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

18 hours ago - 2,5-Furandicarboxylic acid (FDCA) serves as a monomer in various polyesters and is often obtained through the oxidation of 5-hydroxymet...
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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 5hydroxymethylfurfural. 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), 1butanol, 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.

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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-Hydroxymethylfurfural (5-HMF), which is obtained by the dehydration 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 5HMF 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 © XXXX American Chemical Society

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

A

DOI: 10.1021/acs.jced.7b00927 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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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 isobutanol methanol 1-butanol acetic acid ethyl acetate acetonitrile MIBK water terephathalie acid

3238-40-2 78-83-1 67-56-1 71-36-3 64-19-7 141-78-6 75-05-8 108-10-1 7732-18-5 100-21-0

Aladdin Reagent Co., Ltd. Aladdin Reagent Co., Ltd. Hangzhou Gaojing Fine Chemical Industry Co., Ltd.

0.95 0.99 0.99 0.99 0.99 0.99 0.999 0.99 conductivity was less than 5 × 10−4 S·m−1 0.99

Spectrum Chemical Manufacturing Co., Ltd. Shanghai Macklin Biochemical Co., Ltd. Hangzhou Wahaha Co., Ltd. Aladdin Reagent Co., Ltd.

Table 2. Experimental Mole Fraction Solubilities xexp and Reported Solubility Data xref of TPA in Acetic Acid at Varying Temperatures T and Pressure p = 0.1 MPaa

isobutanol) and two binary solvent systems (water + acetonitrile and water + acetic acid) at 313.15−363.15 K. The solubility data was correlated with the WILSON model, NRTL model, and UNIQUAC model.

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EXPERIMENTAL METHODS Chemicals. All chemicals were used without further purification. Deionized water was used throughout all of the experiments. The specifications for the chemicals that were used are shown in Table 1. In Table 1, w is the mass fraction. Apparatus and Procedure. Solubility was measured by the static analytical method. Solvent (pure solvents or specified 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 difficult to measure the equilibrium temperature directly. In the preliminary experiments, we found that the difference between the equilibrium temperature and the water bath temperature was less than 0.1 K. The mixture temperature in the equilibrium cell was nearly equal to the water bath temperature, which was measured with a thermometer (accuracy was 0.1 K). Preexperiments showed that the equilibrium state could be reached with 2 h of vigorous shaking (shaking speed was 200 rpm) and 8 h of static standing. About 0.5 mL of supernatant was sampled with a syringe. The syringe was washed with methanol 5 times to transfer all of the components to the flask. To confirm the accuracy of this experimental procedure, the solubility of terephthalic acid (TPA) in acetic acid was measured with the experimental method reported in this article. The samples were analyzed with the method used in literature.11 The experimental solubility data and the solubility data reported in literature11 are shown in Table 2. In Table 2, T is the equilibrium temperature, xexp is solubility data measured in this article, and xref is the solubility reported in literature.11 δRD is the relative deviation. The solubility data measured in

T (K)

105xexp

105xref

δRD

315.15 325.15 334.15 343.15 354.15 363.15

5.532 7.998 11.023 14.210 20.895 28.010

5.495 8.026 10.53 14.330 20.710 27.000

0.00670 0.00350 0.0468 0.00840 0.00890 0.0374

a Standard uncertainties, u, were u(T) = 0.05 K, ur(p) = 0.05, and ur(xexp) = 0.1.

this article agreed well with that reported in literature, and the experimental method used in this article was reliable. Analysis Method. The samples were weighed by an analytical balance (OHAUS CP214) with an accuracy of 0.1 mg. The samples were transferred to volumetric flasks by washing the syringe 5 times and were diluted with methanol. The diluted samples were analyzed with Shimadzu LC 2016A high-performance liquid chromatography to determine the content of FDCA. A Diamonsil C18 (150 mm × 4.6 mm) chromatographic column and UV detector (265 nm) were used. The mobile phase consisted of two eluents (water (0.02 mol·L−1 aqueous ammonium acetate, PH = 4) + acetonitrile), and the volume fraction of water was 0.8. With the HPLC analysis results, the mole fraction of FDCA could be obtained with eq 1. In eq 1, x is the mole fraction of FDCA. k and c are the parameters of the calibration equation (R2 = 0.998). A is the analysis result of HPLC. V is the dilution ratio of the sample. ms is the mass of the sample. x= B

(kA + c)V ms

(1) DOI: 10.1021/acs.jced.7b00927 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 3. Experimental Mole Fraction Solubilities x of FDCA in Different Pure Solvents at Varying Temperatures T and Pressure p = 0.1 MPaa solvent water

acetic acid

1-butanol

a

T (K)

104x

313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15

2.027 2.253 2.827 3.698 4.206 4.646 5.984 6.408 7.808 9.084 11.002 2.353 2.724 3.305 4.040 4.775 5.546 7.166 8.202 9.652 11.454 13.369 26.633 30.206 34.631 40.763 46.876 52.407 57.177 66.311 74.077 81.953 91.623

solvent

T (K)

104x

solvent

T (K)

104x

methanol

313.15 318.15 323.15 328.15 333.15 338.15 343.15

42.816 48.886 53.960 68.017 80.088 86.856 89.420

acetonitrile

ethyl acetate

313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15

0.778 1.133 1.64 2.379 2.846 3.768 4.64 5.493 6.195 6.586 7.207 16.834 19.840 22.975 26.959 32.271 37.176 41.219 48.187 54.801 60.689 68.216

MIBK

313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15

0.611 0.915 1.120 1.359 1.662 2.118 2.481 2.780 3.408 4.093 4.875 1.363 1.843 2.530 2.960 3.383 4.291 5.356 6.314 6.659 7.209 8.626

isobutanol

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 0.148 0.207 0.267 0.319 0.368 0.589 0.772 0.900 0.078 0.147 0.211 0.266 0.317 0.366 0.587 0.770 0.899

3.214 8.548 14.361 18.293 23.372 25.890 38.386 24.399 8.575 7.363 17.423 29.061 39.424 47.164 52.684 76.627 54.317 23.290

323.15

0.078 0.146 0.209 0.266 0.316 0.366 0.594 0.767 0.900 0.077 0.148 0.206 0.266 0.318 0.367 0.594 0.765 0.899

5.205 11.747 20.650 23.988 28.627 32.499 43.898 28.461 10.538 8.228 21.221 31.049 44.849 55.678 60.739 86.550 60.184 22.883

333.15

0.078 0.147 0.211 0.266 0.317 0.367 0.610 0.751 0.903 0.078 0.146 0.209 0.266 0.315 0.364 0.607 0.748 0.901

6.567 13.503 22.780 26.460 35.723 40.977 56.878 42.961 15.348 11.292 22.778 35.993 51.908 61.559 72.737 102.483 83.462 34.925

343.15

a

353.15

363.15

Standard uncertainties, u, were u(T) = 0.05 K, ur(xwater) = 0.001, ur(p) = 0.05, and ur(x) = 0.1.

C

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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 0.162 0.226 0.286 0.343 0.392 0.455 0.690 0.834 0.926 0.083 0.161 0.226 0.285 0.342 0.392 0.455 0.689 0.832 0.926

2.727 3.546 3.813 4.496 5.015 5.584 6.506 11.797 7.338 5.160 8.920 10.796 11.749 13.028 15.463 17.664 20.802 27.073 21.875 14.661

323.15

0.085 0.160 0.226 0.286 0.343 0.397 0.476 0.690 0.832 0.929 0.085 0.160 0.225 0.286 0.342 0.396 0.455 0.688 0.832 0.925

3.650 4.216 4.375 5.062 5.892 6.992 8.372 13.824 9.366 5.903 11.371 12.861 13.501 15.359 18.758 20.810 23.533 36.860 30.929 16.862

333.15

0.085 0.161 0.229 0.290 0.346 0.392 0.472 0.689 0.838 0.929 0.085 0.161 0.229 0.290 0.346 0.391 0.454 0.688 0.831 0.924

6.027 6.842 7.590 8.508 8.941 10.474 13.017 16.521 13.479 10.368 16.780 18.770 20.761 23.051 25.065 27.147 33.190 42.918 36.659 26.047

343.15

a

353.15

363.15

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

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system

xwater

pH

system

xwater

pH

water + acetic acid + FDCA

0.018 0.176 0.229 0.284 0.343 0.390 0.458 0.689 0.804 0.927

3.85 3.56 3.48 3.4 3.32 3.12 2.53 2.09 2.37 2.58

water + acetonitrile + FDCA

0.081 0.155 0.213 0.267 0.324 0.377 0.591 0.772 0.898

4.16 4.02 3.87 3.59 3.05 2.78 3.29 3.28 3.35

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

very small. Acetonitrile, ethyl acetate, and MIBK are nonprotonic 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. D

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According to the Scatchard−Hildebrand model,12 the solubility was the largest when the solubility parameters of the solute were close to those of the solvent. At a certain binary mixture composition, the solubility parameters of FDCA might be close to those of binary solvents, and the solubility was the largest. Moreover, with the addition of water into the acetic acid system, the self-association of acetic acid was disturbed, and the mole fraction of FDCA in acetic acid increased. When the water content was too large, the solubility parameters of FDCA and the solvents became quite different, and the mole fraction of FDCA decreased. The prevailing pH might highly influence the solubility of FDCA.13 When water was added to acetic acid (or acetonitrile) the pH changed. The pH of the saturated aqueous solution at 298.15 K is shown in Table 6. The pH data was used only to demonstrate the dependency of the FDCA solubility on pH, and the influence of pH was not studied in this article. Three models were used to correlate the solubility data. The determination of the model parameters was as follows. The given initial value of the model parameters to be determined allowed for the calculation of the activity coefficient, γ. Knowing γ, the solubility of FDCA could be calculated from eq 2.14 In eq 2, the influence of the heat capacities was neglected. The calculation data and the experimental data were compared. A nonlinear optimization method, implemented in a MATLAB toolbox, was used to update the value of the model parameters, minimizing the average relative deviation (ARD). The calculation of ARD is shown in eq 3. ln(γx) =

ARD =

ΔHfus ⎛ 1 1 ⎞ ⎟ ⎜ − R ⎝T Tm ⎠

ln ri = ln

∑l Gl ixl

j

(5)

In eq 5, Gij = exp(−αijlij), lij = aij + bij/T, and αij = 0.3. In the WILSON model, the activity coefficient was calculated with eq 6.18 ⎞ ⎛ ln ri = 1 − ln⎜⎜∑ xjΛ ij⎟⎟ − ⎠ ⎝ j

⎛ x k Λk j ⎞ ⎟⎟ ∑Λ x k = 1 ⎝ l kl l ⎠

component

r

q

water methanol acetonitrile acetic acid ethyl acetate MIBK 1-butanol isobutanol FDCA

0.920 1.901 1.870 2.202 3.479 4.618 3.924 3.924 4.624

1.400 2.048 1.724 2.072 3.116 3.952 3.668 3.664 4.040

The model parameters determined by the correlation of the solubility data in the pure solvents are listed in Tables 8, 9, and 10. Except for the solubility in acetonitrile and ethyl acetate, the three models had a high prediction accuracy (ARD was less than 0.1). The models could be applied to predict the solubility of FDCA in pure solvents. To make the figures clear, only the prediction results of the NRTL model for the solubility in the pure solvents is shown in Figure 2. For the solubility in the binary mixtures, the prediction accuracy of the WILSON model was very low. Only the NRTL model and UNIQUAC model were applied to correlate the solubility data. It was of great value to use the interaction parameters in Tables 8 and 9 to predict the solubility of FDCA in the binary mixtures. The interaction parameters of the water−acetonitrile and water−acetic acid were obtained by the correlation of the VLE data in literature.21,22 The prediction accuracy of the NRTL model and UNIQUAC model, when the above interaction parameters were used, is shown in Figures 3, 4, 5, and 6. The prediction accuracy was very low, and the ARD was above 30%. In the water−acetic acid binary mixture, the self-association of the acetic acid molecules was disturbed with the addition of water. In the water−acetonitrile binary mixture, the synergistic effect of water and acetonitrile might influence

(4)

∑ xτ G ⎤ xjGij ⎡ ⎢τij − l l l j l i ⎥ ∑l Gl jxl ⎢⎣ ∑l Gl jxl ⎥⎦

(8)

Table 7. UNIQUAC Structural (Area and Volume) Parameters

(3)

∑

(7)

With this group division method, the calculated volume parameters and surface area parameters of furfural were 3.247 and 2.731 respectively. These values agreed well with those in literature.20 The UNIQUAC structural (area and volume) parameters of the components are listed in Table 7.

In eq 3, K1 was 13.5 for FDCA, and the value of ΔHfus was 34746.61 J·mol−1. In the NRTL model, the activity coefficient was calculated with eq 5.17 +

j

⎤ ⎥ ∑k θkτk j ⎥⎦ θτ j ij

q = 2q−COOH + 2q−CH = C − + q−O −

16

∑j τijGjixj

∑

∑ xjlj

r = 2r −COOH + 2r −CH = C − + r −O −

In eq 2, T is the equilibrium temperature; Tm is the melting temperature of FDCA, 615.15 K;15 and ΔHfus is the enthalpy of fusion at Tm. In eq 3, NDP is the number of experimental points. x is the mole fraction of FDCA in solvents. The 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 eq 4.

ln γi =

ϕ θ Z qi ln i + l i − i ϕi xi 2

In eq 7, ln(lij) = eij + f ij/T. r and q are the volume parameters and surface area parameters, respectively. The molecular volume parameters and surface area parameters of FDCA were calculated from eq 8. The FDCA molecule was constituted with two −COOH groups, two −CHC− groups, and one −O− group. The volume parameters and surface area parameters were obtained from literature.20 The volume parameters and surface area parameters of different solvents were also obtained from literature.20

∑i |(xexp − xcal)/xexp|

ΔHfus = 4.184TmK1

xi

+

⎡ ⎛ ⎞ ⎟ − qi⎢ln⎜⎜∑ θτ j ji ⎟ − 1 + ⎢ ⎠ ⎣ ⎝ j

(2)

NDP

ϕi

∑ ⎜⎜

(6)

In eq 6, ln(Λij) = cij + dij/T. In the UNIQUAC model, the activity coefficient was calculated with eq 7.19 E

DOI: 10.1021/acs.jced.7b00927 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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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 methanol acetonitrile acetic acid ethyl acetate MIBK 1-butanol isobutanol

−12.702 2.196 −1.302 −1.606 −2.647 −0.0115 −0.708 −0.770

5.578 × 103 −403.119 290.660 168.572 456.870 −94.876 6.149 8.450

1.070 1.084 −0.319 4.613 4.140 2.709 4.511 3.855

−15.711 −848.157 1414.300 −347.311 136.280 2.865 −1291.294 −917.385

0.0316 0.0380 0.0991 0.0152 0.299 0.0666 0.0121 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 methanol acetonitrile acetic acid ethyl acetate MIBK 1-butanol isobutanol

0.2638 0.177 9.567 0.134 0.118 −0.553 −0.858 −1.195

13.347 −228.950 −6.990 × 103 −40.763 −191.580 26.001 −578.000 86.306

−0.702 −0.625 1.357 −0.728 0.150 −0.235 −0.0665 0.0215

44.522 396.390 −446.390 45.866 −151.050 7.606 350.990 183.909

0.0342 0.0381 0.0986 0.015 0.297 0.0663 0.0119 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 methanol acetonitrile acetic acid ethyl acetate MIBK 1-butanol isobutanol

−1.867 −4.042 2.956 −1.087 1.634 −1.696 −3.091 0.0353

217.950 710.640 −1.796 × 103 0.949 −1.100 × 103 101.210 1237.400 −126.290

−29.508 0.959 2.273 × 106 −2.959 −38.785 −33.578 −0.646 −2.296

−1.419 × 103 110.610 1.749 × 106 1.548 3182.500 −5.186 × 103 39.743 817.790

0.0343 0.0384 0.0987 0.0159 0.296 0.0664 0.0117 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.

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).

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

interaction parameters in Tables 8 and 9 were used. To predict the solubility of FDCA in the binary mixtures, the model F

DOI: 10.1021/acs.jced.7b00927 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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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).

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).

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 PCSAFT 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

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 G

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Table 11. Model Parameters of the NRTL Model for the Solubility in Binary Mixtures i

j

aij

FDCA water FDCA

water acetonitrile acetonitrile

9.328 −0.309 6.594

FDCA water FDCA

water acetic acid acetic acid

−3.442 1.513 0.704

bij (K) Water + Acetonitrile −1.423 × 103 −489.650 1221.022 Water + Acetic Acid 5.005 × 105 −720.320 1.030 × 103

aji

bji (K)

ARD

4.473 −0.522 5.977

−1.158 × 103 2.247 × 103 −416.963

0.0711

0.477 0.150 0.259

527.924 837.895 −2.498 × 105

0.0820

eji

f ji (K)

ARD

−0.154 −0.0643 −0.507

338.952 −395.986 −1.471 × 104

0.111

Table 12. Model Parameters of the UNIQUAC Model for the Solubility in Binary Mixtures i

j

eij

FDCA water FDCA

water acetonitrile acetonitrile

0.0836 −0.456 −0.0144

FDCA water FDCA

water acetic acid acetic acid

0.161 −1.367 −0.0134

f ij (K) Water + Acetonitrile −1.417 × 104 247.787 −116.903 Water + Acetic Acid 1.043 −1.0067 0.0810

−0.347 0.569 −0.524

0.619 2.624 −2.522

0.0882

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.

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AUTHOR INFORMATION

Corresponding Author

Figure 7. Experimental solubility data and data reported in the literature of three solvents. ■, solubility in methanol measured in this article; ⧫, ref 23, solubility in methanol; □, ref 24, solubility in methanol; ●, solubility in acetic acid measured in this article; ○, ref 24, solubility in acetic acid; ▲, solubility in water measured in this article; ▼, ref 23, solubility in water; Δ, ref 24, solubility in water; ☆, ref 25, solubility in water; and -, calculated with the NRTL model.

*Tel.: 0086-571-56700179; Fax: 0086-571-56700172; E-mail: [email protected]. ORCID

Yongzhao Zhang: 0000-0003-3063-3944 Funding

All of the authors received funding from the Zhejiang Provincial Department of Education (Y201738406) and Hangzhou Vocational and Technical College (ky201832).

0.00365 g/g. The solubility of FDCA could reach 0.0331 and 0.00831 g/g in water + acetonitrile and water + acetic acid binary mixtures, respectively. The addition of acetonitrile or 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 catalyst was used, and the deactivation of the catalyst could be avoided.

Notes

The authors declare no competing financial interest.

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REFERENCES

(1) Rizzi, F.; Van-Eck, N. J.; Frey, M. The production of scientific knowledge on renewable energies: Worldwide trends, dynamics and 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)-

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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 H

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co-poly(lactic acid) copolyesters. Macromol. Chem. Phys. 2014, 215, 2175−2184. (4) Sousa, A. F.; Vilela, C.; Fonseca, A. C.; Matos, M.; Freire, C. S. R.; Gruter, G. M.; Coelho, J. F. J.; Silvestre, A. J. D. Biobased polyesters and other polymers from 2,5-furandicarboxylic acid: a tribute to furan excellency. Polym. Chem. 2015, 6, 5961−5983. (5) Jiang, Y.; Woortman, A. J. J.; Alberda van Ekenstein, G. O. R.; Loos, K. A biocatalytic approach towards sustainable furanic-aliphatic polyesters. Polym. Chem. 2015, 6, 5198−5211. (6) Zhang, Z. H.; Zhen, J. D.; Liu, B.; Lv, K. L.; Deng, K. J. Selective aerobic oxidation of the biomass-derived precursor 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid under mild conditions over a magnetic palladium nanocatalyst. Green Chem. 2015, 17, 1308−1317. (7) Mei, N.; Liu, B.; Zheng, J. D.; Lv, K. L.; Tang, D. G.; Zhang, Z. H. 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 5Hydroxymethylfurfural. 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-hydroxymethylfurfural 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 solventsolvent 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.

(24) Ban, H.; Pan, T.; Cheng, Y. W.; Wang, L. J.; Li, X. Solubilities of 2,5-furandicarboxylic acid in binary acetic acid + water, methanol + water and ethanol + water solvent mixtures. J. Chem. Eng. Data, submitted for publication, 2018. (25) Rose, H.; Greinert, T.; Held, C.; Sadowski, G.; Bommarius, A.; Mutual influence of furfural and furancarboxylic acids on their solubility in aqueous solutions: Experiments and PC-SAFT predictions. J. Chem. Eng. Data, submitted for publication, 2018.10.1021/acs.jced.7b01039 (26) Wan, X. Y.; Zhou, C. M.; Chen, J. S.; Deng, W. P.; Zhang, Q. H.; Yang, Y. H.; Wang, Y. Base-free aerobic oxidation of 5− hydroxymethyl-furfural to 2,5-furandicarboxylic acid in water catalyzed by functionalized carbon nanotube-supported Au-Pd alloy nanoparticles. ACS Catal. 2014, 4, 2175−2185.

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