Isobaric Vaporâliquid Equilibrium for Three Binary Systems of Ethyl

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

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Isobaric Vapor−liquid Equilibrium for Three Binary Systems of Ethyl Acetate + Propyl Acetate, Ethyl Acetate + Propylene Carbonate, and Propyl Acetate + Propylene Carbonate at 101.3 kPa Xiaobin Liu,a Yukai Zhang,a Min Li,a Xin Li,a Guoxuan Li,a Yinglong Wang,*,a and Jun Gaob a

College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao, 266590, China

b

ABSTRACT: In this work, the isobaric vapor−liquid equilibrium (VLE) data for ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate + propylene carbonate systems were measured at a pressure of 101.3 kPa by a modified Rose vapor recirculating-type equilibrium still. The experimental results show that no azeotrope was detected between the three binary systems. Two thermodynamic consistency tests of Herington and van Ness were employed to check the experimental data, respectively. The measured VLE data were correlated by Wilson, universal quasichemical, and nonrandom two-liquid models. The calculated root-mean-square deviation values of the equilibrium temperature and vapor phase mole fractions are not more than 1.07 and 0.0113, respectively. The relative volatilities were calculated and the deviations between the experimental data and Wilson model calculations were compared. All the correlated results are in good agreement with the measured data. Meanwhile, the binary interaction parameters were regressed by the three models for all the binary systems. Propylene carbonate16,17 is a colorless, transparent liquid, which is an excellent organic solvent and intermediate for the synthesis of fine chemicals. Propylene carbonate is widely used in plastics, printing and dyeing, polymer synthesis, gas separation, and electrochemistry fields. Nie et al.18 studied the feasibility of CO2 removal from biogas using propylene carbonate as absorbent, and the results showed that the process has a high absorption efficiency and low energy consumption. Furthermore, propylene carbonate can be used to absorb carbon dioxide and hydrogen sulfide gas in natural gas and synthetic ammonia gas.19−21 In the process of treating packaging printing waste gas, propylene carbonate was selected as an absorbent to absorb the diluent released from the ink. For the simulation and optimization of the gas absorption process, the binary interaction parameters are needed, which were regressed by the vapor− liquid equilibrium (VLE) data.22−25 However, the experimental VLE data for ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate + propylene

1. INTRODUCTION Ethyl acetate1−3 and propyl acetate4,5 are important industrial organic chemicals with the characteristics of good solubility, special aroma, irritation, and low toxicity. The two esters are widely applied in coatings, printing and dyeing, medicine, fragrance, and paper making industries. Ethyl acetate and propyl acetate can be used as an ink diluent to adjust the viscosity of the ink. The solvent based ink used in the packing printing industry6−8 contains 50% to 60% ink diluent. During the printing process, about 70% to 80% of the ink diluent volatilizes when the printing is dried.9,10 So it will inevitably cause serious photochemical pollution and contribute to the greenhouse effect. Absorption11−13 is a common method in the treatment of exhaust gas. The principle of absorption is to use the difference of the solubility of each component in the absorber. Hariz et al.14 studied the absorption process of toluene using vegetable oil−water as absorber. Fang et al.15 developed a new paraffin/ surfactant/water emulsion for controlling volatile organic compounds, and the results indicated that the paraffin/ surfactant/water emulsion has great prospect in organic waste gas treatment with the advantages of economy, high efficiency, and safety. © XXXX American Chemical Society

Received: December 25, 2017 Accepted: March 15, 2018

A

DOI: 10.1021/acs.jced.7b01107 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Suppliers, Boiling Temperatures (Tb) at 101.3 kPa, Densities (ρb) at 298.15 K and Mass Fractions for Ethyl Acetate, Propyl Acetate, Propylene Carbonatea ρb/(g·cm−3)

Tb/Kb CAS

suppliers

exp

lit

exp

lit

mass fraction

purification method

analysis method

ethyl acetate

141-78-6

350.2

350.233

0.8995

0.894835

≥99.5%

none

GCa

propyl acetate

109-60-4

374.4

374.733

0.8860

0.883135

≥99.5%

none

GCa

propylene carbonate

108-32-7

Sinopharm Chemical Reagent Co., Ltd. Nanjing Chemical Reagent Co., Ltd. Shanghai Zhanyun Chemical Co., Ltd.

514.6

514.934

1.2040

1.204836

99.0%

none

GCa

component

a

Gas chromatography bStandard uncertainties u are u(T) = 0.1 K, u(ρ) = 0.005 g·cm−3, u(p) = 0.1 kPa, and u(x1) = u(y1) = 0.001.

carbonate systems at 101.3 kPa were not retrieved from the NIST database. In this article, the VLE data for ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate + propylene carbonate systems at 101.3 kPa were measured by a modified Rose vapor recirculating type equilibrium still.26,27 In addition, two thermodynamic consistency tests of Herington28 and point-to-point van Ness29 were employed to verify the VLE data. To correlate the experimental data, the models of Wilson,30 universal quasichemical (UNIQUAC),31 and nonrandom two liquid (NRTL)32 were adopted.

2. EXPERIMENT SECTION 2.1. Materials. Analytical reagents, ethyl acetate, propyl acetate, and propylene carbonate were used in this work. Gas chromatography was used to check the chemical purities. To measure the density (ρ) of all the chemicals at 298.15 K, a densimeter of Anton Paar DMA 4500 was used, the accuracy of which was 0.005 g·cm−3. The densimeter was calibrated by air and distilled water. For the determination of the boiling temperature (Tb) of the chemicals at 101.3 kPa, a precision mercury thermometer was used, the uncertainty of which was 0.1 K. The measured densities and boiling temperatures were compared with the literature values.33−36 The detailed information of chemicals are listed in Table 1. No further purification was carried out for all of these chemicals. 2.2. Apparatus and Procedures. In this work, a modified Rose-type recirculating still was employed, the structure map of which was presented in Figure 1. The condensed vapor phase and the liquid phase were continuously recirculated in the recirculating still to make the vapor−liquid phase contact fully and establish the balance as soon as possible. In our previous work,25,37 it has been confirmed that the still is reliable. A precision mercury thermometer was used to measure the temperature, the uncertainty of which was 0.1 K and was produced by Tianjin Glass Instrument Factory. A manometer was used to control the system pressure, the uncertainty of which was 0.1 kPa and was produced by Nanjing Hengyuan Automatic Gauge Co., Ltd. The vapor phase and liquid phase was removed at the same time from the equilibrium still, while the system temperature was kept at a constant value for 50 min. 2.3. Analysis. In this work, a gas chromatograph (GC-14C, SHIMADZU) was used to analyze the liquid phase and vapor phase samples to obtain components mass fractions. The GC was equipped with a DB-5 capillary column and a hydrogen flame ionization detector. The gas carrier flow rate of highpurity N2 was set at 30 mL·min−1. For the ethyl acetate + propyl acetate system, the temperature of the oven was 343.15 K. Meanwhile, both the temperature of injector and detector were all 363.15 K. For ethyl acetate + propylene carbonate and propyl

Figure 1. Structure map for the equilibrium still: (1) heating rod, (2) temperature measurement point, (3) liquid sample connection, (4) glass VLE chamber, (5) thermometer, (6) condenser, (7) vapor sample connection.

acetate + propylene carbonate systems, the temperature of the oven was 443.15 K, the temperature of injector was 473.15 K, and the temperature of the detector was 513.15 K. The compositions of all samples were obtained by the N2000 workstation software (Zhejiang University). The composition of each sample was obtained on the basis of more than three analysis results, and the average of three results was adopted. The masses of the standard samples were prepared gravimetrically using FA-1204B electronic balance (Shanghai Tianmei balance instrument co., Ltd.) with an uncertainty of 0.0001 g.

3. RESULTS AND DISCUSSIONS 3.1. Experimental Data. For ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate + propylene carbonate systems, the measured VLE data are expressed in mole fractions and listed in Table 2. For the three binary systems, the T−x−y phase diagrams are shown in Figures 2 to 4. 3.2. Thermodynamic Consistency Tests. The experiments were carried out at the pressure of 101.3 kPa, so the vapor phase can be considered as an ideal gas. The simplified relationship of vapor−liquid equilibrium can be expressed as follows: yp = xiγipis i

(1)

where yi is the vapor phase mole fractions of component i, and xi is the liquid phase mole fractions of component i. γi and P are the B



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Table 2. Isobaric Experimental VLE Data of Temperature T, Liquid Phase x1, Vapor Phase y1, Activity Coefficient γ, and the Absolute Deviation between the Experimental and Calculated Values of Temperature ΔT, Mole Fractions of Vapor Phase Δy1, for the Three Systems at 101.3 kPaa Wilson no.

a

T/K

x1

y1

1 2 3 4 5 6 7 8 9 10 11 12 13

373.1 370.6 369.7 367.3 364.3 362.6 360.0 359.4 357.1 355.8 354.9 353.9 351.6

0.043 0.124 0.154 0.234 0.345 0.412 0.518 0.545 0.646 0.708 0.752 0.803 0.928

0.080 0.222 0.271 0.385 0.515 0.589 0.698 0.723 0.800 0.846 0.877 0.910 0.972

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

351.9 353.3 355.2 357.2 359.0 361.3 363.5 365.1 370.8 372.8 376.6 381.4 386.0 390.2 395.7 403.6 415.4 427.9 447.7 454.7 461.1 468.6

0.953 0.908 0.849 0.791 0.745 0.683 0.628 0.592 0.473 0.436 0.372 0.306 0.255 0.219 0.179 0.140 0.097 0.070 0.044 0.037 0.033 0.030

1.000 0.999 0.999 0.999 0.998 0.998 0.997 0.997 0.994 0.994 0.991 0.989 0.985 0.982 0.976 0.964 0.947 0.917 0.847 0.801 0.757 0.692

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

376.2 378.5 380.4 382.9 387.3 391.2 397.0 404.2 407.9 412.6 417.7 423.7 429.2 439.7 459.1 474.0 487.5

0.950 0.882 0.827 0.761 0.648 0.562 0.448 0.334 0.286 0.236 0.190 0.151 0.123 0.089 0.050 0.031 0.018

0.999 0.997 0.996 0.994 0.990 0.986 0.979 0.969 0.963 0.955 0.944 0.931 0.915 0.879 0.772 0.644 0.493

γ1

γ2

ΔT/K

UNIQUAC Δy1

Ethyl Acetate (1) + Propyl Acetate (2) 0.9286 1.0074 0.08 0.0013 0.9615 1.0069 0.10 0.0024 0.9692 1.0055 0.07 0.0031 0.9722 1.0106 0.02 0.0010 0.9618 1.0289 0.13 0.0120 0.9718 1.0283 0.10 0.0103 0.9907 1.0045 0.02 0.0018 0.9953 0.9954 0.02 0.0004 0.9965 0.9983 0.15 0.0025 1.0014 0.9765 0.21 0.0006 1.0056 0.9493 0.25 0.0013 1.0095 0.9062 0.27 0.0032 1.0054 0.8497 0.18 0.0002 Ethyl Acetate (1)+ Propylene Carbonate (2) 0.9983 2.3656 0.06 0.0000 0.9998 2.2228 0.09 0.0001 1.0047 2.0225 0.11 0.0001 1.0115 1.8442 0.16 0.0000 1.0180 1.7621 0.22 0.0001 1.0327 1.6701 0.23 0.0001 1.0475 1.6298 0.27 0.0000 1.0594 1.5457 0.30 0.0001 1.1181 1.4302 0.25 0.0000 1.1467 1.4088 0.11 0.0001 1.2053 1.3834 0.10 0.0003 1.2826 1.3372 0.34 0.0004 1.3567 1.2760 0.45 0.0003 1.4127 1.2554 0.38 0.0007 1.4963 1.2401 0.45 0.0013 1.5669 1.2658 0.10 0.0042 1.6965 1.1215 0.02 0.0023 1.7507 1.0703 0.18 0.0023 1.7377 0.9925 0.04 0.0054 1.7055 1.0278 0.31 0.0019 1.6405 1.0277 0.33 0.0014 1.4429 1.0420 0.44 0.0141 Propyl Acetate (1) + Propylene Carbonate (2) 1.0007 2.2535 0.02 0.0000 1.0046 2.1808 0.07 0.0000 1.0103 2.0985 0.12 0.0001 1.0208 1.9804 0.19 0.0001 1.0489 1.7934 0.34 0.0002 1.0842 1.6720 0.37 0.0003 1.1535 1.5181 0.43 0.0007 1.2671 1.3802 0.33 0.0013 1.3373 1.3210 0.20 0.0016 1.4367 1.2591 0.02 0.0019 1.5547 1.2020 0.30 0.0017 1.6834 1.1472 0.45 0.0023 1.8008 1.1095 0.58 0.0023 1.9043 1.0663 0.08 0.0017 2.0013 1.0402 0.23 0.0018 2.0357 1.0364 0.07 0.0005 2.1360 1.0117 0.16 0.0026

NRTL

ΔT/K

Δy1

ΔT/K

Δy1

0.15 0.13 0.07 0.01 0.14 0.08 0.04 0.08 0.22 0.28 0.30 0.30 0.17

0.0000 0.0007 0.0010 0.0059 0.0154 0.0124 0.0024 0.0000 0.0025 0.0006 0.0012 0.0031 0.0004

0.16 0.12 0.07 0.02 0.14 0.08 0.04 0.09 0.23 0.27 0.29 0.29 0.16

0.0001 0.0008 0.0013 0.0062 0.0154 0.0124 0.0027 0.0004 0.0031 0.0012 0.0008 0.0028 0.0005

0.01 0.01 0.05 0.11 0.20 0.25 0.35 0.37 0.57 0.51 0.39 0.16 0.08 0.21 0.69 0.86 1.69 1.71 0.51 0.09 0.98 3.99

0.0001 0.0002 0.0003 0.0003 0.0004 0.0005 0.0007 0.0007 0.0012 0.0014 0.0019 0.0024 0.0025 0.0030 0.0035 0.0060 0.0019 0.0004 0.0043 0.0046 0.0143 0.0498

0.02 0.01 0.05 0.11 0.15 0.30 0.39 0.43 0.67 0.81 0.95 0.93 0.69 0.28 0.05 0.75 0.73 0.38 0.49 1.04 0.91 0.96

0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0002 0.0001 0.0002 0.0002 0.0005 0.0008 0.0011 0.0019 0.0031 0.0071 0.0060 0.0055 0.0054 0.0036 0.0026 0.0218

0.00 0.03 0.06 0.11 0.23 0.38 0.60 0.83 0.91 0.93 0.82 0.43 0.06 0.74 0.54 0.19 1.06

0.0000 0.0001 0.0002 0.0002 0.0002 0.0003 0.0002 0.0001 0.0001 0.0003 0.0004 0.0000 0.0008 0.0048 0.0091 0.0050 0.0174

0.06 0.14 0.24 0.37 0.60 0.77 0.75 0.42 0.19 0.07 0.21 0.29 0.13 0.50 0.37 0.30 1.29

0.0003 0.0006 0.0009 0.0012 0.0016 0.0020 0.0027 0.0040 0.0048 0.0058 0.0066 0.0069 0.0064 0.0079 0.0106 0.0084 0.0150

Standard uncertainties are u(T) = 0.1 K, u(p) = 0.1 kPa, and u(x1) = u(y1) = 0.001. C



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component i, which can be calculated by the following extended Antoine equation: C2i ln(pis /kPa) = C1i + + C4iT + C5i ln(T ) + C6iT C7i T + C3i for C8i ≤ T ≤ C9i

(2)

For each pure component i, the Antoine parameters C1i to C9i are listed in Table 3, which were obtained from the Aspen property database. Two thermodynamic consistency tests of Herington28 and van Ness were employed to check the measured experimental data, respectively. The empirical method of the Herington consistency test28 was based on the Gibbs−Duhem38 theorem, which can be expressed by eq 3 and eq 4:

Figure 2. T−x−y diagram for the ethyl acetate (1) + propyl acetate (2) system at 101.3 kPa: (■) T−x for experimental data; (⧫) T−y for experimental data; () Wilson model; (---) UNIQUAC model; (···) NRTL model.

1

∫0 ln(γ1/γ2) dx1 S − S− D = 100 × + = 100 × 1 S+ + S− ∫0 |ln(γ1/γ2)| dx1 Tmax ‐Tmin Tmin

J = 150 ×

(3)

(4)

where the S+ and S− are the area above and below the horizontal coordinate axis in the ln (γ1/γ2) vs x diagram, respectively. Tmax and Tmin are the maximum and minimum boiling points, respectively. The relationship between ln (γ1/γ2) and x1 is shown in Figure 5. The |D − J| values for ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate + propylene carbonate systems are listed in Table 4, and the values are less than 10,39 so the measured data are thermodynamically consistent. The van Ness test29,40 is suitable for testing the reliability of each experimental point, which is expressed as follows: Figure 3. T−x−y diagram for the ethyl acetate (1) + propylene carbonate (2) system at 101.3 kPa: (■) T−x for experimental data; (⧫) T−y for experimental data; () Wilson model; (---) UNIQUAC model; (···) NRTL model.

ΔP =

Δy =

N

1 N

∑ ΔPi =

1 N

∑ Δyi =

i=1 N i=1

N

Pical − Piexp Piexp

1 N

∑ 100

1 N

∑ 100|yical

i=1

(5)

N

− yiexp |

i=1

(6)

where N represents the experimental data points, exp represents the experimental data, cal represents the calculated values with the NRTL model. According to the principle of the van Ness test, if the values of ΔP and Δy are less than 1, the measured data can pass the thermodynamic consistency test. The test results calculated by the Wilson model for ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate+ propylene carbonate systems are reported in Table 5. All of the values are less than 1, which indicated that the measured data are reliable. 3.3. Data Correlation. To describe the phase behaviors of ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate + propylene carbonate systems, the commercial software Aspen Plus V8.8 was used to correlate the measured data with the Wilson, UNIQUAC, and NRTL models, which are expressed as follows:

Figure 4. T−x−y diagram for the propyl acetate (1) + propylene carbonate (2) system at 101.3 kPa: (■) T−x for experimental data; (⧫) T−y for experimental data; () Wilson model; (---) UNIQUAC model; (···) NRTL model.

Wilson: ⎞ ⎛ ln γi = 1 − ln⎜⎜∑ Aij xj⎟⎟ − ⎠ ⎝ j

activity coefficient of component i and the system pressure, respectively. piS is the saturated vapor pressure of pure D

∑ j

Aij xj ∑k A jk xk

(7)



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Table 3. Parameters of the Extended Antoine Equationa

a

component

C1i

C2i

C3i

C4i

C5i

C6i (×106)

C7i

C8i/K

C9i/K

ethyl acetate propyl acetate propylene carbonate

59.9162 108.2522 99.5322

−6227.60 −8433.90 −10819.00

0 0 0

0 0 0

−6.4100 −13.9340 −12.0680

1.7914 × 10−11 10.346 5.4639

6.00 2.00 2.00

189.60 178.15 224.85

523.30 549.73 778.00

Take from Aspen property databank.

Table 4. Herington Method for Thermodynamic Consistency Check system

D

J

|D − J| < 10

ethyl acetate (1) + propyl acetate (2) ethyl acetate (1) + propylene carbonate (2) propyl acetate (1) + propylene carbonate (2)

15.8923 61.0760

10.3758 70.4794

5.5165 9.4034

51.3930

56.2151

4.8221

Table 5. van Ness Test for Thermodynamic Consistency Check system

ΔP < 1

Δy < 1

ethyl acetate (1) + propyl acetate (2) ethyl acetate (1) + propylene carbonate (2) propyl acetate (1) + propylene carbonate (2)

0.04 0.21 0.17

0.3075 0.1600 0.1124

UNIQUAC: ln γi = ln −

∑j θjtτij Φi θ z + qi ln i − qit ln tit − qit + li + qit xi 2 Φi t jt Φi xi

∑ xjlj (9)

j

where ⎛ bij ⎞ τij = exp⎜aij + ⎟ T⎠ ⎝

(10)

NRTL: ln γi =

∑j xjτjiGji ∑k xkGki

+

∑ j

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

(11)

where τij = aij +

bij T

;

Gij = exp(− αijτij)

(12)

In the data regression, the binary interaction parameters were obtained using the maximum likelihood objective function optimized. The objective function is expressed by eq 13: ⎡⎛ exp cal ⎞2 ⎛ P exp − P cal ⎞2 ⎛ x exp − x cal ⎞2 ⎢⎜ Ti − Ti ⎟ i i i ⎟⎟ + ⎜⎜ i OF = ∑ ⎢⎜ ⎟ + ⎜⎜ ⎟⎟ σp σx σT ⎠ ⎝ ⎠ ⎝ ⎠ i = 1 ⎣⎝ N

⎛ y exp − y cal ⎞2 ⎤ i ⎟ ⎥ + ⎜⎜ i y ⎟⎥ σ ⎝ ⎠⎦

Figure 5. ln (γ1/γ2) vs x diagrams for (a) ethyl acetate + propyl acetate, (b) ethyl acetate + propylene carbonate, (c) propyl acetate + propylene carbonate, separately.

where N represents the experimental points, T and P represent the equilibrium temperature and pressure, respectively. xi is the liquid phase mole fractions of component i. yi is the vapor phase mole fractions of component i. σ is the stand deviation. The absolute deviation for the temperature and the vapor phase composition between the calculated and experimental

where

ln Aij = aij +

bij T

(13)

(8) E



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Table 6. Binary interaction parameters RMSD Deviations in the Equilibrium Temperature and Vapor Phase Mole Fractions for the Systems of Ethyl Acetate + Propyl Acetate, Ethyl Acetate + Propylene Carbonate, And Propyl Acetate+ Propylene Carbonate with Wilson, UNIQUAC, and NRTL Models. aij

model

aji

Wilson UNIQUAC NRTL

−26.9683 −9.2039 22.2129

13.4467 9.1278 −21.7179

Wilson UNIQUAC NRTL

0.4591 0 −4.9149

4.4050 0 6.2345

Wilson UNIQUAC NRTL

−1.6438 3.2810 −2.3441

5.0017 −5.4204 1.8736

bij/K

bji/K

Ethyl Acetate (1) + Propyl Acetate (2) 9496.0185 −4672.4259 3347.73 −3320.4117 −8080.3630 7897.3006 Ethyl Acetate (1) + Propylene Carbonate (2) −2154.3859 −1497.0655 −9.8900 −52.4224 1547.9821 −1392.7852 Propyl Acetate (1) + Propylene Carbonate (2) −1137.0240 −1864.7367 −1094.0549 1578.6452 663.8767 108.6600

αij

RMSD (T/K)

RMSD (y1)

0.30

0.15 0.18 0.18

0.0037 0.0059 0.0059

0.30

0.26 1.07 0.61

0.0035 0.0113 0.0055

0.30

0.28 0.59 0.50

0.0025 0.0050 0.0064

values are listed in Table 2. The ΔT and Δyi are defined as follows: ΔT = |Tiexp − Tical|

(14)

Δyi = |yiexp − yical |

(15)

The regressed binary interaction parameters of the three models are listed in Table 6 for ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate + propylene carbonate systems. The root-mean-square deviations (RMSD) were calculated and listed in Table 6. The RMSD (yi) and RMSD (T) are defined as follows: RMSD(yi ) =

1 N

RMSD(T ) =

1 N

∑ (yiexp − yical )2 ∑ (T

exp

(16) Figure 6. Relative volatility of the ethyl acetate + propyl acetate system at 101.3 kPa: (■) experimental data; () Wilson model; (---) + 5% deviation of Wilson model; (···) −5% deviation of Wilson model.

cal 2

−T )

(17)

Figures 2 to 4 show the comparison among the correlated results and the measured data. From Table 6, the RMSDs of vapor phase mole fractions (y1) for ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate+ propylene carbonate systems are not more than 0.0059, 0.0113, 0.0064. The RMSDs of the equilibrium temperature (T) for the three systems are not more than 0.18, 1.07, 0.59. The results showed that the three binary VLE data can be correlated well with the three models. In addition, the relative volatilities (α)41−43 for the three systems were calculated to evaluate the experimental data, which can be expressed as follows: α12 =

y1 /x1 (1 − y1)(1 − x1)

(18)

Figures 6 to 8 show the relative volatilities comparisons between the Wilson model and experimental data for ethyl acetate + propyl acetate, ethyl acetate + propylene carbonate, and propyl acetate + propylene carbonate systems. For the ethyl acetate + propyl acetate and ethyl acetate + propylene carbonate systems, the maximum model deviation is 5%. For the propyl acetate + propylene carbonate system, the maximum model deviation is 10%. The calculated results for three systems agree well with the measured data.

Figure 7. Relative volatility of the ethyl acetate + propylene carbonate system at 101.3 kPa: (■) experimental data; () Wilson model; (---) + 5% deviation of Wilson model; (···) −5% deviation of Wilson model.

ethyl acetate + propylene carbonate, and propyl acetate + propylene carbonate at 101.3 kPa. Three models of Wilson, UNIQUAC, and NRTL were used to correlate the measured data. The Herington and van Ness tests were employed to assess the reliability of the experimental data, respectively. The RMSD values of temperature and mole fractions of vapor phase are less than 1.07 K and 0.0113, respectively. The results show that the correlation results by three models are in good agreement with the measured data for the above three systems, especially the Wilson model.

4. CONCLUSIONS In this work, a modified Rose-type recirculating still was employed to measure the isobaric VLE data for ethyl acetate + propyl acetate, F



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Figure 8. Relative volatility of the propyl acetate + propylene carbonate system at 101.3 kPa: (■) experimental data; () Wilson model; (---) + 10% deviation of Wilson model; (···) −10% deviation of Wilson model.

Relative volatilities of the three systems at 101.3 kPa were also calculated. The comparison results between the Wilson model and the measured data show that the correlation results are in good agreement with the measured data. The obtained binary interaction parameters can be used to design and optimize the process of treating packaging printing waste gas.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Yinglong Wang: 0000-0002-3043-0891 Jun Gao: 0000-0003-1145-9565 Funding

This work is supported by the National Natural Science Foundation of China (No. 21776145) and National Natural Science Foundation of China (No. 21306093). Notes

The authors declare no competing financial interest.

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