity for the existence of
carboxyl groups. Methanol, 1-butanol, and isobutanol are
protonic solvents, and the FDCA molecule would form a
hydrogen bond with the solvent molecule. Moreover, there are
hydrophobic groups in the three alcohols, and the polarity of
FDCA was close to that of the three alcohols. The solubility of
FDCA in these solvents was very large. Although acetic acid is
also a protonic solvent, self-association between the acetonitrile
molecules would prevent the formation of the hydrogen bond,
and the solubility was low. There are no hydrophobic groups in
a water molecule, and the polarity of water was quite different
from that of FDCA. The solubility of FDCA in water was also
1319
very small. Acetonitrile, ethyl acetate, and MIBK are non-
protonic solvents, and the formation of the hydrogen bond
became difficult between the solvent molecule and FDCA
molecule. The solubility of FDCA in these solvents was the
smallest.
The solubility of FDCA was very small in many solvents
(water, acetonitrile, etc.). FDCA may crystallize from the
solvents. The solid particles would precipitate on the surface of
catalyst and blocked the catalyst channels. This catalyst
deactivation mechanism was reported in many literatures.
The influence of temperature on the solubility was very
significant. For example, the solubility in acetic acid at 363.15 K
was about 6 times larger than that at 313.15 K. The
crystallization method was suitable for the separation of
FDCA for this sensitive temperature dependence.
In the two binary mixtures, the mole fraction of FDCA
increased with the increasing temperature. At a certain
temperature, the mole fraction of FDCA increased first and
then decreased with the increasing mole fraction of water. For
the water + acetonitrile mixture, the mole fraction of FDCA
was the largest when the mole fraction of water was about 0.6.
For the water + acetic acid mixture, the mole fraction of FDCA
was the largest when the mole fraction of water was about 0.7.
DOI: 10.1021/acs.jced.7b00927
J. Chem. Eng. Data 2018, 63, 1316−1324
Journal of Chemical & Engineering Data Article

According to the Scatchard−Hildebrand model,12 the solubility ϕi Z θ ϕ

was the largest when the solubility parameters of the solute ln ri = ln + qi ln i + l i − i ∑ xjlj
xi 2 ϕi xi
were close to those of the solvent. At a certain binary mixture
composition, the solubility parameters of FDCA might be close ⎡ ⎛ ⎞ θτ ⎤
to those of binary solvents, and the solubility was the largest. ⎢ ⎜
− qi ln⎜∑ θτ ⎟ ∑ j ij ⎥
⎢ j ji ⎟ − 1 +
Moreover, with the addition of water into the acetic acid ⎣ ⎝ j ⎠ j ∑k θkτk j ⎥⎦
(7)
system, the self-association of acetic acid was disturbed, and the
mole fraction of FDCA in acetic acid increased. When the water In eq 7, ln(lij) = eij + f ij/T. r and q are the volume parameters
content was too large, the solubility parameters of FDCA and and surface area parameters, respectively. The molecular
the solvents became quite different, and the mole fraction of volume parameters and surface area parameters of FDCA
FDCA decreased. The prevailing pH might highly influence the were calculated from eq 8. The FDCA molecule was
solubility of FDCA.13 When water was added to acetic acid (or constituted with two −COOH groups, two −CHC− groups,
acetonitrile) the pH changed. The pH of the saturated aqueous and one −O− group. The volume parameters and surface area
solution at 298.15 K is shown in Table 6. The pH data was used parameters were obtained from literature.20 The volume
only to demonstrate the dependency of the FDCA solubility on parameters and surface area parameters of different solvents
pH, and the influence of pH was not studied in this article. were also obtained from literature.20
Three models were used to correlate the solubility data. The r = 2r −COOH + 2r −CH = C − + r −O −
determination of the model parameters was as follows. The
given initial value of the model parameters to be determined q = 2q−COOH + 2q−CH = C − + q−O − (8)
allowed for the calculation of the activity coefficient, γ.
Knowing γ, the solubility of FDCA could be calculated from With this group division method, the calculated volume
eq 2.14 In eq 2, the influence of the heat capacities was parameters and surface area parameters of furfural were 3.247
neglected. The calculation data and the experimental data were and 2.731 respectively. These values agreed well with those in
compared. A nonlinear optimization method, implemented in a literature.20 The UNIQUAC structural (area and volume)
MATLAB toolbox, was used to update the value of the model parameters of the components are listed in Table 7.
parameters, minimizing the average relative deviation (ARD).
The calculation of ARD is shown in eq 3. Table 7. UNIQUAC Structural (Area and Volume)
Parameters
ΔHfus ⎛ 1 1 ⎞
ln(γx) = ⎜ − ⎟ component r q
R ⎝T Tm ⎠ (2) water 0.920 1.400
methanol 1.901 2.048
∑i |(xexp − xcal)/xexp| acetonitrile 1.870 1.724
ARD =
NDP (3) acetic acid 2.202 2.072
ethyl acetate 3.479 3.116
In eq 2, T is the equilibrium temperature; Tm is the melting MIBK 4.618 3.952
temperature of FDCA, 615.15 K;15 and ΔHfus is the enthalpy of 1-butanol 3.924 3.668
fusion at Tm. In eq 3, NDP is the number of experimental isobutanol 3.924 3.664
points. x is the mole fraction of FDCA in solvents. The FDCA 4.624 4.040
subscripts, exp and cal, are the experimental data and calculated
data, respectively. According to literature,16 the enthalpy of
fusion was a function of the melting temperature, as shown in The model parameters determined by the correlation of the
eq 4. solubility data in the pure solvents are listed in Tables 8, 9, and
10. Except for the solubility in acetonitrile and ethyl acetate, the
ΔHfus = 4.184TmK1 (4) three models had a high prediction accuracy (ARD was less
In eq 3, K1 was 13.5 for FDCA,16 and the value of ΔHfus was than 0.1). The models could be applied to predict the solubility
34746.61 J·mol−1. of FDCA in pure solvents. To make the figures clear, only the
In the NRTL model, the activity coefficient was calculated prediction results of the NRTL model for the solubility in the
with eq 5.17 pure solvents is shown in Figure 2.
For the solubility in the binary mixtures, the prediction
∑j τijGjixj xjGij ⎡ ∑ xτ G ⎤ accuracy of the WILSON model was very low. Only the NRTL
ln γi = + ∑ ⎢τij − l l l j l i ⎥ model and UNIQUAC model were applied to correlate the
∑l Gl ixl ∑l Gl jxl ⎢⎣ ∑l Gl jxl ⎥⎦ (5)
j solubility data. It was of great value to use the interaction
parameters in Tables 8 and 9 to predict the solubility of FDCA
In eq 5, Gij = exp(−αijlij), lij = aij + bij/T, and αij = 0.3.
in the binary mixtures. The interaction parameters of the
In the WILSON model, the activity coefficient was calculated
water−acetonitrile and water−acetic acid were obtained by the
with eq 6.18
correlation of the VLE data in literature.21,22 The prediction
⎛ ⎞ ⎛ x k Λk j ⎞ accuracy of the NRTL model and UNIQUAC model, when the
ln ri = 1 − ln⎜⎜∑ xjΛ ij⎟⎟ − ∑ ⎜⎜ ⎟⎟ above interaction parameters were used, is shown in Figures 3,
k = 1 ⎝ l kl l ⎠
⎝ j ⎠ ∑Λ x 4, 5, and 6. The prediction accuracy was very low, and the ARD
(6)
was above 30%. In the water−acetic acid binary mixture, the
In eq 6, ln(Λij) = cij + dij/T. self-association of the acetic acid molecules was disturbed with
In the UNIQUAC model, the activity coefficient was the addition of water. In the water−acetonitrile binary mixture,
calculated with eq 7.19 the synergistic effect of water and acetonitrile might influence
1320 DOI: 10.1021/acs.jced.7b00927
J. Chem. Eng. Data 2018, 63, 1316−1324
Journal of Chemical & Engineering Data Article

Table 8. Model Parameters of the NRTL Model for the Solubility in Pure Solvents
i j aij bij (K) aji bji (K) ARD
FDCA water −12.702 5.578 × 103 1.070 −15.711 0.0316
methanol 2.196 −403.119 1.084 −848.157 0.0380
acetonitrile −1.302 290.660 −0.319 1414.300 0.0991
acetic acid −1.606 168.572 4.613 −347.311 0.0152
ethyl acetate −2.647 456.870 4.140 136.280 0.299
MIBK −0.0115 −94.876 2.709 2.865 0.0666
1-butanol −0.708 6.149 4.511 −1291.294 0.0121
isobutanol −0.770 8.450 3.855 −917.385 0.0133

Table 9. Model Parameters of the UNIQUAC Model for the Solubility in Pure Solvents
i j cij dij (K) cji dji (K) ARD
FDCA water 0.2638 13.347 −0.702 44.522 0.0342
methanol 0.177 −228.950 −0.625 396.390 0.0381
acetonitrile 9.567 −6.990 × 103 1.357 −446.390 0.0986
acetic acid 0.134 −40.763 −0.728 45.866 0.015
ethyl acetate 0.118 −191.580 0.150 −151.050 0.297
MIBK −0.553 26.001 −0.235 7.606 0.0663
1-butanol −0.858 −578.000 −0.0665 350.990 0.0119
isobutanol −1.195 86.306 0.0215 183.909 0.0126

Table 10. Model Parameters of the WILSON Model for the Solubility in Pure Solvents
i j eij f ij (K) eji f ji (K) ARD
FDCA water −1.867 217.950 −29.508 −1.419 × 10 3
0.0343
methanol −4.042 710.640 0.959 110.610 0.0384
acetonitrile 2.956 −1.796 × 103 2.273 × 106 1.749 × 106 0.0987
acetic acid −1.087 0.949 −2.959 1.548 0.0159
ethyl acetate 1.634 −1.100 × 103 −38.785 3182.500 0.296
MIBK −1.696 101.210 −33.578 −5.186 × 103 0.0664
1-butanol −3.091 1237.400 −0.646 39.743 0.0117
isobutanol 0.0353 −126.290 −2.296 817.790 0.0164

Figure 2. Mole fraction solubility x of FDCA in pure solvents at

313.15−363.15 K. ○, acetonitrile; ☆, MIBK; □, water; Δ, acetic acid;
◇, ethyl acetate; ●, isobutanol; ■, 1-butanol; ★, methanol; ▲, ref 23,
solubility in methanol; ⧫, ref 23, solubility in water; and -, calculated
with the NRTL model.
the FDCA solubility significantly. Moreover, the pH of the
aqueous solution changed with the addition of water. The
interaction parameters obtained by the correlation of the
solubility data in the pure solvents could not consider these
influences. The NRTL model and UNIQUAC model could not
predict the solubility of FDCA in the binary mixtures when the
1321
Figure 3. Mole fraction solubility x of FDCA in the water +
acetonitrile solvent mixture at 313.15−363.15 K. □, T = 313.15 K; ○,
T = 323.15 K; Δ, T = 333.15 K; ◇, T = 343.15 K; ☆, T = 353.15 K; +,
363.15 K; -, calculated with the NRTL model (interaction parameters
correlated with the solubility data in binary mixtures); and ---,
calculated with the NRTL model (interaction parameters were
obtained from Table 7).
interaction parameters in Tables 8 and 9 were used. To predict
the solubility of FDCA in the binary mixtures, the model
DOI: 10.1021/acs.jced.7b00927
J. Chem. Eng. Data 2018, 63, 1316−1324
Journal of Chemical & Engineering Data
Figure 4. Mole fraction solubility x of FDCA in the water +
acetonitrile solvent mixture at 313.15−363.15 K. □, T = 313.15 K; ○,
T = 323.15 K; Δ, T = 333.15 K; ◇, T = 343.15 K; ☆, T = 353.15 K; +,
363.15 K; -, calculated with the UNIQUAC model (interaction
parameters correlated with the solubility data in binary mixtures); and
---, calculated with the UNIQUAC model (interaction parameters
were obtained from Table 8).
Figure 5. Mole fraction solubility x of FDCA in the water + acetic acid
solvent mixture at 313.15−363.15 K. □, T = 313.15 K; ○, T = 323.15
K; Δ, T = 333.15 K; ◇, T = 343.15 K; ☆, T = 353.15 K; +, 363.15 K;
-, calculated with the NRTL model (interaction parameters correlated
with the solubility data in binary mixtures); and ---, calculated with the
NRTL model (interaction parameters were obtained from Table 7).
parameters must be determined by the correlation of the
solubility data in the binary solvent systems. The model
parameters are listed in Tables 11 and 12. The average relative
deviation is also given. The NRTL model and UNIQUAC
model could predict the solubility of FDCA in the binary
mixtures accurately when the interaction parameters in Tables
11 and 12 were used.
Except for the solubility data in ethyl acetate, the calculated
data in the pure solvents agreed well with the experimental
data. The calculation accuracy of the solubility data in ethyl
acetate was low. The possible reason may be that the model
parameters could not reflex the interaction force between
FDCA and ethyl acetate. On the other hand, the average
relative deviations were below 0.05 in most occasions. The
1322
Article
Figure 6. Mole fraction solubility x of FDCA in the water + acetic acid
solvent mixture at 313.15−363.15 K. □, T = 313.15 K; ○, T = 323.15
K; Δ, T = 333.15 K; ◇, T = 343.15 K; ☆, T = 353.15 K; +, 363.15 K;
-, calculated with the UNIQUAC model (interaction parameters
correlated with the solubility data in binary mixtures); and ---,
calculated with the UNIQUAC model (interaction parameters were
obtained from Table 8).
models could be used to calculate the solubility of FDCA in
pure solvents.
To verify the reliability of the experimental solubility data,
the comparison was made with the data reported in literature,
and the comparison is shown in Figure 7. In literature,23 Payne
et al. reported that the solubility of FDCA in water and
methanol was 0.001 and 0.012 g/g at room temperature,
respectively. The solubility data at room temperature was not
measured in this article. The calculated solubility of FDCA in
water and methanol at room temperature was 0.000987 and
0.0131 g/g, respectively, and agreed well with the solubility data
reported in literature.23 In literature,24,25 the solubility of FDCA
in water was measured, and the deviation from the experimental
data in this article was negligible. In literature,24 the solubility
data in acetic acid and methanol were also given, and the
deviation was relatively high. In literature,24 FDCA used in the
experiments was purified with a crystallization method. In this
article, FDCA was used directly without any further
purification. Methanol and water were used as mobile phases
in literature,24 and the peak of FDCA might have a low
symmetry according to our previous experiments. These two
points might lead to a relatively high deviation.
The NRTL model and UNIQUAC model could be applied
to predict the solubility data of FDCA in the two binary
mixtures, and the NRTL model had a higher correlation
accuracy. In literature,14 Grosse Daldrup et al. found that the
solubility of amino acids highly depended on the prevailing pH
value. The PC-SAFT model was applied to correlate the
solubility data. In this article, the influence of the pH of the
solvent was not considered, and the application of the PC-
SAFT model to predict the dissociation/association equilibria
of FDCA in solvent might be conducted in the future. In
literature,26 Wan et al. developed a stable and efficient carbon
nanotube (CNT)-supported Au−Pd alloy catalyst. The CNT
containing more carbonyl/quinone and less carboxyl groups
favored the FDCA formation by enhancing the adsorption of
the reactant and the reaction intermediates, and 5-HMF could
be oxidized to FDCA in water without any bases by using this
catalyst. At 333.15 K, the solubility of FDCA in pure water was
DOI: 10.1021/acs.jced.7b00927
J. Chem. Eng. Data 2018, 63, 1316−1324
Journal of Chemical & Engineering Data Article

Table 11. Model Parameters of the NRTL Model for the Solubility in Binary Mixtures
i j aij bij (K) aji bji (K) ARD
Water + Acetonitrile
FDCA water 9.328 −1.423 × 103 4.473 −1.158 × 103 0.0711
water acetonitrile −0.309 −489.650 −0.522 2.247 × 103
FDCA acetonitrile 6.594 1221.022 5.977 −416.963
Water + Acetic Acid
FDCA water −3.442 5.005 × 105 0.477 527.924 0.0820
water acetic acid 1.513 −720.320 0.150 837.895
FDCA acetic acid 0.704 1.030 × 103 0.259 −2.498 × 105

Table 12. Model Parameters of the UNIQUAC Model for the Solubility in Binary Mixtures
i j eij f ij (K) eji f ji (K) ARD
Water + Acetonitrile
FDCA water 0.0836 −1.417 × 104 −0.154 338.952 0.111
water acetonitrile −0.456 247.787 −0.0643 −395.986
FDCA acetonitrile −0.0144 −116.903 −0.507 −1.471 × 104
Water + Acetic Acid
FDCA water 0.161 1.043 −0.347 0.619 0.0882
water acetic acid −1.367 −1.0067 0.569 2.624
FDCA acetic acid −0.0134 0.0810 −0.524 −2.522

solvents, the solubility of 2,5-furandicarboxylic acid in methanol

was the highest, and acetonitrile was the lowest. The solubility
data in the eight pure solvents could be correlated with the
NRTL model, WILSON model, and UNIQUAC model. In the
two binary mixtures, the mole fraction of FDCA increased first
and then decreased with the increasing mole fraction of water
in the binary mixtures. The mole fraction of FDCA was the
largest when the mole fraction of water was about 0.6 for the
water + acetonitrile mixture and 0.7 for the water + acetic acid
mixture. The solubility data in these two binary mixtures could
be correlated with the NRTL model and UNIQUAC model.
The solubility data could provide valuable data for the analysis
of the catalyst deactivation mechanism and the reaction process
design.

Figure 7. Experimental solubility data and data reported in the

■ AUTHOR INFORMATION
Corresponding Author
literature of three solvents. ■, solubility in methanol measured in this *Tel.: 0086-571-56700179; Fax: 0086-571-56700172; E-mail:
article; ⧫, ref 23, solubility in methanol; □, ref 24, solubility in zhangyzhao@163.com.
methanol; ●, solubility in acetic acid measured in this article; ○, ref ORCID
24, solubility in acetic acid; ▲, solubility in water measured in this
article; ▼, ref 23, solubility in water; Δ, ref 24, solubility in water; ☆, Yongzhao Zhang: 0000-0003-3063-3944
ref 25, solubility in water; and -, calculated with the NRTL model. Funding
All of the authors received funding from the Zhejiang Provincial
Department of Education (Y201738406) and Hangzhou
0.00365 g/g. The solubility of FDCA could reach 0.0331 and Vocational and Technical College (ky201832).
0.00831 g/g in water + acetonitrile and water + acetic acid
binary mixtures, respectively. The addition of acetonitrile or Notes
The authors declare no competing financial interest.

■
acetic acid into water could enhance the solubility of FDCA
significantly. This increase of the solubility could be applied to
prevent the crystallization of FDCA when the heterogeneous REFERENCES
catalyst was used, and the deactivation of the catalyst could be (1) Rizzi, F.; Van-Eck, N. J.; Frey, M. The production of scientific
avoided. knowledge on renewable energies: Worldwide trends, dynamics and

■ CONCLUSION
Solubility of 2,5-furandicarboxylic acid in eight pure solvents
and two binary mixtures (water + acetonitrile and water +
acetic acid) in the temperature range of 313.15−363.15 K was
determined. The solubility of 2,5-furandicarboxylic acid
increased with the increasing temperature. Among the eight
challenges and implications for management. Renewable Energy 2014,
62, 657−671.
(2) Xiong, Y.; Zhang, Z. H.; Wang, X.; Liu, B.; Lin, J. T. Hydrolysis of
cellulose in ionic liquids catalyzed by a magnetically-recoverable solid
acid catalyst. Chem. Eng. J. 2014, 235, 349−355.
(3) Matos, M.; Sousa, A. F.; Fonseca, A. C.; Freire, C. S. R.; Coelho,
J. F. J.; Silvestre, A. J. D. A New Generation of furanic copolyesters
with enhanced degradability: Poly (ethylene 2,5-furandicarboxylate)-

1323 DOI: 10.1021/acs.jced.7b00927

J. Chem. Eng. Data 2018, 63, 1316−1324
Journal of Chemical & Engineering Data Article

co-poly(lactic acid) copolyesters. Macromol. Chem. Phys. 2014, 215, (24) Ban, H.; Pan, T.; Cheng, Y. W.; Wang, L. J.; Li, X. Solubilities of
2175−2184. 2,5-furandicarboxylic acid in binary acetic acid + water, methanol +
(4) Sousa, A. F.; Vilela, C.; Fonseca, A. C.; Matos, M.; Freire, C. S. water and ethanol + water solvent mixtures. J. Chem. Eng. Data,
R.; Gruter, G. M.; Coelho, J. F. J.; Silvestre, A. J. D. Biobased submitted for publication, 2018.
polyesters and other polymers from 2,5-furandicarboxylic acid: a (25) Rose, H.; Greinert, T.; Held, C.; Sadowski, G.; Bommarius, A.;
tribute to furan excellency. Polym. Chem. 2015, 6, 5961−5983. Mutual influence of furfural and furancarboxylic acids on their
(5) Jiang, Y.; Woortman, A. J. J.; Alberda van Ekenstein, G. O. R.; solubility in aqueous solutions: Experiments and PC-SAFT
Loos, K. A biocatalytic approach towards sustainable furanic-aliphatic predictions. J. Chem. Eng. Data, submitted for publication,
polyesters. Polym. Chem. 2015, 6, 5198−5211. 2018.10.1021/acs.jced.7b01039
(6) Zhang, Z. H.; Zhen, J. D.; Liu, B.; Lv, K. L.; Deng, K. J. Selective (26) Wan, X. Y.; Zhou, C. M.; Chen, J. S.; Deng, W. P.; Zhang, Q.
aerobic oxidation of the biomass-derived precursor 5-hydroxymethyl- H.; Yang, Y. H.; Wang, Y. Base-free aerobic oxidation of 5−
furfural to 2, 5-furandicarboxylic acid under mild conditions over a hydroxymethyl-furfural to 2,5-furandicarboxylic acid in water catalyzed
magnetic palladium nanocatalyst. Green Chem. 2015, 17, 1308−1317. by functionalized carbon nanotube-supported Au-Pd alloy nano-
(7) Mei, N.; Liu, B.; Zheng, J. D.; Lv, K. L.; Tang, D. G.; Zhang, Z. H. particles. ACS Catal. 2014, 4, 2175−2185.
A novel magnetic palladium catalyst for the mild aerobic oxidation of
5-hydroxymethylfurfural into 2,5-furandicarboxylic acid in water. Catal.
Sci. Technol. 2015, 5, 3194−3202.
(8) Partenheimer, W.; Grushin, V. V. Synthesis of 2, 5-Diformylfuran
and 2, 5-furandicarboxylic acid by Catalytic Air-Oxidation of 5-
Hydroxymethylfurfural. Unexpectedly Selective Aerobic Oxidation of
Benzyl Alcohol to Benzaldehyde with Metal/Bromide Catalysts. Adv.
Synth. Catal. 2001, 343, 102−111.
(9) Hansen, T. S.; Sadaba, I.; Garcia-Suarez, E. J.; Riisager, A. Cu
catalyzed oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran
and 2,5-furandicarboxylic acid under benignreaction conditions. Appl.
Catal., A 2013, 456, 44−50.
(10) Saha, B.; Abu-Omar, M. M. Advances in 5-hydroxymethylfur-
fural production from biomass in biphasic solvents. Green Chem. 2014,
16, 24−38.
(11) Ma, P. S.; Xia, Q. Determination and correlation for solubility of
aromatic acids in solvents. Chin. J.Chem. Eng. 2001, 9, 39−44.
(12) Maitra, A.; Bagchi, S. Study of solute−solvent and solvent-
solvent interactions in pure and mixed binary solvents. J. Mol. Liq.
2008, 137, 131−137.
(13) Grosse Daldrup, J.-B.; Held, C.; Sadowski, G.; Schembecker, G.
Modeling pH and solubilities in aqueous multisolute amino acid
solutions. Ind. Eng. Chem. Res. 2011, 50, 3503−3509.
(14) Grosse Daldrup, J.-B.; Held, C.; Ruether, F.; Schembecker, G.;
Sadowski, G. Measurement and modeling solubility of aqueous
multisolute amino-acid solutions. Ind. Eng. Chem. Res. 2010, 49,
1395−1401.
(15) Sahu, R.; Dhepe, P. L. Synthesis of 2,5-furandicarboxylic acid by
the aerobic oxidation of 5-hydroxymethyl furfural over over supported
metal catalysts. React. Kinet., Mech. Catal. 2014, 112, 173−187.
(16) Li, Y.; Ma, P. S.; Chen, M. M.; Liang, Y.; Wang, J. F.
Determination and correlation of the solubilities with the ethanol as
solvent and the main components of pure terephthalic acid
manufacture residue as solute. Chem. J. Chi. Univ 2006, 20, 282−286.
(17) Luo, W. P.; Ruan, D.; Liu, D. W.; Xie, K. L.; Li, X. Q.; Deng, W.;
Guo, C. C. Measurement and Correlation for Solubilities of Adipic
Acid in Acetic Acid + ε-Caprolactone Mixtures and Cyclohexanone +
ε-Caprolactone Mixtures. J. Chem. Eng. Data 2016, 61, 2474−2480.
(18) Xia, Q.; Chen, S. N.; Chen, Y. S.; Zhang, M. S.; Zhang, F. B.;
Zhang, G. L. Solubility of decanedioic acid in binary solvent mixtures.
Fluid Phase Equilib. 2011, 304, 105−109.
(19) Farajnezhad, A.; Afshar, O. A.; Khansary, M. A.; Shirazian, S.;
Ghadiri, M. Correlation of interaction parameters in Wilson, NRTL
and UNIQUAC models using theoretical methods. Fluid Phase Equilib.
2016, 417, 181−186.
(20) Magnussen, T.; Rasmussen, P.; Fredenslund, A. UNIFAC
parameters table for prediction of liquid-liquid equilibria. Ind. Eng.
Chem. Process Des. Dev. 1981, 20, 331−339.
(21) Han, S. J. The relationship of vapor-liquid equilibria in
acrylonitrile-acetonitrile-water. Chin. J. Chem. Eng. 1980, 31, 242−254.
(22) Gmehling, B.; Onken, U.; Arlt, W. Vapor-liquid equilibrium data
collection; Dechema: Frankfurt, 1977.
(23) Payne, S. M.; Kerton, F. M. Solubility of bio-sourced feedstocks
in ‘green’ solvents. Green Chem. 2010, 12, 1648−1653.

1324 DOI: 10.1021/acs.jced.7b00927

J. Chem. Eng. Data 2018, 63, 1316−1324