Experimental Measurement and Modeling of Ternary VaporâLiquid

Article pubs.acs.org/jced

Experimental Measurement and Modeling of Ternary Vapor−Liquid Equilibrium for Water + 2‑Propanol + Glycerol Lianzhong Zhang,* Weidong Zhang, and Bo Yang Zhejiang Province Key Laboratory of Biofuel, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China ABSTRACT: Isobaric vapor−liquid equilibrium (VLE) data for the ternary system water + 2-propanol + glycerol are reported at 100 kPa. The ternary VLE data, together with literature values of binary VLE and activity coefficients at infinite dilution for water + 2-propanol, were correlated by the NRTL activity coefficient model. The correlation appears to be satisfactory for all the data. The experimental results were compared graphically with those of calculations, showing good agreement. With the addition of glycerol, the azeotrope of water + 2-propanol can be removed at a glycerol mass fraction of 0.229. Glycerol is a potentially effective entrainer for dehydration of 2-propanol by extractive distillation.

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INTRODUCTION Glycerol is a byproduct in the production of biodiesel. It is nontoxic, environment compatible, highly available, and inexpensive.1,2 These features have encouraged the search for its new uses, e.g., as entrainer for extractive distillation. Researches have shown that glycerol is applicable in the process of bioethanol dehydration,3−5 substituting ethylene glycol, which is toxic, environmentally harmful, and therefore can be forbidden in the future.5 Vapor−liquid equilibrium (VLE) data have been reported for the ternary system water + ethanol + glycerol by Souza et al.6 and Pla-Franco et al.7 At the temperatures of extractive distillation operation, the vapor pressure of glycerol is very low. In this sense glycerol has properties similar to ionic liquids,8,9 which have been studied extensively for potential use in extractive distillation.10−15 The mixture of water + 2-propanol forms a minimum boiling point azeotrope. Recent researches regarding choice of appropriate entrainer were mainly focused on ionic liquids. Various ionic liquids have been studied for their ability of breaking the azeotrope, including 1-ethyl-3-methylimidazolium tetrafluoroborate, by Li et al.;11 1-butyl-3-methylimidazolium tetrafluoroborate, by Li et al.,12 Kim et al.,13 Navarro et al.,14 and Zhang et al.;16 1-ethyl-3-methylimidazolium ethylsulfate, by Kim et al.;13 1-butyl-3-methylimidazolium acetate, by Deng et al.;17 1-butyl-3-methylimidazolium chloride, by Deng et al.18 Zhang et al.19 compared performance of 5 different ionic liquids for the same azeotropic mixture. In this work, we have measured isobaric VLE data for the ternary system water + 2propanol + glycerol, aiming at breaking the azeotrope with glycerol as solvent. The measurements were performed in a relatively wide range of glycerol mass fractions up to 0.8 and in a relatively complete composition range for the quasi-binary pair of water + 2-propanol. This system has been studied by Verhoeye et al.20 However, the measurements were limited to a glycerol mass fraction of 0.53 and a value of 0.78 for 2-propanol mole faction on glycerol-free basis, lacking data at higher glycerol mass fractions and in the 2-propanol-rich region. © XXXX American Chemical Society

EXPERIMENTAL SECTION Materials. Water was double distilled. 2-Propanol (mass fraction purity 0.998) and glycerol (mass fraction purity 0.995) were supplied by Sinopharm Chemical Reagent Co. Ltd. and were used without further purification. Their purities were checked by GC. Water mass fraction of 2-propanol and glycerol was typically 4.8 × 10−4 and 7.6 × 10−4, respectively. Determination of Vapor-Phase Composition. As glycerol is slightly volatile, the vapor-phase samples were treated as ternary mixture of water, 2-propanol, and glycerol. Glycerol mass fraction, w3, was analyzed by gas chromatograph (Fuli 9790J), equipped with a capillary column of OV-1301 (20 m × 0.32 mm × 0.25 μm). Injector and column temperatures were 523.2 and 393.2 K, respectively. Carrier gas was nitrogen, and detection was by FID at 553.2 K. 1,6-Hexanediol was used as internal standard and was added quantitatively in the sample. A calibration curve was prepared for the GC analysis. Each sample was analyzed three times. Deviations were less than 15%. At the same time, water mass fraction, w1, was measured by Karl Fischer titration (SF-3 Titrator, Zibo Zifen Instrument, Ltd.). When w1 is higher than 0.02, sample was first diluted with 2-propanol quantitatively, and water mass fraction was calculated by the ratio of dilution and the water content of the diluted mixture. Using w1 and w3, vapor-phase mole fractions, y1 and y2, were calculated. The relative standard uncertainty was estimated to be 0.01 for y1 and y2. Apparatus and Procedure. VLE were measured by an ebulliometer. Pressure measurement was by a U-tube filled with water, with a standard uncertainty of 0.05 kPa. Temperature measurement was by a standard platinum thermometer and a 6−1/2-digit multimeter. Standard uncertainty of the temperature measurement was 0.08 K. Details of the experimental Received: August 2, 2014 Accepted: October 16, 2014

A

dx.doi.org/10.1021/je500724p | J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Experimental Vapor−Liquid Equilibrium Data for Temperature T, Liquid-Phase Mole Fraction on Glycerol-Free Basis x′, Liquid-Phase Mass Fraction w, Vapor-Phase Mole Fraction y, Calculated Results for Activity Coefficient γ, and Relative Volatility α, for the Ternary System Water (1) + 2-Propanol (2) + Glycerol (3) at p = 100 kPaa x′2

a

w3

T/K

0.0979 0.0987 0.0991 0.1000 0.0996 0.1008 0.1006 0.1005

0.7984 0.7024 0.6038 0.5002 0.4002 0.3011 0.2030 0.1012

373.79 367.11 363.08 360.52 358.92 357.81 357.08 356.52

0.2003 0.2001 0.2002 0.2001 0.2002 0.2002 0.2002 0.2002

0.8004 0.6988 0.6016 0.5018 0.4018 0.3011 0.2016 0.1012

369.70 363.64 360.52 358.57 357.31 356.43 355.78 355.30

0.4017 0.4016 0.4001 0.4007 0.3994 0.3997 0.4017 0.3995

0.8063 0.7041 0.6057 0.5022 0.4034 0.3017 0.2034 0.1005

368.05 362.98 360.20 358.40 357.11 356.05 355.20 354.44

0.5979 0.6009 0.6000 0.6005 0.6001 0.6004 0.6004 0.6004

0.8005 0.7013 0.6020 0.5027 0.4001 0.3022 0.2016 0.0998

367.22 363.27 360.91 359.20 357.74 356.51 355.30 354.13

0.8011 0.8030 0.8009 0.8015 0.8004 0.8007 0.8016 0.8008

0.7909 0.7049 0.6003 0.5036 0.4008 0.3001 0.2009 0.1018

367.01 364.05 361.88 360.41 358.99 357.63 356.25 354.79

0.9502 0.9500 0.9502 0.9502 0.9509 0.9503 0.9502 0.9502

0.8044 0.7022 0.6038 0.5013 0.3995 0.3016 0.2034 0.1020

367.89 364.63 362.76 361.38 360.16 358.95 357.62 356.10

y1 x′2 = 0.1 0.4363 0.4498 0.4616 0.4624 0.4838 0.4880 0.4977 0.5078 x′2 = 0.2 0.3097 0.3407 0.3670 0.3880 0.4082 0.4239 0.4418 0.4534 x′2 = 0.4 0.1785 0.2202 0.2587 0.2952 0.3264 0.3579 0.3850 0.4096 x′2 = 0.6 0.1078 0.1371 0.1705 0.2050 0.2385 0.2721 0.3016 0.3354 x′2 = 0.8 0.0491 0.0637 0.0850 0.1017 0.1280 0.1504 0.1757 0.2028 x′2 = 0.95 0.0106 0.0151 0.0201 0.0261 0.0330 0.0414 0.0494 0.0603

y2

γ1

γ2

α21

0.5636 0.5502 0.5384 0.5376 0.5161 0.5120 0.5023 0.4922

0.91 0.96 1.00 1.01 1.05 1.05 1.06 1.07

5.55 5.48 5.41 5.36 5.14 5.01 4.86 4.72

11.90 11.17 10.60 10.46 9.65 9.36 9.02 8.67

0.6902 0.6593 0.6330 0.6120 0.5918 0.5761 0.5582 0.5466

0.93 0.99 1.04 1.06 1.09 1.10 1.12 1.13

4.23 3.91 3.64 3.41 3.21 3.05 2.89 2.78

8.90 7.73 6.89 6.30 5.79 5.43 5.05 4.82

0.8214 0.7797 0.7412 0.7048 0.6736 0.6421 0.6150 0.5904

0.91 1.00 1.09 1.17 1.23 1.30 1.37 1.42

3.20 2.70 2.38 2.12 1.94 1.79 1.66 1.57

6.85 5.28 4.29 3.57 3.10 2.69 2.38 2.17

0.8921 0.8628 0.8295 0.7950 0.7615 0.7279 0.6984 0.6646

0.95 1.03 1.13 1.26 1.38 1.51 1.63 1.79

2.69 2.19 1.87 1.65 1.49 1.37 1.28 1.20

5.57 4.18 3.24 2.58 2.13 1.78 1.54 1.32

0.9508 0.9362 0.9149 0.8983 0.8719 0.8496 0.8243 0.7972

0.95 1.04 1.18 1.27 1.48 1.65 1.88 2.14

2.33 1.92 1.61 1.42 1.28 1.18 1.11 1.06

4.81 3.61 2.68 2.19 1.70 1.41 1.16 0.98

0.9892 0.9848 0.9798 0.9738 0.9670 0.9586 0.9505 0.9396

0.91 1.01 1.14 1.31 1.52 1.78 2.03 2.43

2.28 1.77 1.49 1.30 1.18 1.09 1.04 1.01

4.89 3.44 2.55 1.95 1.52 1.21 1.01 0.82

u(T) = 0.08 K, u(p) = 0.05 kPa, u(w3) = 0.003, ur(x′2) = 0.01, ur(y1) = 0.01, and ur(y2) = 0.01.

apparatus have been described previously.19 The VLE measurements were performed in a way in which the glycerol mass

fraction, w3, changed from high to low, while x′2, defined as x′2 = x2/(x1 + x2), remained almost unchanged. At the beginning B



Article sat sat sat α21 = (γ2/γ1)·(psat 2 /p1 ). The ratio of vapor pressures, p2 /p1 , is insensitive to temperature and is in a range of 1.95 to 1.97. Therefore, the effect of glycerol on α21 is mainly related with its effect on the activity coefficients. With the increase of x3, as shown in Figure 2, the activity coefficient of water decreases,

of measurement, a certain amount of 2-propanol and glycerol were introduced into the ebulliometer. Water content was determined by Karl Fischer analysis. Additional water was added to meet the prescribed value of x′2. Every sample added in or taken out of the ebulliometer was weighed by an electronic balance (Mettler-Toledo AL204). The overall synthetic masses for the first measurement were thus obtained. When equilibrium was established, the vapor condensate was sampled and analyzed. Liquid compositions were calculated on the basis of mass balance.16,21 The next measurement was carried out by replacement of a certain amount of the mixture in the boiler with water and 2-propanol to reduce w3 and keep x′2 unchanged. The measurement was repeated until w3 became close to 0.1.22 Standard uncertainty of w3 was estimated to be 0.003. The relative standard uncertainty of x′2 was estimated to be 0.01.

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RESULTS AND DISCUSSION The experimental VLE data for the ternary system water (1) + 2-propanol (2) + glycerol (3) are listed in Table 1, including liquid phase mole fraction of 2-propanol on an glycerol free basis (x′2), liquid phase mass fraction of glycerol (w3), vapor phase mole fraction of 2-propanol (y2), equilibrium temperature (T), the activity coefficients of water (γ1) and 2-propanol (γ2), and the relative volatility of 2-propanol to water (α21). The experimental measurements were performed at p = 100 kPa, with x′2 kept approximately unchanged at 0.1, 0.2, 0.4, 0.6, 0.8, and 0.95, respectively. For each x′2, w3 was changed from 0.8 down to 0.1. In the calculation of the activity coefficients the vapor phase was regarded as an ideal gas, and the saturated vapor pressures were calculated by parameters in the literature.23 Effects of glycerol on the phase behavior of water and 2propanol are illustrated in Figures 1 to 4. In Figure 1 the relative volatility of 2-propanol to water, α21, is shown in relation with glycerol mole fraction, x3. At all the six 2-propanol mole fractions, enhancement of α21 can be observed by the addition of glycerol. The effect of glycerol on α21 can be separately depicted by its effect on γ1 and γ2 with the relation

Figure 2. Experimental and calculated activity coefficients of (a) water, γ1, and (b) 2-propanol, γ2, in relation with glycerol mole fraction, x3, for the saturated mixture water (1) + 2-propanol (2) + glycerol (3) at p = 100 kPa: ○, x′2 = 0.1; ●, x′2 = 0.2; □, x′2 = 0.4; ■, x′2 = 0.6; ◊, x′2 = 0.8; ⧫, x′2 = 0.95. Lines were calculated by NRTL parameters in Table 2 at p = 100 kPa and at x′2 = 0.1, 0.2, 0.4, 0.6, 0.8, and 0.95, respectively.

while the activity coefficients of ethanol increases. Both of these opposite trends are favorable for the enhancement of relative volatility because both the increase of γ2 and the decrease of γ1 will lead to the increase of α21. In Figure 3, γ1 and γ2 are also

Figure 3. Experimental and calculated activity coefficients of (a) water, γ1, and (b) 2-propanol, γ2, in relation with 2-propanol mole fraction on solvent-free basis, x′2, for the saturated mixture water (1) + 2-propanol (2) + glycerol (3) at p = 100 kPa: ○, w3 = 0.1; □, w3 = 0.3; ◊, w3 = 0.5; ●, w3 = 0.6; ■, = 0.7; ⧫, w3 = 0.8. Lines were calculated by NRTL with parameters in Table 2 at p = 100 kPa: solid lines, w3 = 0.1, 0.3, 0.5, 0.6, 0.7, and 0.8, respectively; dashed line, w3 = 0.

shown in relation with x′2. While γ2 decreases rapidly with increasing x′2 at all given w3, γ1 varies with x′2 in a more complicated manner. When glycerol mass fraction is low, for example, at w3 = 0.1 and 0.3, γ1 increases with increasing x′2. At the same time, γ1 tends to have a maximum with changing x′2 at higher glycerol mass fractions. Owing to the rapid decrease of γ2, α21 decreases rapidly with increasing x′2, as shown in Figure 4. The vapor−liquid phase behavior of the ternary system were modeled using the nonrandom two-liquid (NRTL) equation.24 For the simplicity of application, the values of nonrandomness

Figure 1. Experimental and calculated relative volatility of 2-propanol to water, α21, in relation with glycerol mole fraction, x3, for the saturated mixture water (1) + 2-propanol (2) + glycerol (3) at p = 100 kPa: ○, x′2 = 0.1; ●, x′2 = 0.2; □, x′2 = 0.4; ■, x′2 = 0.6; ◊, x′2 = 0.8; ⧫, x′2 = 0.95. Lines were calculated by NRTL parameters in Table 2 at p = 100 kPa: solid line, x′2 = 0.1, 0.2, 0.4, 0.6, 0.8, and 0.95, respectively; dashed line, x′2 = 1. C



Article

Table 3. Mean Average Deviations, δT and δy, in the Calculation of Binary VLE of Water (1) + 2-Propanol (2) and Ternary VLE of Water (1) + 2-Propanol (2) + Glycerol (3), Based on Correlation by NRTL Equation

factors c12, c13, and c23 were set as 0.3. In the correlation of binary energy parameters, data of binary VLE (Marzal et al.,25 at 30, 60, and 100 kPa; Li et al.,11 at 101.32 kPa; Li et al.,12 at 101.32 kPa) and activity coefficients at infinite dilution (Kojima et al.26) for water + 2-propanol were used, together with ternary VLE data in Table 1. The binary energy parameters were obtained by minimization of the following objective function:

data points

δT/K

δy

this work ref 25 ref 25 ref 25 ref 11 ref 12

48 27 26 25 11 12

0.17 0.40 0.27 0.28 0.27 0.18

0.0032 0.0126 0.0067 0.0078 0.0097 0.0084

(1)

N

Fternary =

source of data

experimental temperature and composition ranges, with δT = 0.17 K and δy = 0.0032. VLE data for the same ternary system at p = 101.3 kPa have been reported by Verhoeye et al.20 By using parameters proposed in Table 2, the literature ternary data were calculated. Results showed generally good agreement, with mean absolute deviations of δT = 0.40 K and δy = 0.0151. Using the binary parameters of water + 2-propanol, isobaric VLE were calculated and compared with literature values, as shown in Table 3. For correlation of isobaric VLE at 30, 60, and 100 kPa, Marzal et al.25 used three different sets of binary parameters. At 60 kPa, the present correlation has deviations of δT = 0.27 K and δy = 0.0067. This result is better than that in the original literature, which has deviations of δT = 0.36 K and δy = 0.0095. Similarly, the present correlation has deviations of δT = 0.28 K and δy = 0.0078 for data at 30 kPa. This is slightly better as compared with that of δT = 0.28 K and δy = 0.0085 in the original literature. In Figure 5, calculated vapor mole

Figure 4. Experimental and calculated relative volatility of 2-propanol to water, α21, in relation with 2-propanol mole fraction on solvent-free basis, x′2, for the saturated mixture water (1) + 2-propanol (2) + glycerol (3) at p = 100 kPa: ○, w3 = 0.1; □, w3 = 0.3; ◊, w3 = 0.5; ●, w3 = 0.6; ■, = 0.7; ⧫, w3 = 0.8. Lines were calculated by NRTL with parameters in Table 2 at p = 100 kPa: solid lines, w3 = 0.1, 0.3, 0.5, 0.6, 0.7, and 0.8, respectively; dashed line, w3 = 0.

F = Fternary + Fbinary + 5Finf

data type ternary VLE at 100 kPa binary VLE at 100 kPa binary VLE at 60 kPa binary VLE at 30 kPa binary VLE at 101.32 kPa binary VLE at 101.32 kPa

N

∑ (γ1,cal /γ1,exp − 1)2 + ∑ (γ2,cal /γ2,exp − 1)2 n=1

n=1

(1a) N

Fbinary =

N

∑ (γ1,cal/γ1,lit − 1)2 + ∑ (γ2,cal/γ2,lit − 1)2 n=1

n=1

∞ ∞ ∞ ∞ Finf = (γ1,cal /γ1,lit − 1)2 + (γ2,cal /γ2,lit − 1)2

(1b) (1c)

where N is the number of data points. In the correlation, temperature-dependent parameters were used for water + 2propanol, while parameters for water + glycerol and 2-propanol + glycerol were supposed to be temperature-independent. Results are summarized in Table 2. Using the obtained parameters, ternary VLE data were calculated in comparison with the experimental values. Results are shown in Table 3, in which δT and δy are, respectively, mean absolute deviations of equilibrium temperature and vapor phase mole fraction. The NRTL model, using temperatureindependent parameters for water + glycerol and 2-propanol + glycerol, appeared to be adequate for the ternary system in the

Figure 5. Composition diagram for the vapor−liquid equilibrium of water (1) + 2-propanol (2): □, Li et al. (ref 11), at p = 101.32 kPa; ○, Li et al. (ref 12), at p = 101.32 kPa; ◊, Marzal et al. (ref 25), at p = 100 kPa; solid lines, calculated by NRTL with parameters in Table 2 at p = 100 kPa.

fractions were compared with literature values at 100 and 101.32 kPa. Literature values of Marzal et al.25 show some extent of deviation from those of Li et al.11,12 In this sense, the

Table 2. Estimated Values of Binary Parameters in the NRTL Equationa

a

component i

component j

aij

bij/K

aji

bji/K

cij

water water 2-propanol

2-propanol glycerol glycerol

5.3852 0 0

−1005.06 617.62 259.42

−2.5041 0 0

850.87 −499.09 402.30

0.3 0.3 0.3

τij = Δgij/RT = aij + bij/T; Gij = exp(−cijτij). D



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present correlation is satisfactory. Activity coefficients at infinite dilution for water (1) + 2-propanol (2) were calculated and are given in Table 4, in comparison with those of Kojima et al.26

a

T/K

literature valuea

calculated value

relative deviation

γ∞ 1 γ∞ 2

355.35 373.15

3.1 12.63

2.94 11.62

5.2% 8.0%

Kojima et al. (ref 26).

The calculated value of γ1∞ was 2.94. This is in good agreement with the literature value of 3.1. For γ2∞, the calculation had relatively large deviation. The calculated value of 11.62 is somewhat smaller than the literature value of 12.63. However, this result appears better than that reported by Marzal et al.25 using only VLE data at 100 kPa in the correlation, giving a calculated value of 9.51 for γ2∞. Calculated results for the ternary VLE of water + 2-propanol + glycerol are also shown in Figures 1 to 4, in comparison with experimental values. Generally good agreement can be observed. As shown in Figure 4, α21 decreases with the addition of glycerol at x′2 < 0.05, showing a salting-in effect. This provide additional information because salting-out effect can always be observed in the experimental composition region at x′2 > 0.1. The salting-in effect is mainly due to rapid decrease of γ2 with the addition of glycerol in the water-rich region, as shown in Figure 3. Further, relative volatility of 2-propanol to water was calculated at x′2 = 1 in relation with glycerol mole fraction. Results are shown in Figure 1. The minimum amount of glycerol needed for breaking the water + 2-propanol azeotrope is 0.162 in mole fraction, or 0.229 in mass fraction. The required mass fraction of glycerol for breaking the azeotrope is comparable with that of [emim]OAc (0.222), [bmim]OAc (0.235), and [bmim]Cl (0.223) and is less than that of [emim][N(CN)2] (0.265), [bmim][N(CN)2] (0.350), [emim]BF4 (0.318), and [bmim]BF4 (0.406).19 This indicates that glycerol is a potentially effective entrainer for dehydration of 2-propanol by extractive distillation.

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CONCLUSIONS Isobaric VLE were measured for the ternary system water (1) + 2-propanol (2) + glycerol (3). The experimental ternary data, together with binary VLE data and activity coefficients at infinite dilution for water + 2-propanol, were correlated by NRTL equation. The experimental results were compared graphically with those of calculation, showing good agreement. With the addition of glycerol, the azeotrope of water + 2propanol can be removed at a glycerol mass fraction of 0.229. Glycerol is a potentially effective entrainer for dehydration of 2propanol by extractive distillation.

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REFERENCES

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Table 4. Deviations in the Calculation of Activity Coefficients at Infinite Dilution, γ∞, of Water (1) + 2Propanol (2), Based on Correlation by NRTL Equation data

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The authors wish to acknowledge the financial support by the National Natural Science Foundation of China (21476205). Notes

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