Vapor Pressure and Isobaric VaporâLiquid Equilibrium for Binary

Article pubs.acs.org/jced

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

Vapor Pressure and Isobaric Vapor−Liquid Equilibrium for Binary Systems of Furfural, 2‑Acetylfuran, and 5‑Methylfurfural at 3.60 and 5.18 kPa Huidong Zheng,* Xiheng Luo, Guanghua Yin, Jingjing Chen, and Suying Zhao College of Chemistry and Chemical Engineering, Fuzhou University, Xueyuan Road No. 2, Minhou, Fuzhou, Fujian 350108, China ABSTRACT: The saturated vapor pressures of furfural (FUR), 2-acetylfuran (2AF), and 5-methylfurfural (5MF) and the isobaric vapor−liquid equilibrium (VLE) data for three binary systems (FUR + 2AF, FUR + 5MF, and 2AF + 5MF) at 3.60 and 5.18 kPa were experimentally measured in a Rose−Williams still. The saturated vapor pressures were correlated by the Antoine equation; the binary VLE data were correlated by the nonrandom two-liquid, Wilson, and universal quasichemical models. The VLE of the ternary system of FUR + 2AF + 5MF was predicted by the obtained binary interaction parameters for each model, and the predictions fit well with the experimental data.

1. INTRODUCTION The high dependence of the petrochemical products derived from fossil resources has led to concern about climatic changes, and the search of an alternative and eco-friendly substitute source has been urgent for sustainable development.1 Biochemicals derived from biomass can provide promising alternatives for the replacement of the fuels and chemicals produced from the nonrenewable crude oil and coal.2 Furfural (FUR, CASRN 98-01-1) and its derivatives, 2-acetylfuran (2AF, CASRN 1192-62-7) and 5-methyl furfural (5MF, CASRN 620-02-0), are three representative biochemicals produced from the hydrolysis of biomass and have been extensively applied as materials or intermediates in petroleum, pharmacy, flavorant, and agroindustry.3−5 These furanic compounds are the main components in the fermentation liquor of corncob, and vacuum distillation is the most important process in the industrial purification of these furans. Thus, the vapor−liquid equilibrium (VLE) data of FUR, 2AF, and 5MF are essential for the design and simulation of the separation process. There have been several reports about the saturated vapor pressures of FUR (from 278.14 to 362.87 K)6,7 and 5MF (from 303.15 to 453.15 K),8 and VLE data for the binary system of FUR + 5MF.9,10 However, these reports are not enough for the accurate prediction of ternary VLE in the actual vacuum distillation. In this paper, the saturated vapor pressures of FUR, 2AF, and 5MF at low pressures were measured, respectively, and the vapor pressure data were fitted by an Antoine equation. The isobaric VLE data for FUR + 2AF, FUR + 5MF, and 2AF + 5MF at 3.60 and 5.18 kPa were measured, and the binary VLE data were regressed by nonrandom two-liquid (NRTL), Wilson, and universal quasichemical (UNIQUAC) models. With the obtained binary interaction parameters of each model, prediction of the ternary VLE for FUR + 2AF + 5MF was © XXXX American Chemical Society

made and was compared with the experimental data measured at 3.60 kPa.

2. EXPERIMENTAL SECTION 2.1. Chemicals. FUR, 2AF, and 5MF were provided by Aladdin Reagents (Shanghai) Co., Ltd. The materials were used without further purification and their purities were determined by a gas chromatograph. The description of the materials are presented in Table 1. Table 1. Details of the Materials material furfural 2-acetylfuran 5-methylfurfural 1-octanol

purity/ wt % purification

source Aladdin Reagents (Shanghai) Co., Aladdin Reagents (Shanghai) Co., Aladdin Reagents (Shanghai) Co., Aladdin Reagents (Shanghai) Co.,

analysis method

99.5

none

GC

99.0

none

GC

98.0

none

GC

99.5

none

GC

LTD LTD LTD LTD

2.2. Apparatus and Procedures. The apparatus for the VLE measurement is a Rose−Williams still (Beiyang Analytical Instrument Co., LTD) equipped with a vacuum control system (Figure 1). The vacuum control system consists of an electromagnetic valve, an intelligent controller (HP604 model, Zhejiang Chint Electric Co., LTD), a vacuum pump, and an absolute pressure transmitter (Shanghai Welltech Automation Co., LTD) with Received: June 22, 2017 Accepted: December 4, 2017

A

DOI: 10.1021/acs.jced.7b00574 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Shimadzu Corporation) equipped with a flame ionization detector (FID) and a capillary column (RTX-5, 30 m × 0.25 mm × 0.25 μm). The temperatures of the column, injection, and detector were set to 373.15, 523.15, and 533.15 K, respectively. The injection volume is 0.2 μL. The split ratio was 30/1. Nitrogen was used as carrier gas. The pressures of nitrogen, hydrogen and air were 20.0, 50.0, and 35.0 kPa, respectively. The quantitative analysis of the samples was based on the calibration curves, which were obtained by a series of prepared standard solutions using an electronic balance (BSA224S, standard uncertainty of 0.0001 g). The real concentration was calibrated, and the linear correlation coefficients were more than 0.999. The absolute deviations of the compositions were less than 0.005.

3. RESULTS AND DISCUSSION 3.1. Validation Experiment. The vapor pressure of 1-octanol was measured and compared with the reported data13 to validate the reliability and accuracy of the apparatus. The results are presented in Table 2 and Figure 2, where

Figure 1. Schematic diagram of the apparatus: (1) heating rod; (2) liquid-phase sampling port; (3) precision mercury thermometer; (4) vapor-phase sampling port; (5) coolant inlet; (6) coolant outlet; (7) condenser; (8) absolute pressure transmitter; (9) intelligent controller; (10) pressure buffer tank; (11) vacuum pump.

a measurement accuracy of 1 Pa. The details of the apparatus and experimental procedure have been provided in the previous work.11,12 The VLE system was heated by a heating rod under the set pressure and the temperature of the VLE system was determined by a precision mercury thermometer with an uncertainty of 0.1 K. In the measurements of vapor pressures of pure components, about 45 mL of pure component was introduced into the equilibrium vessel. The vacuum pump was started and the valve “b” was closed. The valve “a” was turned off when the system reached an appropriate pressure and the pressure was automatically controlled at the desired pressure by the intelligent controller. Both the vapor and liquid phases were continuously circulating in the still to provide intimate contact of the phases. When a constant boiling temperature was achieved in the system and was kept for at least 0.5 h, the boiling temperature and the pressure were recorded. In the measurements of VLE data of the binary or ternary systems, the multicomponent mixture was introduced into the vessel, and the samples of both the vapor and the liquid phases were taken with a syringe for analysis when the system was equilibrated for at least 1 h. 2.3. Analysis. The compositions of the vapor and liquid phases were analyzed by a gas chromatograph (GC-2014,

Figure 2. Vapor pressure of 1-octanol compared with the reported data.

superscripts exp and lit represent the experimental data and reported values, respectively; n is the number of data points. The measured data coincide with the literature data very well. The maximum absolute deviation of 1-octanol is 0.612 kPa, and the root-mean square deviation (rmsd) is 0.208 kPa. These values indicate that the measurements applied in this apparatus are reliable.

Table 2. Vapor Pressure Data for 1-Octanola no.

Texp

ps, exp

ps,lit

ADb

K

kPa

kPa

kPa

0.854 1.067 1.511 2.008 2.994 4.012 5.006

0.878 1.079 1.494 1.960 3.001 4.027 4.983

0.024 0.012 0.017 0.048 0.006 0.015 0.023 0.612

1 354.85 2 358.15 3 363.55 4 368.25 5 376.05 6 381.75 7 386.05 max absolute deviation

no. 8 9 10 11 12 13 14 rmsdc

Texp

ps, exp

ps,lit

ADb

K

kPa

kPa

kPa

389.95 393.15 396.05 398.55 400.95 410.15 417.35

6.014 7.011 8.024 9.019 9.986 14.969 19.908

6.008 6.974 7.958 8.896 9.881 14.526 19.296

0.007 0.036 0.066 0.122 0.105 0.443 0.612 0.208

Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.075 kPa. Literature data ps, lit are from ref 13. bAbsolute deviation (AD) = |ps, exp − ps, lit|. rmsd = (∑i n= 1 (ps,exp − ps,lit)2/n)1/2.

a c

B



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Table 3. Saturated Vapor Pressure Data of FUR, 2AF, and 5MFa T/K exp

p/kPa cal

b

exp

cal

b

AE(T)c

AE(p)d

K

kPa

FUR 326.05 331.85 335.35 338.85 342.35 344.55 346.85 349.75 353.05 356.45 364.35 375.75 383.35 394.25 402.55 409.55 415.15

326.03 331.83 335.33 338.83 342.34 344.54 346.86 349.77 353.08 356.51 364.56 375.62 383.17 394.29 402.59 409.47 415.24

1.455 2.031 2.506 3.014 3.623 4.021 4.524 5.190 6.022 7.039 10.042 15.063 20.068 30.102 39.870 49.805 59.743

337.95 342.65 349.75 353.35 355.05 360.65 363.95 367.65 370.55 373.55 376.35 386.55 394.15 405.55 414.25

337.93 342.63 349.75 353.34 355.07 360.67 363.98 367.66 370.60 373.56 376.31 386.49 394.14 405.52 414.29

1.545 2.013 3.061 3.624 4.017 5.181 6.020 7.028 8.031 9.034 10.041 15.044 20.067 29.891 39.934

339.05 343.25 347.05 353.15 357.45 360.95 366.75 369.25 376.65 380.15 383.25 385.95 388.45 398.25 405.85 417.55

339.04 343.25 347.05 353.15 357.46 360.96 366.79 369.30 376.61 380.10 383.20 385.91 388.41 398.33 405.95 417.48

0.858 1.127 1.405 2.002 2.501 3.004 4.020 4.523 6.017 7.024 8.030 9.043 10.037 15.024 19.962 29.890

1.600 2.165 2.586 3.074 3.641 4.040 4.501 5.143 5.967 6.938 9.762 15.190 20.206 30.083 39.853 49.833 59.717

0.02 0.02 0.02 0.02 0.01 0.01 0.01 0.02 0.03 0.06 0.21 0.13 0.18 0.04 0.04 0.08 0.09

0.145 0.134 0.080 0.060 0.018 0.019 0.023 0.047 0.055 0.101 0.280 0.127 0.138 0.019 0.017 0.028 0.026

1.657 2.127 3.056 3.642 3.956 5.136 5.963 7.012 7.956 9.014 10.097 15.100 20.075 29.908 39.914

0.0161 0.0208 0.0013 0.0057 0.0207 0.0190 0.0273 0.0088 0.0460 0.0131 0.0406 0.0569 0.0100 0.0305 0.0444

0.112 0.114 0.005 0.018 0.061 0.045 0.057 0.016 0.075 0.020 0.056 0.056 0.008 0.017 0.020

0.919 1.166 1.437 1.987 2.476 2.948 3.902 4.388 6.108 7.114 8.119 9.098 10.086 14.943 19.886 29.927

0.01 0.00 0.00 0.00 0.01 0.01 0.04 0.05 0.04 0.05 0.05 0.04 0.04 0.08 0.10 0.07

0.061 0.039 0.032 0.015 0.025 0.056 0.118 0.135 0.091 0.090 0.089 0.055 0.049 0.081 0.076 0.037

Figure 3. Saturated vapor pressure data for FUR, 2AF, and 5MF.

the pressure of the three components. The literature data of FUR and 5MF are figured in Figure 3 as well, and the measured data in this work show good agreements with the reported ones.7−9 Antoine equation14,15 (eq 1) was employed in the correlation of the measured saturated vapor pressure (ps, kPa) and boiling temperature (T, K): B ln ps = A + (1) T+C

2AF

where A, B, and C are Antoine constants. The maximum likelihood principle is applied in the data correlation by minimizing the objective function (OF): ⎡⎛ exp ⎛ pexp − pcal ⎞2 ⎤ cal ⎞2 ⎢⎜ Tm − Tm ⎟ m m ⎟ ⎥ OF = ∑ ⎢⎜ ⎟ + ⎜⎜ ⎟⎥ σ σ ⎠ T ,m p,m ⎝ ⎠⎦ m = 1 ⎣⎝ n

(2)

where n is the total number of experimental points; superscripts exp and cal represent the experimental data and the calculated values, respectively; σT and σp are standard deviation of the temperature and pressure, respectively (σT = 0.1 K and σp = 0.075 kPa). The root-mean-square deviations of the temperature (δT) and the pressure (δp) were calculated as

5MF

⎡1 δT = ⎢ ⎢⎣ n ⎡1 δp = ⎢ ⎢⎣ n

⎤1/2

n

∑

(Tmexp

−

Tmcal)2 ⎥ ⎥⎦

m=1

⎤1/2

n

∑ m=1

(pmexp

(3)

−

pmcal )2 ⎥ ⎥⎦

(4)

The correlated parameters are listed in Table 4 and the calculated values were given in Table 3 and Figure 3. Good agreements are observed between with the experimental and calculated values: the root-mean-square deviations of FUR, 2AF, and 5MF are 0.08, 0.03, and 0.05, respectively, for the temperature and 0.103, 0.057, and 0.073 kPa, respectively, for the pressure. As a result, the Antoine equation can precisely describe the saturated vapor pressures of the three components and meet the needs of engineering application. 3.3. VLE for the Binary Systems. The isobaric VLE data for the three binary systems (FUR + 2AF, FUR + 5MF, 2AF + 5MF) at 3.60 and 5.18 kPa were measured and were listed in mole fraction in Tables 5, 6, and 7, respectively.

a

Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.075 kPa. Calculated values were regressed by the maximum likelihood, and pcal was calculated by Tcal. cAE(T) = |Texp − Tcal|. dAE(p) = |pexp − pcal|. b

3.2. Vapor Pressure for Pure Components. The saturated vapor pressures of FUR, 2AF, and 5MF were determined in the apparatus, and the corresponding boiling temperatures are shown in Table 3 and Figure 3. There are obvious positive correlations between the temperature and C



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Table 4. Antoine Constants for FUR, 2AF, and 5MF substance

A

B

C

Tmin/K

Tmax/K

δT/K

δp/kPa

FUR 2AF 5MF

15.6331 14.2381 15.1274

−4313.65 −3477.45 −4017.62

−41.5514 −84.7206 −74.9369

326.05 337.95 339.05

415.15 414.25 417.55

0.08 0.03 0.05

0.103 0.057 0.073

Table 5. VLE Data and Activity Coefficients for FUR (1) and 2AF (2) at 3.60 and 5.18 kPaa T/K

x1

y1

353.10 352.15 352.05 350.85 349.95 349.25 347.35 346.65 346.35 342.11

0.0000 0.0752 0.0936 0.2206 0.3164 0.4167 0.6253 0.6811 0.7145 1.0000

360.86 358.55 357.75 356.70 356.05 355.45 354.85 354.15 351.95 349.93

0.0000 0.2452 0.3086 0.4128 0.4754 0.5429 0.5716 0.6524 0.9104 1.0000

p = 3.60 kPa 0.0000 0.1472 0.1734 0.3627 0.4531 0.5484 0.7380 0.7820 0.8079 1.0000 p = 5.18 kPa 0.0000 0.3589 0.4352 0.5510 0.6143 0.6745 0.6961 0.7543 0.9409 1.0000

γ1

1.2308 1.1701 1.0959 0.9942 0.9432 0.9229 0.9273 0.9260 1.0000

1.0005 0.9977 0.9882 0.9841 0.9713 0.9775 0.9571 0.9435 1.0000

Table 6. VLE Data and Activity Coefficients for FUR (1) and 5MF (3) at 3.60 and 5.18 kPaa

γ2

T/K

1.0000 0.9656 0.9596 0.9124 0.9332 0.9349 0.9286 0.9406 0.9400

1.0000 0.9444 0.9427 0.9269 0.9189 0.9157 0.9386 0.9670 1.0036 /

a Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.075 kPa, u(x) = 0.005, u(y) = 0.004.

The activity coefficients γi were calculated as16 γi =

pyi φi V pis xiφis

(5)

D = 100 ×

1

∫0 J = 150 ×

( ) dx ln( ) dx

Tmax − Tmin Tmin

0.0000 0.1859 0.2047 0.3261 0.3789 0.4083 0.4913 0.5415 0.6259 0.7815 0.8435 0.8994 0.9441 0.9755 1.0000

/ 0.9077 0.9214 0.9370 0.9340 0.9409 0.9409 0.9426 0.9458 0.9345 0.9258 1.0000

1.0000 1.0249 1.0129 0.9933 0.9847 0.9531 0.9376 0.9051 0.8971 0.8544 0.8480

0.9758 0.9690 0.9831 0.9921 0.9961 0.9860 0.9890 0.9868 0.9681 0.9589 0.9520 0.9458 0.9543 1.0000

1.0000 1.0749 1.0572 0.9979 0.9709 0.9480 0.9152 0.8781 0.8733 0.8747 0.8650 0.8591 0.8633 0.8571

⎡ exp ⎛ pexp − pcal ⎞2 cal 2 ⎢⎛ Tm − Tm ⎞ m m ⎟ ⎜ ⎟ OF = ∑ ⎢⎜ ⎟ + ⎜⎜ σT , m σp , m ⎟⎠ ⎝ ⎠ ⎝ m=1 ⎢ ⎣ n

1

γ1

γ2

372.92 366.05 365.85 363.25 362.05 361.45 359.85 358.85 357.05 354.35 353.45 352.65 352.05 351.35 349.93

γ3

where Tmax and Tmin are the maximum and minimum boiling temperatures of the system, respectively. The charts of ln (γ1/γ2) versus liquid mole fraction x for the three binary systems were plotted in Figures 4, 5, and 6, respectively. According to the calculated results, the experimental data in this work are thermodynamically consistent since the values of (D − J) for each binary system are all within 10 (Table 8). Three thermodynamic models, that is, NRTL, Wilson, and UNIQUAC models,18 were applied to correlate the isobaric VLE data. The models are taken from Aspen Plus V8.0 and are presented in Table 9. The interaction parameters of these models were regressed by minimizing the following OF:19

γ1

γ2

0.0000 0.2811 0.3832 0.5337 0.5841 0.6358 0.6972 0.7605 0.8030 0.8855 0.9346 1.0000

γ1

Standard uncertainties u are u(T) = 0.1K, u(p) = 0.075 kPa, u(x) = 0.005, u(y) = 0.004.

The thermodynamic consistency of the measured data was checked to ensure the reliability of the VLE data by the semiempirical method suggested by Herington.17 The values of D and J are calculated as 1

365.09 357.05 354.65 351.35 350.45 349.45 348.35 347.25 346.45 345.35 344.75 342.11

y1 p = 3.60 kPa 0.0000 0.5035 0.6274 0.7673 0.8038 0.8423 0.8784 0.9125 0.9317 0.9644 0.9805 1.0000 p = 5.18 kPa 0.0000 0.3635 0.3942 0.5722 0.6381 0.6731 0.7492 0.7936 0.8470 0.9220 0.9472 0.9677 0.9825 0.9927 1.0000

a

where i represents the component FUR (1), 2AF (2), or 5MF (3); x and y denote the liquid- and vapor-phase mole fraction; φV and φS stand for the fugacity coefficients in the vapor phase and in the pure phase, respectively. As the experiments were conducted at such low pressure, the vapor phase could be considered as the ideal gas which resulted in φsi = 1 and φVi = 1. Thus, eq 5 could be simplified as py γi = s i pi xi (6)

∫0 ln

x1

2

2 ⎛ x exp − x cal ⎞2 ⎛ y exp − y cal ⎞ ⎤ 1, m 1, m 1, m 1, m ⎟ ⎥ ⎜ ⎟ + + ⎜⎜ ⎟ ⎜ σ ⎟⎥ σx , m y,m ⎝ ⎠ ⎝ ⎠ ⎥⎦

(7)

(8) D

(9)



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Table 7. VLE Data and Activity Coefficients for 2AF (2) + 5MF (3) at 3.60 and 5.18 kPaa T/K

x2

365.09 362.85 362.15 361.85 361.45 359.05 358.25 357.55 356.95 356.35 353.1

0.0000 0.1034 0.1393 0.1649 0.2106 0.4186 0.4825 0.5916 0.6434 0.7101 1.0000

372.92 368.25 367.75 367.25 366.25 365.65 363.95 363.05 362.35 361.35 360.86

0.0000 0.2508 0.3039 0.3418 0.4410 0.4966 0.6901 0.7862 0.8814 0.9647 1.0000

y2 p = 3.60 kPa 0.0000 0.1781 0.2311 0.2689 0.3280 0.5612 0.6199 0.7066 0.7499 0.8019 1.0000 p = 5.18 kPa 0.0000 0.3733 0.4392 0.4855 0.5841 0.6382 0.7932 0.8633 0.9270 0.9786 1.0000

γ2

γ3

/ 1.0937 1.0872 1.0832 1.0535 1.0123 1.0067 0.9669 0.9704 0.9671 1.0000

1.0000 1.0210 1.0295 1.0237 1.0151 1.0131 1.0261 1.0396 1.0460 1.0506

1.0718 1.0634 1.0682 1.0405 1.0366 0.9997 0.9943 0.9828 0.9918 1.0000

Figure 5. Charts of ln (γ1/γ3) versus liquid mole fraction x1 for the binary system of FUR (1) + 5MF (3).

1.0000 1.0369 1.0223 1.0154 1.0132 1.0070 1.0142 1.0149 1.0107 1.0453

a Standard uncertainties u are u(T) = 0.1K, u(p) = 0.075 kPa, u(x) = 0.005, u(y) = 0.004.

Figure 6. Charts of ln (γ2/γ3) versus liquid mole fraction x2 for the binary system of 2AF (2) + 5MF (3).

Table 8. Thermodynamic Consistency Check for Three Binary Systems (FUR + 2AF, FUR + 5MF, 2AF + 5MF) system

p/kPa

Tmax/K

Tmin/K

D

J

D−J

FUR + 2AF

3.60 5.18 3.60 5.18 3.60 5.18

351.10 360.86 365.09 372.92 365.09 372.92

342.11 349.93 342.11 349.93 353.10 360.86

11.2630 1.9607 19.2924 10.0642 8.7537 0.8683

3.9417 4.6852 10.0757 9.8548 5.0935 5.0130

7.3213 −2.7245 9.2167 0.2094 3.6603 −4.1448

FUR + 5MF 2AF + 5MF

Figure 4. Charts of ln (γ1/γ2) versus liquid mole fraction x1 for the binary system of FUR (1) + 2AF (2).

⎡ n ⎤1/2 exp cal 2 δy = ⎢ ∑ (ym − ym ) /n⎥ ⎢⎣ m = 1 ⎥⎦

where σx and σy are standard deviations of the liquid and vapor concentrations, respectively (σT = 0.1 K, σp = 0.075 kPa, σx = 0.005, and σy= 0.004). The experimental points are presented in Figures 7, 8, and 9, respectively, and the predictions by the NRTL model were figured as well. The obtained interaction parameters for the NRTL, Wilson, and UNIQUAC models are reported in Table 10. The root-mean-square deviations of the liquid and vapor mole fractions (δx and δy, respectively) were calculated as well: ⎡ n ⎤1/2 exp cal 2 δx = ⎢ ∑ (xm − xm ) /n⎥ ⎢⎣ m = 1 ⎥⎦

(11)

As seen from Figures 7, 8, and 9 and Table 10, the maximum of the calculated rmsd of temperature (δT), pressure (δp), liquid (δx), and vapor fractions (δy) for the three binary systems by each model were 0.20 K, 0.131 kPa, 0.0174, and 0.0074 respectively. It indicates that all the three models could describe the VLE of the three binary systems very well. There is no obvious difference among the predicted lines by the NRTL, Wilson, and UNIQUAC models, while the rmsd values show that the NRTL model is better for the binary systems. The VLE of the FUR+5MF system at 3.49 and 4.98 kPa was predicted by the obtained NRTL parameters and the results coincide well

(10) E



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Table 9. Mathematical Formulas of NRTL, Wilson, and UNIQUAC Equations Used in This Work model

NRTL

equation

ln γi =

∑j xjτjiGji ∑k xkGki

+

∑ j

∑ x τ G ⎞ xjGij ⎛ ⎜⎜τij − m m mj mj ⎟⎟ ∑k xkGij ⎝ ∑k xkGkj ⎠

Gij = exp( − αijτij), τij = aij + bij /T , Wilson

⎞ ⎛ ln γi = 1 − ln⎜⎜∑ Aijxj⎟⎟ − ⎠ ⎝ j ln γi = ln

UNIQUAC

φi xi

+

∑ j

αij was set as 0.2

Aji xj ∑k Ajk xk

, ln Aij = aij + bij /T

φi θ z q ln i − qi ln ti − qi∑ θτ j ij / t j + li + qi − 2 i φi xi j

∑ xjlj j

z li = (ri − qi) + 1 − ri , θi = qixi /∑ qkxk , φi = rx i i / ∑ rkxk , ti 2 k k =

∑ θkτki , τij = exp(aij + bij /T ) k

Figure 9. Experimental and calculated T−x2−y2 diagram for the binary system 2AF (2) + 5MF (3) at 3.60 and 5.18 kPa.

Figure 7. Experimental and calculated T−x1−y1 diagram for the binary system FUR (1) + 2AF (2) at 3.60 and 5.18 kPa.

3.4. Prediction of the Ternary VLE. With the obtained interaction parameters of the three models, the ternary VLE of FUR (1) + 2AF (2) + 5MF (3) were predicted and were compared with the measured ternary VLE data given in Table 11. The maximum absolute deviation and mean absolute deviation of boiling temperature and vapor composition were listed in Table 12. All three models were applied to predict the ternary VLE of the FUR + 2AF + 5MF system based on the binary interaction parameters, and low deviations were achieved (Table 12). Unlike the binary systems, for the prediction of ternary system, the Wilson model gives the smallest mean absolute deviations compared with the NRTL and UNIQUAC models. The residue curves of the ternary system were predicted by Wilson model, and the connecting lines of the liquid and vapor points are tangent to the residue curves (Figure 11). All the residue curves start from the slightest component (FUR) and move toward the heaviest component (5MF), and the mixture becomes the richest in 2AF at the inflection of the residue curves. No node is found along all the residue curves, which indicates that there is no azeotrope in the ternary system. The results demonstrate that the residue curves predicted by the Wilson model fit well with the experimental data, and the obtained Wilson interaction parameters can accurately predict the ternary VLE of FUR (1) + 2AF (2) + 5MF (3) in the simulation of an actual vacuum distillation process.

Figure 8. Experimental and calculated T−x1−y1 diagram for the binary system FUR (1) + 5MF (3) at 3.60 and 5.18 kPa.

with the reported data in ref 9 (Figure 10). Figures 7−9 show that the binary system of FUR + 5MF has more extensive vapor−liquid phase region compared to the systems of FUR + 2AF and 2AF + 5MF, which indicate that it is more beneficial to separate and purify the system of FUR + 5MF in industrial operation. F



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Table 10. Correlated Binary Interaction Parameters and Root-Mean-Square Deviations for the Systems binary interaction parameters model

aij

aji

NRTL Wilson UNIQUAC

43.9104 32.7034 −1.4536

−21.1919 −14.9618 −0.4052

NRTL Wilson UNIQUAC

12.4697 6.3152 −2.8785

−3.1658 −3.0685 4.3175

NRTL Wilson UNIQUAC

13.4858 10.4488 −4.0581

−19.0684 −6.8032 5.8149

bij

bji

FUR (1) + 2AF (2) −26877.20 12606.10 −11901.57 5559.94 308.04 320.98 FUR (1) + 5MF (3) −7064.42 1387.03 −2794.22 1422.49 1236.70 −1816.86 2AF (2) + 5MF (3) −9403.49 13267.10 −4045.75 2627.06 1610.20 −2295.71

δT /K

δp/kPa

δx

δy

0.17 0.20 0.17

0.002 0.002 0.002

0.0165 0.0174 0.0170

0.0069 0.0069 0.0074

0.05 0.05 0.05

0.123 0.131 0.125

0.0054 0.0060 0.0060

0.0047 0.0049 0.0050

0.02 0.02 0.02

0.047 0.050 0.048

0.0030 0.0031 0.0031

0.0022 0.0023 0.0023

4. CONCLUSION In this work, the saturated vapor pressures of FUR, 2AF, and 5MF were measured and the corresponding Antoine constants were correlated. The isobaric vapor−liquid equilibrium data for three binary systems (FUR + 2AF, FUR + 5MF, 2AF + 5MF) were determined at 3.60 and 5.18 kPa, respectively. The measured VLE data could all satisfy the Herington thermodynamic consistency testing criterion. The isobaric VLE data were correlated by the NRTL, Wilson, and UNIQUAC models; binary interaction parameters for each model were obtained. Good agreements were observed between the experimental and predicted data. The ternary VLE data were predicted by the obtained binary interaction parameters. The NRTL model gives the lowest deviations for the three binary systems and the rootmean-square deviations of temperature, pressure, vapor and liquid mole fraction are no more than 0.17 K, 0.123 kPa, 0.0165 and 0.0069, respectively. The Wilson model is the best model

Figure 10. Reported data and predicted values for the binary system FUR (1) + 5MF (3) at 3.49 and 4.98 kPa.

Table 11. Experimental VLE Data for the Ternary System of FUR (1) + 2AF (2) + 5MF (3) at 3.60 kPaa T/K 347.75 348.45 349.35 350.25 351.25 353.25 356.55 358.95 360.35 360.86 a

x1 0.5065 0.4832 0.4535 0.4234 0.3813 0.3069 0.2142 0.1486 0.1276 0.1153

x2 0.4935 0.4765 0.4418 0.4107 0.3764 0.2970 0.1870 0.1113 0.0854 0.0704

y1 0.6428 0.6191 0.6044 0.5850 0.5504 0.4832 0.3847 0.2933 0.2443 0.2257

γ1 0.9744 0.9525 0.9509 0.9463 0.9450 0.9424 0.9304 0.9218 0.8423 0.8430

y2 0.3572 0.3647 0.3511 0.3415 0.3338 0.2979 0.2254 0.1613 0.1313 0.1169

γ2 0.9419 0.9619 0.9549 0.9555 0.9706 0.9960 1.0227 1.0986 1.0933 1.1538

γ3 0.9311 0.9408 0.9351 0.9559 0.9963 0.9908 0.9943 0.9987 0.9909

Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.075 kPa, u(x) = 0.005, u(y) = 0.004.

Table 12. Absolute Deviations of Equilibrium Boiling Point and Vapor-Phase Mole Fraction for the Ternary System maximum absolute deviationa

a

mean absolute deviationb

model

ΔmaxT/K

Δmaxy1

Δmaxy2

Δmaxy3

ΔT /K

Δy1

Δy2

Δy3

NRTL Wilson UNIQUAC

0.64 0.56 0.91

0.0131 0.0130 0.0171

0.0114 0.0149 0.0157

0.0099 0.0180 0.0230

0.41 0.32 0.52

0.0084 0.0059 0.0108

0.0057 0.0051 0.0102

0.0046 0.0043 0.0062

ΔmaxT and Δmaxy are the maximum deviation of boiling point and vapor mole fraction, respectively. bCalculations: n

ΔT = (1/n)

∑ |Tmexp − Tmcal|, m=1

n

Δyi = (1/n)

− yical | ∑ |yiexp ,m ,m m=1

G



Article

from biomass: (Furfuryl alcohol + toluene), (furfuryl alcohol + ethanol), or (furfural + toluene). Fuel 2014, 122, 247−253. (7) Tai, W. P.; Lee, H. Y.; Lee, M. J. Isothermal vapor−liquid equilibrium for binary mixtures containing furfural and its derivatives. Fluid Phase Equilib. 2014, 384, 134−142. (8) Lomba, L.; Giner, B.; Lopéz, M. C.; Aldea, L.; Lafuente, C. Thermophysical Properties of Furfural Compounds. J. Chem. Eng. Data 2014, 59, 329−338. (9) Fele, L.; Grilc, V. Separation of Furfural from Ternary Mixtures. J. Chem. Eng. Data 2003, 48, 564−570. (10) Fele, L. Z.; Grile, V. Separation of furfural from industrial three component mixtures. Zb. Ref. Posvetovanja Slov. Kem. Dnevi. 2000, 955−960. (11) Wang, Y.; Guo, C.; Liu, X.; Huang, S.; Wang, B.; Zheng, H. Isobaric vapor−liquid equilibrium (VLE) for pinane, dihydromyrcene (DHM) and dihydromyrcenol (DHMOH) at 6 kPa. Fluid Phase Equilib. 2013, 342, 47−51. (12) Wang, Y. S.; Huang, N. R.; Xu, B. H.; Wang, B. Y.; Bai, Z. S. Measurement and Correlation of the Vapor Pressure of a Series of αPinene Derivatives. J. Chem. Eng. Data 2014, 59, 494−498. (13) Yaws, C. L.; Yang, H. C. To estimate vapor pressure easily. Hydrocarb. Process. 1989, 68, 65. (14) Yao, G.; Yang, Z.; Zhang, B.; Xu, H.; Zhao, H. Vapor pressure and isobaric vapor−liquid equilibrium for dichloronitrobenzene ssomers. Fluid Phase Equilib. 2014, 367, 103−108. (15) Thomson, G. W. The Antoine equation for vapor-pressure data. Chem. Rev. 1946, 38, 1−39. (16) Smith, J. M.; Ness, V.; Abbott, M. M. Introduction to Chemical Engineering Thermodynamics. J. Chem. Educ. 1950, 27, 584. (17) Yang, Q.; Jin, F.; Feng, X.; Zhi, J.; Yang, C. Isobaric Vapor− Liquid Equilibrium for Two Binary Systems (n-Butanol + 1, 4Butanediol and γ-Butyrolactone + 1,4-Butanediol) at p = (30.0, 50.0, and 70.0) kPa. J. Chem. Eng. Data 2016, 61, 3034−3040. (18) Zhou, F.; Zhong, L.; Chen, C.; Li, Y.; Xu, C. Isobaric Vapor− Liquid Equilibrium for Binary and Ternary Systems of Isoamyl Alcohol + Isoamyl Acetate + Dimethyl Sulfoxide at 101.33 kPa. J. Chem. Eng. Data 2017, 62, 691−697. (19) Liu, H.; Cui, X.; Zhang, Y.; Feng, T.; Zhang, K. Isobaric Vapor− Liquid Equilibrium for the Binary and Ternary System with Isobutyl Alcohol, Isobutyl Acetate and Dimethyl Sulfoxide at 101.3 kPa. J. Chem. Eng. Data 2017, 62, 1902−1909.

Figure 11. Residue curves of the ternary system of FUR (1) + 2AF (2) + 5MF (3): (●) experimental liquid phase composition; (○) experimental vapor phase composition; () residue curves; (---) connecting lines of liquid and vapor points.

for the ternary VLE prediction, and the maximum absolute deviations of boiling temperature and vapor mole fraction are 0.56 K and 0.0180, respectively.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Huidong Zheng: 0000-0002-8346-7284 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No. 21376053, No. 21476049), the Regional Development Project of Fujian Province (No. 2016H4023), the Special Project for Joint Innovation of Industrial Technology of Fujian Province (No. FG-2016005), and the Large-Scale Instrument and Equipment Open Sharing Fund of Fuzhou University (Grant 2017T030).

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REFERENCES

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