Solubilities of 2,5-Furandicarboxylic Acid in Binary Acetic Acid + Water

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Solubilities of 2,5-Furandicarboxylic Acid in Binary Acetic Acid + Water, Methanol + Water, and Ethanol + Water Solvent Mixtures Heng Ban, Teng Pan, Youwei Cheng,* Lijun Wang, and Xi Li Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. China ABSTRACT: The solubilities of 2,5-furandicarboxylic acid (FDCA) in binary acetic acid + water, methanol + water, and ethanol + water solvent mixtures were measured by a static analytical method with the mass fraction of water in the solvent varying from 0 to 0.3 at atmospheric pressure. Furthermore, the molar enthalpy of fusion (ΔfusH = 55.131 kJ/mol) and fusion temperature (Tfus = 614.45 K) of FDCA were determined by differential scanning calorimetry. The non-random two liquid (NRTL) model and the measured parameters were used to correlate these solubility data, and the relevant parameters were regressed by the least-squares method. The NRTL model was found to provide a satisfactory representation of the experimental data.

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INTRODUCTION 2,5-Furandicarboxylic acid (FDCA) is a significant organic intermediate derived from biomass materials that is widely used to synthesize plastics, anticorrosion materials, coatings, medical intermediates, and so on.1−7 Because of its chemical structure, which is similar to that of mass-produced terephthalic acid (TA) derived from nonrenewable petroleum, FDCA can also be copolymerized with ethylene glycol (EG) into poly(ethylene 2,5-furandicarboxylate) (PEF), which has properties and applications comparable to those of poly(ethylene terephthalate) (PET) synthesized from TA and EG.8,9 Most importantly, these high-performance copolyester materials based on the platform chemical FDCA, which exhibit great renewability and biodegradability, are considered to have significant application value and prospects.10,11 As a consequence, FDCA was recognized as one of the top 12 valueadded chemicals from biomass by the U.S. Department of Energy.12 In the Mid-Century (MC) process, 5-hydroxymethylfurfural (HMF) is used as the starting material and is oxidized into FDCA in acetic acid over a ternary Co−Mn−Br catalyst system, with water formed as the byproduct.13−17 In other words, the actual solvent is a mixture of acetic acid and water. To reduce the operation cost and enhance commercial interest, the solution after the reaction and the FDCA dissolved in the reaction solution need to be further recycled. To meet the standards of the polyester industry, the crude FDCA prepared by oxidation needs to be further purified by crystallization in binary acetic acid + water solvent mixtures18 or by esterification with methanol or ethanol to give dimethyl furan-2,5-dicarboxylate or diethyl furan2,5-dicarboxylate, respectively, with the formation of water.19−21 Thus, the solubilities of FDCA in binary acetic acid + water, methanol + water, and ethanol + water solvent mixtures are required in order to determine the feed composition, reaction and crystallization conditions, etc., and the solubilities of FDCA © XXXX American Chemical Society

in these binary solvent mixtures are essential solid−liquid equilibrium data for these processes. Unfortunately, there are no literature reports about the solubilities of FDCA in these solvent mixtures. Therefore, it is highly crucial to measure the solubilities of FDCA to provide basic data and a theoretical foundation for the improvement of existing industrial processes and the development of new ones. Thus, in this work the solubilities of FDCA in binary acetic acid + water, methanol + water, and ethanol + water solvent mixtures with water mass fractions varying from 0 to 0.3 were measured by a static analytical method.

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EXPERIMENTAL SECTION Chemicals. FDCA was obtained from Aladdin Chemistry Co., Ltd. and added to a suitable amount of water that was heated to 423.15 K later to ensure the complete dissolution of FDCA. Then two crystallization experiments were carried out to remove the impurities and obtain purer FDCA with a mass fraction of 0.995 as determined by using high-performance liquid chromatography (HPLC). The fusion temperature and molar fusion enthalpy of purified FDCA are reported in Table 2 and compared with the literature data. Methanol, ethanol, and acetic acid of AR grade were supplied by Sinopharm Chemical Reagent Co., Ltd. HPLC-grade methanol from USA Tedia Co. was used as the mobile phase in HPLC analysis. Deionized water was used throughout all the experiments. All of the above chemicals except for FDCA were used without further purification. All major information about these materials is given in Table 1. Apparatus and Procedure. The solubility measurement was carried out in a 50 mL glass bottle with one mouth for Received: December 26, 2017 Accepted: April 20, 2018

A

DOI: 10.1021/acs.jced.7b01112 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Properties of Materials Used in This Work

a

chemical name

CASRN

source

mass-fraction purity

purification method

analysis method

2,5-furandicarboxylic acid methanol ethanol acetic acid methanol deionized water

3238-40-2 67-56-1 64-17-5 64-19-7 67-56-1 7732-18-5

Aladdin Chemistry Co. Sinopharm Chemical Reagent Co. Sinopharm Chemical Reagent Co. Sinopharm Chemical Reagent Co. USA Tedia Co. Hangzhou Wahaha Co.

>0.98 ≥0.995 ≥0.995 ≥0.995 ≥0.999 ≥0.999

recrystallization none none none none none

HPLCa GCb GCb GCb GCb GCb

High-performance liquid chromatography. bGas chromatography.

feeding and temperature measurement. The bottle was sealed with a rubber stopper to prevent evaporation of the solvent and put into a superthermostatic water circulator bath in which water was circulated continuously with a stirring paddle and the temperature uncertainty was controlled to within ±0.05 K using an advanced PID thermoelectric control system. In addition, a mercury glass thermometer with a minimum precision of ±0.2 K was inserted into the solution to detect the equilibrium temperature. The feasibility and reliability of the experimental apparatus has been recognized in our previous work.22−28 Solubility Measurements. In each experiment, an excess amount of FDCA was added to a 50 mL sealed glass bottle with the preprepared solvent. Then the equilibrium flask was heated to the required temperature in a superthermostatic water circulator bath and kept isothermal for at least 24 h with periodic agitation to make the solution saturated. The equilibrium was verified by repetitive sampling and analysis until the measured results were reproducible within ±1%. About 2 mL of supernatant liquid withdrawn from the bottle using a preheated glass syringe was immediately transferred to a 100 mL volumetric flask that had been weighed in advance. Subsequently, the total mass of the sample and the volumetric flask was determined using an analytical balance with a minimum precision of ±0.0001 g. The sample was then diluted to 100 mL with methanol, and the solution was homogeneously mixed by shaking the volumetric flask up and down at least 20 times. Each measurement was repeated at least three times until the relative error was within ±1% to ensure the accuracy of the experimental results.

Table 2. Fusion Temperature and Molar Enthalpy of Fusion of 2,5-Furandicarboxylic Acid at p = 0.1 MPaa property

exp.

lit.

Tfus/K ΔfusH/(kJ/mol)

614.45 55.131

615.15b −

a

The standard uncertainty in the temperature is u(T) = 0.3 K, and the relative standard uncertainties in the pressure and molar enthalpy of fusion are ur(p) = 0.05 and ur(ΔfusH) = 0.03, respectively. bReference 3.

Figure 1. Differential scanning calorimetry curve of 2,5-furandicarboxylic acid.

Figure 2. Determined solubilities and literature data of 2,5-furandicarboxylic acid (FDCA) in (a) pure water, (b) acetic acid, (c) methanol, and (d) ethanol: △, experimental data from this work; □, experimental data from ref 29; ○, experimental data from ref 30. B



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Analytical Methods. The concentrations of FDCA in the samples were determined by HPLC, and every sample was analyzed at least twice until the relative error was within ±1%. The measurements were carried out using an Agilent 1100 series chromatograph equipped with an Agilent SB-C18 chromatographic column (4.6 mm × 250 mm) and a diode array detector (270 nm). Gradient elution was adopted to separate samples completely at 30 °C. The mobile phase consisted of methanol. Each analysis took about 10 min. The molar enthalpy of fusion (ΔfusH) and the fusion temperature (Tfus) of FDCA were determined by differential scanning calorimetry (DSC), using a Netzsch DSC 214 Polyma differential scanning calorimeter. The temperature-rising speed was 5 K/min from (323.15 to 673.15) K, and the FDCA sample was sealed in a pressure crucible. As listed in Table 2, ΔfusH was found to be 55.131 kJ/mol, and Tfus was measured as 614.45 K, which is quite close to the reported fusion temperature of 615.15 K. The detailed DSC results are shown in Figure 1, where the area, Tpeak m , and Tmonset represent the molar enthalpy of fusion, peak temperature, and fusion temperature of FDCA, respectively.

calculated values of the mole-fraction solubility respectively, and w2 represents the mass fraction of water in the solvent mixtures. The data in these figures and tables demonstrate that within the measured temperature range the solubilities of FDCA in all of the mixtures show a remarkably increasing trend with increasing temperature. Correlation of Experimental Data. The dependence of the solubility on the temperature is given by eq 1: ln(γ1x1) = −

ΔfusH ⎛ 1 1 ⎞ ⎟ ⎜ − R ⎝T Tfus ⎠

(1)

where γ1 is the activity coefficient of the solute, x1 is the real mole fraction of the solute in the solution (denoted as xexp in this work), R is the ideal gas constant (R = 8.314 J mol−1 K−1), T is the absolute temperature, ΔfusH is the molar enthalpy of fusion of the solute, and Tfus is the fusion temperature. According to the DSC results in Figure 1, it has been recognized that ΔfusH = 55.131 kJ/mol and Tfus = 614.45 K.

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RESULTS AND DISCUSSION Credibility Analysis. To verify the reliability of the above experimental method, the solubility data of FDCA in pure acetic acid, water, methanol, and ethanol measured by the above method were compared with the works of other authors.29,30 As shown in Figure 2, the deviations of the FDCA solubility data in water and ethanol are significantly small and can be neglected, which further testifies to the accuracy of our experimental results. However, the solubility data of FDCA in acetic acid and methanol measured by us are bigger than those of Zhang et al.,29 which may be attributed to the different method and shorter time taken by Zhang et al., preventing the system from fully reaching the solid− liquid equilibrium state because of the extremely low solubility of FDCA in these solvents.29 Solubility Data. The mole-fraction solubilities of FDCA in binary acetic acid + water, methanol + water, and ethanol + water solvent mixtures are shown in Figures 3 to 5 and listed in Tables 3 to 5, in which xexp and xcal stand for experimental data and

Figure 4. Mole-fraction solubilities of 2,5-furandicarboxylic acid in binary methanol + water solvent mixtures in the temperature range from (297.35 to 332.65) K: ■, 0% H2O; ●, 5.0% H2O; ▲, 10.0% H2O; □, 20.0% H2O; ○, 30.0% H2O. Solid lines were calculated from the NRTL model.

Figure 3. Mole-fraction solubilities of 2,5-furandicarboxylic acid in binary acetic acid and water solvent mixtures in the temperature range from (303.55 to 352.25) K: ■, 0% H2O; ●, 5.0% H2O; ▲, 10.0% H2O; □, 20.0% H2O; ○, 30% H2O; △, 100% H2O. Solid lines were calculated from the NRTL model.

Figure 5. Mole-fraction solubilities of 2,5-furandicarboxylic acid in binary ethanol + water solvent mixtures in the temperature range from (299.35 to 346.35) K: ■, 0% H2O; ●, 5.0% H2O; ▲, 10.0% H2O; □, 20.0% H2O; ○, 30.0% H2O. Solid lines were calculated from the NRTL model. C



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in which x1 and x2 are the mole fractions of FDCA and water, respectively, in the saturated solution, x3 is used to represent the mole fraction of the other component in the solvent mixture (here acetic acid, methanol, or ethanol), and Gij and τij are the model parameters of the NRTL equation, which can be calculated by the following equations:

There are many equations describing the relationship between activity coefficients and mole fractions,31−33 among which the non-random two liquid (NRTL) equation is adopted often because it can be applicable to both partially miscible and completely miscible mixtures. The NRTL activity coefficient model used in this work is expressed as follows: 3

ln γ1 =

∑ j = 1 τj1Gj1xj 3

∑k = 1 Gk1xk

3

+

∑ j=1

Gij = exp( −αijτij),

3 ⎛ ∑ xτ G ⎞ ⎜τ − k = 1 k kj kj ⎟ j 1 3 3 ∑k = 1 Gkjxk ⎜⎝ ∑k = 1 Gkjxk ⎟⎠

aij = αji

(3)

xjG1j

τij =

(2)

gij − gjj (4)

RT

Table 3. Mole-Fraction Solubilities of FDCA (1) in Binary Acetic Acid (3) + Water (2) Solvent Mixtures Where the Mass Fraction of Water Varied from 0 to 1.00 from (303.55 to 352.25) K at p = 0.1 MPaa w2 0

0.05

0.10

T/K

xexp×104

xcal×104

δRD/%

w2

T/K

xexp×104

xcal×104

δRD/%

303.55 313.25 322.95 332.75 342.45 352.25 303.55 313.25 322.95 332.75 342.45 352.25 303.55 313.25 322.95 332.75 342.45 352.25

2.424 3.188 4.706 6.563 8.737 11.14 2.732 4.285 6.422 10.15 16.59 20.90 3.541 4.820 7.506 11.67 16.90 22.19

2.386 3.351 4.643 6.370 8.601 11.51 2.694 4.262 6.817 10.69 15.64 21.05 3.333 4.866 7.230 10.86 15.97 22.59

1.58 −5.10 1.34 2.94 2.67 −3.28 1.39 0.54 −6.16 −5.30 5.75 −0.72 5.89 −0.95 3.68 7.00 5.48 −1.80

0.20

303.55 313.25 322.95 332.75 342.45 352.25 303.55 313.25 322.95 332.75 342.45 352.25 303.55 313.25 322.95 332.75 342.45 352.25

4.088 5.862 8.221 11.84 17.16 21.65 5.102 6.443 8.562 12.57 17.67 23.12 1.407 1.946 3.023 4.705 6.717 8.727

4.385 6.064 8.462 11.94 16.82 23.51 4.764 6.485 8.858 12.19 16.73 22.94 1.356 2.065 3.072 4.495 6.426 9.060

−7.26 −3.44 −2.93 −0.84 1.96 −8.58 6.63 −0.65 −3.45 3.05 5.33 0.78 3.62 −6.12 −1.65 4.48 4.32 −3.81

0.30

1.00

a

w2 is the mass fraction of water in the solvent mixture, and xexp and xcal are the experimental and calculated solubilities in the binary acetic acid (3) + water (2) solvent mixture, respectively. δRD is the relative deviation between the experimental solubility and the calculated value. The standard uncertainty in the temperature is u(T) = 0.2 K. The relative standard uncertainty in w2 is ur(w2) = 0.01, and the relative standard uncertainties in the pressure and mole-fraction solubility are ur(p) = 0.05 and ur(x) = 0.05, respectively.

Table 4. Mole-Fraction Solubilities of FDCA (1) in Binary Methanol (4) + Water (2) Solvent Mixtures Where the Mass Fraction of Water Varied from 0 to 0.3 from (297.35 to 332.65) K at p = 0.1 MPaa w2 0

0.05

0.10

T/K

xexp×103

xcal×103

δRD/%

w2

T/K

xexp×103

xcal×103

δRD/%

297.35 303.35 309.35 315.25 321.15 326.85 332.65 297.35 303.35 309.35 315.25 321.15 326.85 332.65 297.35 303.35 309.35 315.25

3.711 4.079 4.840 5.631 6.607 7.578 8.837 3.201 3.653 4.219 4.988 5.968 6.888 8.056 2.783 3.047 3.456 4.218

3.498 4.098 4.807 5.624 6.575 7.636 8.878 3.199 3.650 4.202 4.885 5.745 6.771 8.013 2.891 3.241 3.712 4.337

5.75 −0.48 0.68 0.12 0.50 −0.77 −0.46 0.07 0.07 0.39 2.07 3.75 1.70 0.53 −3.88 −6.37 −7.42 −2.82

0.10

321.15 326.85 332.65 297.35 303.35 309.35 315.25 321.15 326.85 332.65 297.35 303.35 309.35 315.25 321.15 326.85 332.65

5.203 6.112 7.251 2.314 2.536 2.957 3.527 4.300 5.103 6.081 1.890 2.047 2.420 2.864 3.501 4.185 5.143

5.143 6.084 7.185 2.293 2.551 2.963 3.527 4.229 5.024 6.020 1.773 2.016 2.405 2.911 3.521 4.246 5.258

1.15 0.45 0.90 0.88 −0.59 −0.22 −0.02 1.66 1.55 1.00 6.19 1.53 0.61 −1.66 −0.57 −1.46 −2.22

0.20

0.30

a

w2 is the mass fraction of water in the solvent mixture, and xexp and xcal are the experimental and calculated solubilities in the binary methanol (4) + water (2) solvent mixture, respectively. δRD is the relative deviation between the experimental solubility and the calculated value. The standard uncertainty in the temperature is u(T) = 0.2 K. The relative standard uncertainty in w2 is ur(w2) = 0.01, and the relative standard uncertainties in the pressure and mole-fraction solubility are ur(p) = 0.05 and ur(x) = 0.05, respectively. D



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Table 5. Mole-Fraction Solubilities of FDCA (1) in Binary Ethanol (5) + Water (2) Solvent Mixtures Where the Mass Fraction of Water Varied from 0 to 0.3 from (299.35 to 346.35) K at p = 0.1 MPaa T/K

xexp×103

xcal×103

δRD/%

w2

T/K

xexp×103

xcal×103

δRD/%

299.35 305.35 311.25 319.25 323.15 328.95 334.75 340.55 346.35 299.35 305.35 311.25 319.25 323.15 328.95 334.75 340.55 346.35 299.35 305.35 311.25 319.25 323.15

2.980 3.374 3.997 4.779 5.257 6.205 7.202 8.137 9.300 2.395 2.782 3.332 3.989 4.448 5.232 5.997 6.854 8.023 1.709 2.110 2.664 3.211 3.741

2.757 3.294 3.894 4.831 5.343 6.175 7.095 8.109 9.221 2.260 2.712 3.222 4.032 4.480 5.215 6.040 6.958 8.111 1.846 2.226 2.664 3.371 3.769

7.48 2.38 2.55 −1.10 −1.64 0.48 1.48 0.34 0.85 5.63 2.52 3.30 −1.07 −0.70 0.31 −0.71 −1.51 −1.10 −8.03 −5.51 −0.01 −4.99 −0.75

0.10

328.95 334.75 340.55 346.35 299.35 305.35 311.25 319.25 323.15 328.95 334.75 340.55 346.35 299.35 305.35 311.25 319.25 323.15 328.95 334.75 340.55 346.35

4.413 5.056 5.894 7.087 1.164 1.523 1.842 2.462 2.733 3.390 4.010 4.730 5.781 0.785 1.019 1.302 1.723 1.997 2.400 2.853 3.649 4.445

4.429 5.179 6.023 7.142 1.220 1.495 1.825 2.381 2.704 3.253 3.890 4.616 5.612 0.804 1.009 1.266 1.719 1.989 2.455 2.999 3.620 4.469

−0.36 −2.44 −2.19 −0.79 −4.83 1.85 0.97 3.28 1.05 4.03 3.01 2.41 2.93 −2.51 0.89 2.73 0.25 0.43 −2.26 −5.11 0.80 −0.54

w2 0

0.05

0.10

0.20

0.30

a

w2 is the mass fraction of water in the solvent mixture, and xexp and xcal are the experimental and calculated solubilities in the binary ethanol (5) + water (2) solvent mixture, respectively. δRD is the relative deviation between the experimental solubility and the calculated value. The standard uncertainty in the temperature is u(T) = 0.2 K. The relative standard uncertainty in w2 is ur(w2) = 0.01, and the relative standard uncertainties in the pressure and mole-fraction solubility are ur(p) = 0.05 and ur(x) = 0.05, respectively. 1/2 ⎡ n ⎛ ⎞2 ⎤ − x x 1 i i exp, cal, ⎟⎟ ⎥ × 100% RMSD = ⎢ ∑ ⎜⎜ ⎢n x ⎝ ⎠ ⎥⎦ i exp, ⎣ i=1

In eq 3, considering the molecular polarity and self-association behaviors of the solute and solvent, the value of αij can be fixed at 0.47, as recommended by Renon and Prausnitz.34 In eq 4, gij is an energy parameter characterizing the interaction of substances i and j. The expression for τij can be simplified to eq 5:

Values of δRD are given in Tables 3 to 5. It can be seen from Figures 3 to 5 that the calculated values show satisfactory agreement with the experimental results, and the RMSDs between the simulated values and experimental data for the binary acetic acid + water, methanol + water, and ethanol + water solvent systems are 4.22%, 2.36%, and 3.88% respectively.

bij

τij = aij +

(5)

T

where aij and bij are the binary interaction parameters of the NRTL equation. Equations 1 and 5 were used to correlate the experimental results on the solubility of FDCA in binary acetic acid + water, methanol + water, and ethanol + water solvent mixtures. Comparisons between the experimental data and the calculated values are shown in Tables 3 to 5. The NRTL binary parameters were regressed using the least-squares method, and the values are listed in Tables 6 to 8.

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i

j

aij

aji

bij/K

bji/K

HAc H2 O H2 O

1.088 −1.582 −30.55

4.892 5.638 −0.3682

−639.5 1020 12163

−1810 −2597 620.0

CONCLUSION

In this work, solubility data of FDCA in binary acetic acid + water, methanol + water, and ethanol + water solvent mixtures were determined by the static analytical method. Several conclusions are listed as follows: (a) the solubilities of FDCA in these solutions show a remarkably increasing trend with increasing temperature; (b) at a given temperature, the solubilities of FDCA in these solvents ranked as methanol > ethanol > acetic acid; (c) the solubilities of FDCA in aqueous methanol and aqueous ethanol solutions decreased with the increasing water content, which may be attributed to augmentation of the polarity of the solution and stronger hydrogen-bonding interactions between water and methanol or ethanol upon the addition of water; (d) within the measured temperature range, acetic acid with a mass fraction of 70% proved to be the best solvent for FDCA, which is called the “maximum-solubility effect” predicted by the Scatchard− Hildebrand theory and verified by Chen and Ma;26,35 (e) the experimental data show satisfactory agreement with calculated results derived from the NRTL model; (f) the experimental data and equilibrium equations determined in this work can be used to

Table 6. Binary Interaction Parameters of the NRTL Model for the Ternary FDCA (1) + Acetic Acid (3) + Water (2) Mixtures FDCA FDCA HAc

(7)

The relative deviation (RD) between the experimental value xexp and the calculated value xcal and the root-mean-square deviation (RMSD) are defined as follows: xexp, i − xcal, i δ RD, i = × 100% xexp, i (6) E



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Table 7. Binary Interaction Parameters of the NRTL Model for the Ternary FDCA (1) + Methanol (4) + Water (2) Mixtures i

j

aij

aji

bij/K

bji/K

FDCA FDCA CH3OH

CH3OH H2O H2O

3.054 × 101 −1.940 × 102 −2.652 × 102

2.976 × 108 −7.536 × 101 −1.553 × 101

−7.482 × 102 1.835 × 104 4.964 × 104

−1.638 × 108 2.819 × 104 5.000 × 103

Table 8. Binary Interaction Parameters of the NRTL Model for the Ternary FDCA (1) + Ethanol (5) + Water (2) Mixtures i

j

aij

aji

bij/K

bji/K

FDCA FDCA C2H5OH

C2H5OH H2O H2O

2.512 × 101 1.436 × 101 1.989 × 101

7.999 × 10° 2.528 × 101 −5.259 × 105

−4.562 × 103 −5.086 × 103 −7.400 × 103

−4.060 × 103 −8.423 × 103 1.822 × 103

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simulate and optimize crystallization and esterification processes of FDCA in industry.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Youwei Cheng: 0000-0001-7494-3974 Notes

The authors declare no competing financial interest.

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REFERENCES

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Solubilities of 2,5-Furandicarboxylic Acid in Binary Acetic Acid + Water

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