LiquidâLiquid Equilibrium for Ternary Systems ... - ACS Publications

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

Liquid−Liquid Equilibrium for Ternary Systems, Water + 5‑Hydroxymethylfurfural + (1-Butanol, Isobutanol, Methyl Isobutyl Ketone), at 313.15, 323.15, and 333.15 K Yongzhao Zhang,*,† Xia Guo,‡ Jian Xu,† Yuxiang Wu,† and Meizhen Lu§ †

Hangzhou Vocational and Technical College, Hangzhou 310018, People’s Republic of China Zhejiang Zanyu Technology Co., Ltd, Hangzhou 310009, People’s Republic of China § Zhejiang Province Key Lab of Biofuel, Hangzhou 310014, People’s Republic of China Downloaded via DURHAM UNIV on July 26, 2018 at 16:46:05 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

‡

ABSTRACT: Liquid−liquid equilibrium (LLE) data was very important for the process design and optimization of 5-hydroxymethylfurfural (5-HMF) production. To provide this fundamental data, experimental liquid−liquid equilibrium data for ternary systems, {water + 5-HMF + 1-butanol}, {water + 5-HMF + isobutanol}, and {water + 5-HMF + methyl isobutyl ketone}, were measured at 313.15, 323.15, and 333.15 K. Partition coefficients were used to assess the extraction capacity of organic solvents in the biphasic systems. 1-Butanol and isobutanol were desirable extractants with good extraction performance and environmental benign properties. The NRTL model was used to correlate the experimental data and the binary interaction parameters were obtained. The average relative deviation was lower than 10%.

1. INTRODUCTION Concerns about the global warming and energy security have led to the interest in the alternatives for the fossil resources to supply chemicals and energy. It was estimated that the global production of the biomass was about 1.0 × 1011 tons per year.1 The biomass is a promising alternative for fuels and chemicals. Carbohydrate makes up majority of the biomass, and it was predicted that about 30% of the chemicals would be produced from the carbohydrate feedstock in the future.2 To achieve this goal, more and more attention had been attached on the conversion of carbohydrate into useful chemicals. 5-Hydroxymethylfurfural (5-HMF) is an important biomassbased platform and has been listed as the top ten biobased chemicals.3 Oxidation of 5-HMF could generate several important furan chemicals such as 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-furancarboxylic (HMFCA), and 2,5-furandicarboxylic acid (FDCA).4,5 The structure of FDCA is similar to that of terephthalic acid and can be used as a potential monomer to replace terephthalic acid.6 5-HMF can also be converted into caprolactam, which is the monomer for nylon-6.7 5-HMF is also an important pharmaceutical intermediate.8 5-HMF is an important platform, and exploration of new method for the synthesis of 5-HMF is of great value. The development of efficient method for 5-HMF production from carbohydrates had been ongoing for almost a century. The method for 5-HMF production can be divided into three types of processes: single-phase systems, biphasic systems, and ionic liquid-based systems.9,10 In the single-phase systems, 5-HMF is synthesized in some high boiling-point solvents, such as DMSO, DMF, DMAC, and so forth. The drawback of this © XXXX American Chemical Society

method is that the separation of 5-HMF from these solvents was energy extensive. For the ionic liquid-based systems, the ionic liquid was expensive, and the ionic liquid is prone to be deactivated by water, formed in the production of 5-HMF.11 Because of the aforementioned disadvantages of the singlephase systems and ionic liquid-based systems, current research efforts had directed toward the utilization of biphasic systems in the production of 5-HMF.12 Aqueous or modified aqueous solution was used as the reactive phase for the starting substrates conversion into 5-HMF. The organic layer acted as an extracting phase for continuous accumulation of 5-HMF into organic phase immediately after its formation in the reactive phase. Thus, the side reactions were limited and the 5-HMF yield was improved. For the biphasic systems, some low boilingpoint organic solvents, such as 1-butanol, isobutanol, methyl isobutyl ketone (MIBK), 2-butanone, and so forth, were often used.13 Roman-Leshkov and Dumesic studied the impact of solvent choice on the dehydration of fructose into 5-HMF. The partition coefficient, equal to the concentration of 5-HMF in the organic phase normalized by the concentration in the aqueous phase, would influence the yield of 5-HMF significantly. The biphasic systems containing C4 solvents generated the highest 5-HMF yields.14 Ordomsky et al. used zeolites in a water−methyl isobutyl ketone (MIBK) system for fructose dehydration.15 The selectivity Received: February 6, 2018 Accepted: July 13, 2018

A

DOI: 10.1021/acs.jced.8b00120 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Properties of Chemicals at T = 298.15 K and P = 0.1 MPaa ρ (kg·m−3)b CAS number 5-HMF 1-butanol isobutanol MIBK acetonitrile isopropylbenzene methanol N,N-dimethylformamide water

67-47-0 71-36-3 78-83-1 108-10-1 75-05-8 98-82-8 67-56-1 68-12-2 7732-18-5

exp

nDb lit

exp

lit

805.877d 801.6e 800.6e 785.7e 864.0e 791.8e 944.5e 996.993d

1.3975 1.3940 1.3964 1.3452 1.4907 1.3279 1.4279 1.3324

1.3972d 1.3958e 1.3958e 1.3441e 1.4915e 1.3284e 1.4282e 1.3325d

c

1241 805.881 801.652 800.589 785.712 864.115 791.814 944.689 996.989

w 0.99 0.99 0.99 0.99 0.999 0.99 0.99 0.99

a Standard uncertainties, u, u(T) = 0.1 K, and u(P) = 0.005 MPa. bStandard uncertainties, u, u(ρ) = 5 kg·m−3, and u(nD) = 0.0005. cProvided by Aladdin. dReference 19. eReference 21.

important thermodynamic data. The LLE data reported in literature was measured at 298.15 K, and the influence of temperature on liquid−liquid equilibrium was not considered. It might be unwise to apply the LLE data at room temperature to the synthesis process of 5-HMF in the biphasic systems. In this paper, liquid−liquid equilibrium data for ternary systems, water + 5-HMF + 1-butanol, water + 5-HMF + isobutanol, water + 5-HMF + methyl isobutyl ketone (MIBK), was measured at 313.15, 323.15, and 333.15 K. The experimental LLE data was correlated with the NRTL model to determine the binary interaction parameters.

of 5-HMF formation during the addition of MIBK was significantly increased. An initial increase in the selectivity to 5-HMF over zeolites after addition of organic solvent is attributed to the suppression of humins formation due to filling of the pores of zeolite with MIBK. Fan et al. used a solid heteropolyacid salt Ag3PW12O40 catalyst for the production of 5-HMF from fructose and glucose in a water−MIBK biphasic system.16 At 120 °C, the fructose was selectively dehydrated into 5-HMF with the 5-HMF yield as high as 77.7% and selectivity of 93.8% within 60 min. Zhao et al. developed another heteropolyacid, Cs2.5H0.5 PW12O40, and obtained up to a 74% yield at 78% conversion.17 The reactions were conducted at 115 °C for 60 min in 1:3 water−MIBK with 30 wt % fructose initial loading. The effect of reaction time, ratio of aqueous and organic solvents, and catalyst loading were also studied in this literature. Generally, higher yields came at longer reaction times, greater amounts of MIBK, and higher catalyst loadings. From above illustrations, some important conclusions could be obtained. Synthesis of 5-HMF in biphasic systems was a promising technology. Organic solvents type, reaction temperature, reactant loading, and catalyst would influence the reaction process. In biphasic systems, mass transfer of 5-HMF from water to organic phase would influence the 5-HMF selectivity significantly. The partition coefficient of 5-HMF was a valuable parameter, and the liquid−liquid equilibrium data was of great importance for the reaction process design. In literature,18 Mohammad et al. studied liquid−liquid equilibrium of water + 5-HMF + 1-butanol at 298.15 K under atmospheric pressure. Based on the LLE data, the partition coefficient of 5-HMF was determined. 5-HMF preferably partitioned to the 1-butanol phase, and 1-butanol might be a suitable solvent for the extraction of 5-HMF from the aqueous phase. In literature,19 Irede Dalmolin et al. reported liquid−liquid equilibrium data for systems containing water + 5-HMF + {1-butanol, 2-butanol or 2-pentanol} at 298.2 K and atmospheric pressure. Experimental data were correlated with the NRTL model to calculate the activity coefficient, and the average root-mean-square deviation was equal to 0.65% for all systems. In literature,20 some LLE data for the water + 5-HMF + MIBK at 298.15 K under atmospheric pressure was also reported, and the LLE data was compared with that when the inorganic salt added. In biphasic systems, low boiling point solvents, such as C4 alcohols, MIBK, and so forth. were often used. The LLE data for systems containing water + 5-HMF + organic solvent was

2. EXPERIMENTAL SECTION 2.1. Materials. All chemicals which were used in this study were listed in Table 1. In Table 1, the mass fraction (w) of all chemicals was also given. 5-HMF and isobutanol were purchased from Aladdin (Shanghai, China). Concerning the low melting point of 5-HMF, 5-HMF was stored at about 277 K. 1-Butanol and methanol were obtained from Gaojing fine chemical Co, ltd (Shanghai, China). MIBK was purchased from MACKLIN (Shanghai, China). Acetonitrile was obtained from Spectrum (Shanghai China). N,N-dimethylformamide was purchased from Kermel Fine Chemical Co., ltd (Tianjin, China). For all experiments, water purchased from Wahaha Co., ltd (Hangzhou, China) was used, and the conductivity of water was less than 5 × 10−4 S·m−1. In this study, all chemicals were used without further purification. To characterize the chemicals used in this study, the density (ρ) and refractive index (nD) was measured, and the measured data was compared with that reported in literatures. Density was measured with MH300A densimeter (Jingcheng, China, accuracy is 0.001 kg·m−3). Refractive index was measured with abbe refractometer (Baihe, China, accuracy is 0.0005). 2.2. Apparatus and Procedure. A 20 mL thick-walled glass cell, a thermostatically controlled bath, a gas chromatograph, and a liquid chromatograph were used to measure the LLE data for the ternary systems. A mixture of 1-butanol (MIBK or isobutanol), 5-HMF, and water was loaded into the thick-walled glass cell. The cell was shaken vigorously for 3 h to mix thoroughly, then left to settle for at least 20 h to reach the phase equilibrium. The temperature was kept constant using a thermostatically controlled bath. The preliminary verification experiments showed that the extension of shaking and settling time almost had no effect on the experimental results. The method used in this paper could ensure the phase equilibrium. Because the equilibrium cell had a small volume, it was difficult to measure the equilibrium temperature directly. In preliminary B



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In some literatures,19,20 the mass fraction of water was determined by volumetric Karl Fischer titration. In this paper, the syringe was washed with methanol or N,N-dimethylformamide five times to transfer all the components from the syringe. The water in methanol or N,N-dimethylformamide would influence the analytical results significantly. According to this point, the mass fraction of water in two phases was obtained from the mass balance. The mass fraction of water could be determined by subtracting mass fraction of 5-HMF and1-butanol (isobutanol or MIBK) from 1.

experiments, we found that the difference between equilibrium temperature and the water bath temperature was less than 0.1 K. The mixture temperature in the equilibrium cell nearly equaled to the water bath temperature which was measured with a thermometer (accuracy was 0.1 K). After the ternary mixture formed two phases, samples were taken from two phases using a syringe, and the samples were weighed with an analytical balance (accuracy 0.1 mg). Each sample was about 0.5 g. The syringe was washed with methanol or N,N-dimethylformamide to transfer all the components to the volume flask. After dilution, the samples were analyzed with gas chromatograph(GC 2014, Shimadzu) and liquid chromatograph (LC 16, Shimadzu). 2.3. Analytical Method. 5-HMF was analyzed with liquid chromatograph. The liquid chromatograph was equipped with a UV detector (264 nm) and a C18 column (inertsustain, 4.6 × 250 μm). The volume fraction of acetonitrile in the mobile phase was held at 25%. The total flow was 1 mL/min, and the injection volume was 20 μL. Calibration was carried out with 5-HMF solutions (solvent was methanol) in a concentration range of 10 to 200 μg·mL−1. The calibration equation was y = 1.814 × 10−5x − 6.851 (R2 = 0.999). y was the concentration of 5-HMF, and x was the peak area obtained from the analytical results. R was the linear correlation coefficient. Samples with high 5-HMF mass fraction were diluted with methanol using dilution factors of up to 1:625. Each sample was analyzed at least 2 times with a deviation of less than 1%. From the HPLC analysis results, the mass fraction of 5-HMF (w2) could be calculated from eq 1. In eq 1, k and b are calibration equation coefficients of HPLC. V is dilution volume. ms is mass of sample, and A is the peak area of 5-HMF. w2 =

(kA + b)V ms

3. MASS BALANCE The quality and accuracy of result from the liquid−liquid equilibrium experiments were tested according to the method developed by Marcilla et al.22 It consisted of calculating the masses for both liquid phases and comparing their sum with the real value of total mass used in the experiments, thus a relative deviation for each point of the overall mixture was obtained. According to this method, there were i independent component balances with i being each component of the system, given by eq 3. In eq 3, m was the mass. Superscript oc referred to the overall composition of the system. Superscripts org and aq were organic phase and aqueous phase, respectively. mocwioc = maq wiaq + morg wiorg

kA AI + b

3

ms

aq

With these i equations, the values of m and m could be org calculated from the experimental values of waq i and wi using a org least-squares fitting. The calculated values of m and maq were compared with moc to obtain the relative deviation of overall mass balance (δ). δ=

(1)

|moc − maq − morg | moc

(4)

In eq 5, the mass balance relative deviation for each compound i (δi) was shown.

Organic solvent (1-butanol, isobutanol, or MIBK) was quantified with gas chromatograph. The gas chromatograph was equipped with a FID detector and a capillary column (Rtx1701, 30 m × 0.32 mm × 0.25 μm). The oven temperature was held at 413.15 K for 6 min. The detector and injector temperature were 473.15 and 543.15 K, respectively. The nitrogen was used as the carrier gas. The injection volume was about 0.5 μL. The aqueous and organic phase samples were diluted with N,N-dimethylformamide to about 5 and 10 mL, respectively. For quantitative analysis, isopropylbenzene (about 0.17 g) were added into the dilutions as internal standard. Calibration was performed by measuring the mixture of 1-butanol (MIBK or isobutanol) standard and isopropylbenzene. Calibration equation was y = 1.5392x + 0.00520 (R2 = 0.999), y = 1.425x + 0.0181 (R2 = 0.999), y = 1.1.436x + 0.0189 (R2 = 0.999) for 1-butanol, isobutanol, and MIBK, respectively. y was equal to the mass of organic solvent normalized by the mass of isopropylbenzene, and x was the peak area ratio of organic solvent to isopropylbenzene. Each sample was analyzed at least 2 times with a deviation of less than 1%. From the GC analysis results, the mass fraction of 1-butannol (isobutanol or MIBK), w3, could be calculated from eq 2. In eq 2, k and b are calibration equation coefficients of GC. A and AI are peak area of 1-butanol and isopropylbenzene, respectively. mI is the mass of isopropylbenzene, and ms is mass of sample.

( )m w =

(3) org

δi =

|mocwioc − maq wiaq − morg wiorg| mocwioc

(5)

4. THERMODYNAMIC MODELING NRTL model was applied to correlate the LLE data for the systems. In NRTL model, the activity coefficient was calculated with eq 6.23

I

Figure 1. Experimental and literature LLE data for water + 5-HMF + 1-butanol system. ■, reference (19); ●, measured in this paper.

(2) C



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Table 2. LLE Data (Mass Fraction) for the System {Water (1) + 5-HMF (2) + 1-Butanol (3)} at Temperature T and Pressure P ≈ 0.1 MPaa organic phase

aqueous phase

temperature T

w3

w2

w1

w3

w2

w1

D

313.15 K

0.758 0.719 0.677 0.614 0.571 0.520 0.748 0.671 0.602 0.547 0.493 0.740 0.664 0.542 0.477

0.019 0.041 0.078 0.122 0.154 0.183 0.021 0.080 0.116 0.150 0.179 0.014 0.047 0.147 0.177

0.223 0.239 0.245 0.264 0.276 0.296 0.231 0.249 0.282 0.303 0.328 0.246 0.289 0.311 0.346

0.069 0.068 0.081 0.080 0.088 0.103 0.066 0.083 0.089 0.096 0.115 0.069 0.090 0.098 0.117

0.007 0.016 0.039 0.059 0.081 0.109 0.007 0.035 0.058 0.083 0.108 0.005 0.020 0.082 0.104

0.924 0.915 0.880 0.861 0.830 0.788 0.927 0.881 0.853 0.821 0.777 0.925 0.890 0.820 0.779

2.876 2.563 1.990 2.054 1.885 1.677 3.044 2.269 2.003 1.863 1.645 2.619 2.329 1.786 1.704

323.15 K

333.15

a

Standard uncertainties u are u(T) = 0.1 K, u(P) = 0.01 MPa, u(w1) = u(w2) = u(w3) = 0.01.

Table 3. LLE Data (Mass Fraction) for the System {Water (1) + 5-HMF (2) + Isobutanol (4)} at Temperature T and Pressure P ≈ 0.1 MPaa organic phase

aqueous phase

temperature T

w4

w2

w1

w4

w2

w1

D

313.15 K

0.562 0.615 0.696 0.746 0.801 0.559 0.623 0.677 0.725 0.782 0.538 0.603 0.631 0.683 0.733

0.180 0.154 0.114 0.081 0.038 0.172 0.146 0.113 0.074 0.038 0.181 0.149 0.129 0.083 0.037

0.258 0.231 0.190 0.173 0.161 0.269 0.230 0.210 0.201 0.180 0.281 0.248 0.241 0.233 0.230

0.129 0.101 0.087 0.083 0.083 0.121 0.107 0.096 0.087 0.080 0.113 0.099 0.088 0.083 0.068

0.103 0.086 0.060 0.039 0.015 0.106 0.082 0.058 0.035 0.013 0.107 0.084 0.062 0.036 0.014

0.768 0.813 0.854 0.879 0.902 0.773 0.811 0.846 0.878 0.907 0.780 0.818 0.850 0.881 0.918

1.742 1.797 1.914 2.093 2.547 1.619 1.787 1.959 2.100 2.933 1.690 1.781 2.087 2.298 2.568

323.15 K

333.15 K

a

ÄÅ ÉÑ ∑l xlτljGli ÑÑÑ xjGij ÅÅÅ ÅÅτ − ÑÑ Å ij Ñ ∑l Gljxl ÑÑÑ ∑l Gljxl ÅÅÅ Ç Ö


inγi =

∑j τijGjixj ∑l Glixl

+

∑ j

components in aqueous phase and organic phase, γiaq and γiorg. Knowing γiaq and γiorg, the mass fraction of components in two phases could be calculated from eq 8. The calculation data and the experimental data were compared. A nonlinear optimization method implemented in MATLAB toolbox was used to update the value of model parameters, minimizing the objective composition function (eq 9).

(6)

In eq 6, Gij = exp(−αijlij), lij = aij + bij/T. According to phase rule, the freedom, f, for the three ternary systems was calculated with eq 7. In eq 7, the influence of pressure on LLE was neglected. f=C−P+1

xiaqγiaq = xiorgγiorg

(7)

∑ xiaq = ∑ xiorg = 1

In eq 7, C was the number of components in the system and P was the number of phases. For the three systems in this study, C was equal to 3 and P was equal to 2. The number of free variables was 2. The temperature and mass fraction of 5-HMF in organic phase were chosen as the free variables. The determination of model parameters was as following. At the specified temperature and 5-HMF mass fraction in organic phase, the given initial value of model parameters to be determined allowed the calculation of activity coefficient of

D

OF =

K

∑n = 1 ∑i = 1 N

(8)

cal wiexp , n − wi , n

wiexp ,n

(9)

In eq 9, OF was the objective composition function. w was mass fraction. N was the number of experimental data. Subscripts i and n were component and temperature, respectively. D



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Table 4. LLE Data (Mass Fraction) for the System {Water (1) + 5-HMF (2) + MIBK (5)} at Temperature T and Pressure P ≈ 0.1 MPaa organic phase

aqueous phase

temperature T

w5

w2

w1

w5

w2

w1

D

313.15 K

0.839 0.862 0.887 0.913 0.935 0.830 0.856 0.873 0.903 0.925 0.829 0.845 0.871 0.898 0.910

0.149 0.116 0.090 0.059 0.036 0.149 0.116 0.095 0.060 0.037 0.145 0.124 0.092 0.060 0.034

0.012 0.022 0.023 0.028 0.029 0.021 0.028 0.033 0.037 0.038 0.027 0.031 0.038 0.042 0.056

0.032 0.020 0.019 0.018 0.016 0.026 0.020 0.016 0.017 0.016 0.022 0.019 0.018 0.017 0.015

0.131 0.100 0.073 0.049 0.027 0.129 0.092 0.076 0.051 0.029 0.131 0.103 0.074 0.051 0.028

0.837 0.880 0.907 0.933 0.957 0.845 0.888 0.908 0.932 0.955 0.847 0.878 0.907 0.932 0.957

1.139 1.151 1.222 1.199 1.330 1.155 1.261 1.237 1.178 1.269 1.110 1.199 1.235 1.182 1.202

323.15 K

333.15 K

a


Superscripts exp and cal were experimental data and calculated data, respectively. K was the total number of components and D was the total number of temperature. Average relative deviations (ARD) between the experimental and calculated compositions in both phases were calculated with eq 10. In eq 10, w was mass fraction of components. Subscripts exp and cal were experimental data and calculated data, respectively. N was the number of LLE data. ∑i ARD =

(wexp − wcal) wexp

N

(10)

5. RESULTS AND DISCUSSION The components studied in this work had the following notation: water (1), 5-HMF (2), 1-butanol (3), isobutanol (4), and MIBK (5). To confirm the reliability of the experiment technique in this study, the LLE data for the water + 5-HMF + 1-butanol system at 298.15 K was measured. The experimental LLE data was compared with that reported in literature.19 The deviation was shown in Figure 1. The measured data in this paper agreed well with that reported in literature, and this result validated the experiment technique used in this study. Experimental liquid−liquid equilibrium data were shown in Tables 2 to 4. The extraction efficiency of the organic solvent (1-butanol, isobutanol, or MIBK) for 5-HMF was assessed by partition coefficient (D), defined in eq 11. D=

w2org w2aq

Figure 2. The value of D for the systems water + 5-HMF + {1-butanol, isobutanol, and MIBK} at 313.15 K for different 5-HMF mass fraction. ■, 1-butanol; ●, isobutanol; ▲, MIBK.

hydrophobic group (furan ring) and hydrophilic group (hydroxymethyl group). There are also hydrophobic groups (alkyl group) and hydrophilic group (hydroxyl group) in 1-butanol and isobutanol molecule. There are no hydrophilic groups in MIBK molecule. The polarity of 1-butanol and isobutanol was close to that of 5-HMF and 5-HMF in the two alcohols had a higher partition coefficient. The value of D highly depended on the mass fraction of 5-HMF. A rough trend could be concluded from Figure 2 that value of D decreased with increasing of 5-HMF mass fraction in organic phase. With the increasing of 5-HMF mass fraction, the polarity difference between aqueous phase and organic phase became small, and the value of D decreased. In the industrial production of 5-HMF, a high concentration of 5-HMF was usually preferred for the reactor efficiency and production efficiency. The high 5-HMF concentration would decrease the partition coefficient and this led to the accumulation of 5-HMF in the aqueous phase. To overcome this disadvantage, some inorganic salts, such as KCl, NaCl, and so forth, were added into the aqueous phase to enhance the partition coefficient. The dependency of D on temperature for the three systems was shown in Figures 3 to 5. In the figures, worg 2 was the mass

(11)

5-HMF partition coefficient values indicated 5-HMF solubilized preferably in the organic phase (the partition coefficient was larger than 1), and this was a valuable information to claim the solvents used was suitable for 5-HMF transfer from water to organic solvent. The properties of organic solvents would influence D significantly. The partition coefficients of 5-HMF in the three ternary systems at 313.15 K were shown in Figure 2. The value of D for MIBK system was much smaller than that for 1-butanol and isobutanol system. 5-HMF molecule is constituted with E



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Table 5. Overall and Compound Mass Balances Relative Deviation Given for Water (1) + 5-HMF (2) +{1-Butanol (3), Isobutanol (4), and MIBK (5)} Ternary Systems at Temperature T and Pressure P ≈ 0.1 MPa T/K

organic solvent (y)

100δ1

100δ2

100δy

100δ

313.15

3 4 5 3 4 5 3 4 5

0.121 0.879 0.912 1.435 2.810 0.611 0.0893 5.918 0.727

14.403 11.876 5.817 16.367 10.893 4.888 9.162 12.989 7.805

0.725 1.209 1.148 2.296 5.598 0.702 1.107 2.586 1.557

0.707 0.650 0.400 1.085 0.867 0.347 0.593 0.561 0.552

323.15

333.15

Table 6. Binary Interaction Parameters of NRTL Model for Water (1) + 5-HMF (2) + {1-Butanol (3), Isobutanol (4), and MIBK (5)} Ternary Systems

Figure 3. The value of D for water + 5-HMF + 1-butanol system at 298.15, 313.15, 323.15, and 333.15 K for different 5-HMF mass fraction. ■, 298.15 K, ref 19; ●, 333.15 K; ▲, 313.15 K; ★, 323.15 K.

pair ij

aij

bij/K

aji

bji/K

αij

12 13 23 14 24 15 25

−13.448 7.209a −0.0780 4.213b −1.887 10.713c 12.375

2475.367 −925.660a −505.833 −88.984b 48.121 −1670.042c −4337.270

3.307 −2.054a 27.825 −0.394b −0.685 −3.305c −30.974

−1123.648 561.985a −10000.000 123.965b −1277.722 1215.373c 7915.764

0.3 0.3 0.3 0.3 0.3 0.2 0.3

a

Obtained from literature refs 24 and 25. bObtained from literature ref 26. cObtained from literature ref 27.

value of D. It was necessary to measure the LLE data at different temperature to study the influence of temperature. On the other hand, the influence of temperature was insignificant compared with influence of 5-HMF mass fraction. The reason might be that the dissolution heat of 5-HMF in water and organic solvent had a relatively small difference. Overall mass balance and mass balance for each compound average relative deviation, given by eq 4 and eq 5, were shown in Table 5. The maximum of overall mass balance deviation was about 1.3%, and the average relative deviation for water and organic solvents were lower than 1.7%. High deviations were observed for 5-HMF. These results were considered acceptable for its low mass fraction of 5-HMF in the two phases, and the small fluctuation of mass fraction of 5-HMF might cause high relative deviation. Phase equilibrium data were correlated with NRTL model. Binary interaction NRTL parameters determined from the experimental data were presented in Table 6. It was of great value to predict the LLE of ternary systems with the binary interaction parameters obtained from the correlation of LLE data of binary systems. In Table 6, the binary interaction parameters of 1-butanol (isobutanol or MIBK)-water was obtained from literatures.24−27 To make the figures clear, only experimental and calculated LLE data for the three ternary systems studied at 313.15 K were compared in Figures 6 to 8, and the average relative deviation (ARD) was shown in Table 7. As could be seen, the average relative deviation for water + 5-HMF + MIBK system was the highest, and the value of ARD was about 10%. The mass fraction of water in organic phase and the mass fraction of MIBK in aqueous phase were very low for water + 5-HMF + MIBK system. The small fluctuation would lead to a large value of ARD. According to this point, this correlation result for water + 5-HMF

Figure 4. The value of D for water + 5-HMF-1 + isobutanol system at 313.15, 323.15, and 333.15 K for different 5-HMF mass fraction. ■, 313.15 K; ●, 323.15 K; ▲, 333.15 K.

Figure 5. The value of D for water + 5-HMF + MIBK system at 298.15, 313.15, 323.15, and 333.15 K for different 5-HMF mass fraction. ■, 313.15 K; ●, 323.15 K; ▲, 333.15 K; ★, 298.15 K, ref 20.

fraction of 5-HMF in organic phase. From these figures, it could be concluded that temperature would also influence the F



Article

Figure 6. Liquid−liquid equilibrium experimental data for water (1) + 5-HMF (2) + 1-butanol (3) system at T = 333.15 K, and atmospheric pressure (0.1 MPa). ■, LLE data measured in this study; ●, overall phase compositions; −, calculated with NRTL model.

Figure 8. Liquid−liquid equilibrium experimental data for water (1) + 5-HMF (2) + MIBK (5) system at T = 333.15 K and atmospheric pressure (0.1 MPa). ■, LLE data measured in this study; ●, overall phase compositions; −, calculated with NRTL model.

Table 7. ARD between Experimental and NRTL Calculated Phase Composition system

ARD

water-5-HMF-1-butanol water-5-HMF-isobutanol water-5-HMF-MIBK

0.0454 0.0418 0.108

Figure 7. Liquid−liquid equilibrium experimental data for water (1)+5-HMF (2)+isobutanol (4) system at T = 333.15 K and atmospheric pressure (0.1 MPa). ■, LLE data measured in this study; ●, overall phase compositions; -, calculated with NRTL model.

+ MIBK system was acceptable. NRTL model could be used to predict the phase behavior of the three ternary systems. An important goal of this study was to investigate the influence of temperature on liquid−liquid equilibrium. Whether or not the NRTL parameters obtained in this study could be used to predict the liquid−liquid equilibrium at the temperature out of the range in this paper would influence the value of this study. In Figures 9 and 10, the LLE data calculated from the NRTL parameters obtained in this study was compared with that reported in literature refs 19 and 20. The consistent LLE data for water + 5-HMF + isobutanol system was not found, and only the water + 5-HMF + 1-butanol and water + 5-HMF + MIBK ternary systems were presented in Figures 9 and 10. The influence of temperature on LLE could be predicted with the NRTL parameters obtained in this paper.

Figure 9. Liquid−liquid equilibrium experimental data for the system water + 5-HMF + 1-butanol at T = 298.15 K and atmospheric pressure (0.1 MPa). ■, LLE data measured in literature ref 19; −, calculated with NRTL model parameters in Table 6.

determined at 313.15, 323.15, and 333.15 K. Partition coefficients related to extraction of 5-HMF were also experimentally determined. Low deviations were obtained for the overall mass balance. When the three organic solvents were used, 5-HMF showed similar preference for the organic phase. Higher partition coefficient values for 1-butanol and isobutanol were found in comparison with MIBK, indicating these two solvents were the suitable solvents for 5-HMF removal from water. NRTL model parameters were determined from the correlation of experimental data, and the average relative deviation was lower than 10%. The NRTL binary parameters could also be used to predict the

6. CONCLUSIONS New experimental liquid−liquid equilibrium data for water + 5-HMF + {1-butanol, isobutanol or MIBK} ternary systems were G



Article

2-furfural modifies intracellular sickle haemoglobin and inhibits sickling of red blood cells. Br. J. Haematol. 2005, 128, 552−561. (9) Tian, G.; Tong, X. L.; Cheng, Y.; Xue, S. Tin-catalyzed efficient conversion of carbohydrates for the production of 5-hydroxymethylfurfural in the presence of quaternary ammonium salts. Carbohydr. Res. 2013, 370, 33−37. (10) Bao, Q. X.; Qiao, K.; Tomida, D.; Yokoyama, C. Preparation of 5-hydroymethylfurfural by dehydration of fructose in the presence of acidic ionic liquid. Catal. Commun. 2008, 9, 1383−1388. (11) Saha, B.; Gupta, D.; Abu-Omar, M. M.; Modak, A.; Bhaumik, A. Porphyrin-based porous organic polymer-supported iron(III) catalyst for efficient aerobic oxidation of 5-hydroxymethyl-furfural into 2,5-furandicarboxylic acid. J. Catal. 2013, 299, 316−320. (12) Roman-Leshkov, Y.; Chheda, J. N.; Dumesic, J. A. Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose. Science 2006, 312, 1933−1937. (13) Saha, B.; Abu-Omar, M. M. Advances in 5-hydroxymethylfurfural production from biomass in biphasic solvents. Green Chem. 2014, 16, 24−38. (14) Roman-Leshkov, Y.; Dumesic, J. A. Solvent Effects on Fructose Dehydration to 5-Hydroxymethylfurfural in Biphasic Systems Saturated with Inorganic Salts. Top. Catal. 2009, 52, 297−303. (15) Ordomsky, V. V.; van der Schaaf, J.; Schouten, J. C.; Nijhuis, T. A. The effect of solvent addition on fructose dehydration to 5hydroxymethylfurfural in biphasic system over zeolites. J. Catal. 2012, 287, 68−75. (16) Fan, C. Y.; Guan, H. Y.; Zhang, H.; Wang, J. H.; Wang, S. T.; Wang, X. H. Conversion of fructose and glucose into 5hydroxymethylfurfural catalyzed by a solid heteropolyacid salt. Biomass Bioenergy 2011, 35, 2659−2665. (17) Zhao, Q.; Wang, L.; Zhao, S.; Wang, X. H.; Wang, S. T. High selective production of 5-hydroymethylfurfural from fructose by a solid heteropolyacid catalyst. Fuel 2011, 90, 2289−2293. (18) Mohammad, S.; Grundl, G.; Muller, R.; Kunz, W.; Sadowski, G.; Held, C. Influence of electrolytes on liquid-liquid equilibria of water/1-butanol and on the partitioning of 5-hydroxymethylfurfural in water/1-butanol. Fluid Phase Equilib. 2016, 428, 102−111. (19) Dalmolin, I.; Pinto, R. R.; de Oliveira, L. H.; Follegatti-Romero, L. A.; Costa, A. C.; Aznar, M. Liquid-liquid Equilibrium in Systems Used for the Production of 5-Hydroxymethylfurfural from Biomass Using Alcohols as Solvents. J. Chem. Thermodyn. 2017, 111, 80−87. (20) Mohammad, S.; Held, C.; Altuntepe, E.; Kose, T.; Sadowski, G. Influence of Salts on the Partitioning of 5-Hydroxymethylfurfural in Water/MIBK. J. Phys. Chem. B 2016, 120, 3797−3808. (21) Speight, J. G. Lange’s handbook of chemistry, 16th ed.; McgrawHill: New York, 2005. (22) Marcilla, A.; Ruiz, F.; Garcia, A. N. Liquid-liquid-solid equilibria of the quaternary system water-ethanol-acetone-sodium chloride at 25 °C. Fluid Phase Equilib. 1995, 112, 273−289. (23) 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. (24) Liu, J. Q.; Zhang, J. H. Determination, correlation and prediction of liquid-liquid equilibrium data of n-butyl alcohol-waterbutyl acetate ternary system. Chin. J. Chem. Eng. 1988, 39, 266−275. (25) Marongiu, B.; Ferino, I.; Monaci, R.; Solinas, V.; Torrazza, S. Thermodynamics properties of aqueous non-electrolyte mixtures alkanols+water systems. J. Mol. Liq. 1984, 28, 229−247. (26) Yang, C. F.; Qian, Y.; Zhang, L. J.; Jiang, Y. B. Measurement and correlation of liquid-liquid equilibrium data for methyl isobutyl ketonewater-phenol ternary systems. Chin. J. Chem. Eng. 2007, 58, 805−809. (27) Jin, C. Y.; Lin, J. Q. Solubility and liquid-liquid equilibrium on the binary system of water-isobutanol. J. Huaqiao. Univ 2014, 35, 58−60.

Figure 10. Liquid−liquid equilibrium experimental data for the system water + 5-HMF + MIBK at T = 298.15 K, and atmospheric pressure (0.1 MPa). ■, LLE data measured in literature (20); −, calculated with NRTL model parameters in Table 6.

phase behavior at the temperature out of the temperature range in this study.

■

AUTHOR INFORMATION

Corresponding Author

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

Yongzhao Zhang: 0000-0003-3063-3944 Notes

The authors declare no competing financial interest.

■ ■

ACKNOWLEDGMENTS Acknowledgement was expressed for the financial support from Zhejiang Provincial department of education (No. FX2017152). REFERENCES

(1) Zhang, Z. H.; Wang, Q.; Xie, H. B.; Liu, W. J.; Zhao, Z. B. Catalytic Conversion of Carbohydrates into 5-Hydroxymethylfurfural by Germanium(IV) Chloride in Ionic Liquids. ChemSusChem 2011, 4, 131−138. (2) Wang, T. F.; Nolte, M. W.; Shanks, B. H. Catalytic dehydration of C6 carbohydrates for the production of hydroxymethylfurfural (HMF) as a versatile platform chemical. Green Chem. 2014, 16, 548−572. (3) van Putten, R. J.; van der Waal, J. C.; de Jong, E.; Rasrendra, C. B.; Heeres, H. J.; de Vries, J. G. Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources. Chem. Rev. 2013, 113, 1499−1597. (4) van Dam, H. E.; Kieboom, A. P. G.; van Bekkum, H. The Conversion of Fructose and Glucose in Acidic Media: Formation of Hydroxymethylfurfural. Starch 1986, 38, 95−101. (5) Roman-Leshkov, Y.; Barrett, C. J.; Liu, Z. Y.; Dumesic, J. A. Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature 2007, 447, 982−985. (6) 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: oly(ethylene 2,5-furandicarboxylate)co-poly(lactic acid) Copolyesters. Macromol. Chem. Phys. 2014, 215, 2175−2184. (7) De, S.; Dutta, S.; Saha, B. One-Pot Conversions of Lignocellulosic and Algal Biomass into Liquid Fuels. ChemSusChem 2012, 5, 1826−1833. (8) Abdulmalik, O.; Safo, M. K.; Chen, Q.; Yang, J. S.; Brugnara, C.; Ohene-Frempong, K.; Abraham, D. J.; Asakura, T. 5-hydroxymethylH


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