Chin. J. Chem. Eng.

, 15(1) 102109 (2007)

A Modification of in SRK Equation of State and Vapor-Liquid Equilibria Prediction

LUO Mingjian()a,b, MA Peisheng()b,* and XIA Shuqian()b
a b

School of Chemistry and Chemical Engineering, Daqing Petroleum Institute, Daqing 163318, China Key Laboratory for Green Chemical Technology School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Abstract Based on results of saturated vapor pressures of pure substances calculated by SRK equation of state, the factor in attractive pressure term was modified. Vapor-liquid equilibria of mixtures were calculated by original and modified SRK equation of state combined with MHV1 mixing rule and UNIFAC model, respectively. For 1447 saturated pressure points of 37 substance including alkanes; organics containing chlorine, fluorine, and oxygen; inorganic gases and water, the original SRK equation of state predicted pressure with an average deviation of 2.521% and modified one 1.673%. Binary vapor-liquid equilibria of alcohols containing mixtures and water containing mixtures also indicated that the SRK equation of state with the modified had a better precision than that with the original one. Keywords SRK equation of state, vapor liquid equilibrium, saturated pressure, prediction

INTRODUCTION Equations of state (EOS), especially, cubic equations of state are frequently used in modeling phase equilibrium for chemical process of designing. Among cubic equations of state, SRK[1] equation of state and PR[2] equation of state are the most commonly used. These two equations of state are similar in form. They are also similar in the correction factor of parameter a. When phase equilibria of mixtures were calculated, equations of state must be combining with mixing rules. van der Waals mixing rule was a conventional used one. GE mixing rules derived by Huron and Vidal[3] were progressed by several studies[48]. Orbey and Sandler[9] had recommended this method in their monograph. Graboski and Daubert[10] revised the constant of in SRK equation of state. Mathias and Copeman[11] give a new expression of , but three constants were needed for every substance. In this article, factor in SRK equation of state was modified. Vapor-liquid equilibria predicted by SRK equation of state with the original and with the modified one were compared for several systems. 2 SRK EQUATION OF STATE AND THE MODIFICATION The original SRK equation of state is: RT a (T ) p= (1) v b v (v + b )

The saturated vapor pressures of pure substances were calculated by SRK equation of state for both liquid and vapor with the following constraint:
fi l = fi v

(6)

The deviations of saturated vapor pressures calculated by Antoine equation were small enough when Antoine parameters were available. Compared to the results of Antoine equation, the saturated vapor pressure calculated by original SRK equation of state have similar tendencies in deviation as it shown in Figs.1 and 2, which increases at first and then decreases. The deviations are found to be negative, when Tr0.65, and positive, when Tr0.7. This implies the curve (T)Tr is too bend toward downward. In this article, the correction factor (T) was modified as following:

(T ) = 1 + (0.32877 + 1.1317 ) (Tr0.5 Tr )

(7)

As shown in Figs.1 and 2, the deviations were obviously improved when Eq.(7) was used.

a(T ) = ac (T )
ac = 0.42747 R 2Tc2 pc

(2) (3)
Figure 1 Comparison of predicted saturated pressure of propane, n-pentane, and m-xylene pentane with original ; pentane with modified ; propane with original ; propane with modified ; m-xylene with original ; m-xylene with modified

(T )0.5 = 1 + ( 0.480 + 1.574 0.176 2 ) (1 Tr0.5 ) (4)

b = 0.08664 RTc pc (5)

Received 2005-11-23, accepted 2006-06-06. * To whom correspondence should be addressed. E-mail: mapeisheng@tju.edu.cn

A Modification of in SRK Equation of State and Vapor-Liquid Equilibria Prediction

103

Figure 2

Comparison of predicted saturated pressure of acetone and water acetone with original ; acetone with modified ; water with original ; water with modified

Figure 3

Differences between the original correction factor and the modified correction factor : 10; 20.1; 30.3; 40.5

Figure 3 shows the differences of Eqs.(4) and (7). The original is larger than the modified one when Tr0.65 and smaller when Tr0.7. In concert with the analysis of Figs.1 and 2, the tendency shows the reason why Eq.(7) can improve Eq.(4).
Table 1 Substance CH4 C2H6 C3H8 n-C4 H10 i-C4 H10 n-C5 H12 i-C5 H12 t-C5 H12 n-C6 H14 n-C7 H16 n-C8 H18 n-C10 H22 C2H4 C3H6 c-2-butene t-2-butene C2H2 C3H4 C6H6 C7H8 o-C8H10 m-C8H10 p-C8H10 CF4 CCl4 CH3Cl CH3OH C2H5OH Tc, K 190.56 305.32 369.83 425.12 407.8 469.7 460.4 433.8 507.6 540.2 568.7 617.7 282.34 364.9 435.5 428.6 308.3 402.4 562.05 591.75 630.3 617.0 616.2 227.55 556.31 416.26 512.5 514.0

The comparison of SRK equation of state with original and modified one was based on the results of Antoine equation. Average relative deviations were shown in Table 1. The calculation range was for every 5 from 0.5 Tc to Tc, when Antoine parameters were available. Only five of thirty-seven substances listed

Comparisons of deviation of saturated vapor pressures of pure substance Range of Tr 0.51 0.51 0.51 0.50.68, 0.751 0.50.67, 0.730.97 0.51 0.50.85, 0.91 0.60.69, 0.731 0.50.7, 0.741 0.50.71, 0.771 0.51 0.51 0.50.61, 0.711 0.51 0.50.82 0.50.66, 0.731 0.631 0.51 0.51 0.50.69, 0.741 0.50.7, 0.751 0.50.71, 0.751 0.51 0.51 0.51 0.51 0.51 0.50.68, 0.721 No. data points 19 30 35 36 35 47 42 31 47 47 55 61 23 36 29 38 22 40 56 53 57 57 60 23 55 42 51 48
Average relative deviation , %

Orig. 1.4073 1.205 1.211 1.409 1.789 1.132 1.498 0.689 2.268 2.269 1.216 2.565 0.719 0.853 0.694 2.225 1.762 0.832 0.714 1.515 3.830 2.123 2.827 2.465 1.250 1.467 7.868 3.123

Mod. 1.1849 0.609 0.425 0.570 1.540 0.785 0.445 0.351 0.814 1.521 1.894 3.820 0.480 0.311 0.898 1.500 1.112 1.003 1.233 0.726 2.148 0.479 1.164 1.950 1.064 0.991 4.075 2.648

Chin. J. Ch. E. 15(1) 102 (2007)

104 Table 1 (Continued) Substance CH3OCH3 CH3CHO CH3COCH3 CH3COOH HCOOCH3 N2 O2 CO2 H2O

Chin. J. Ch. E. (Vol. 15, No.1)

Tc, K 400.2 466 508.1 590.7 487.0 126.1 154.58 304.19 647.13

Range of Tr 0.51 0.580.8 0.510.69, 0.731 0.51 0.580.9 0.50.65 0.50.65 0.891 0.51

No. data points 40 21 46 59 32 9 10 7 48 1447

Average relative deviation, % Orig. 2.425 8.967 2.527 8.774 1.480 2.399 2.476 0.546 5.133 2.521 Mod. 1.630 8.527 0.541 5.511 0.989 1.826 1.975 0.169 2.859 1.673

total

Antoine parameters taken from Ref.[1214]. Orig.: Original SRK equation of state; Mod.: Modified SRK equation of state. Saturated pressure table taken from Ref.[12].

have larger relative deviations with modified . For most substance, the results of the modified one were much better.
3 BINARY VAPOR-LIQUID PHASE EQUILIBRIUM WITH THE MODIFIED SRK EQUATION OF STATE Multicomponents vapor-liquid phase equilibrium calculation is based on the following equation: xiil = yiiv (8)

b = xi bi
i =1

(9) (10)

n a b 1 GE n a = xi i + + xi ln bRT i =1 bi RT q1 RT i =1 bi

where q1 =0.593 for SRK EOS in Michelsens[5] study, this value was changed to q1 = 0.64663 in Holderbaum and Gmehlings[6] study. The second value was used in this article. To compare the original SRK equation of state and the modified one in multicomponents phase equilibrium prediction, vapor-liquid equilibrium prediction results of mixtures with alcohols or water were listed in Tables 2 and 3, where

It was desired to select mixing rule when calcu lating il and iv . In this article, the MHV1[5] mixing rule was selected. And GE was calculated by UNIFAC[15] group contribution method. The MHV1 mixing rule is:
Table 2

Comparison of binary vapor-liquid phase equilibria results calculated by original SRK and modified SRK (isothermal data) System T, K 308.15 328.15 308.15 322.45 313.1 318.15 328.15 293.15 453.15 273.15 313.15 373.15 273.15 303.15 333.15 No. data points 10 10 21 21 12 15 13 11 10 11 11 11 11 11 11 p/p(100) Mod. Orig. 10.794 7.824 8.824 7.628 8.078 4.881 7.553 5.699 11.411 11.362 11.433 9.142 11.953 9.822 10.688 7.630 7.142 4.329 23.424 10.733 3.062 2.427 7.989 5.110 18.431 15.339 8.960 6.598 2.825 3.655 y(100) Orig. Mod. 3.258 2.907 2.431 2.442 1.477 1.305 2.006 2.035 0.658 0.521 3.442 3.483 6.952 6.946 6.316 5.784 1.912 1.972

methanol-tetrachloromethane methanol-chloroform methanol-propane methanol-cyclohexane methanol-benzene methanol-ethanol

methanol-1-propanol

February, 2007

A Modification of in SRK Equation of State and Vapor-Liquid Equilibria Prediction Table 2 (Continued) System methanol-2-propanol methanol-acetone methanol-methyl formate methanol-methyl acetate

105

T, K 328.15 298.15 473.15 298.15 293.15 313.15 318.15 338.15 333.15 372.7 397.7 422.6

No. data points 22 14 10 17 9 9 15 17 16 10 12 12 14 12 15 9 9 9 11 16 11 11 11 16 14 10 10 10 16 16 17 18 12 14 18 15 15 15 15 15 14 14 10 21 12

p/p(100) Orig. Mod. 2.834 10.755 3.957 7.056 12.343 7.493 3.359 3.044 2.781 4.416 3.409 2.091 6.481 4.680 4.957 5.094 4.588 3.415 6.221 5.406 4.035 4.574 3.234 3.394 6.917 8.141 5.144 4.648 2.037 0.587 0.764 6.228 12.276 8.339 4.718 9.94 7.938 6.593 18.187 12.753 10.219 8.186 7.033 7.090 2.445 3.207 6.245 2.443 4.556 7.544 5.324 1.630 2.464 2.335 6.096 5.315 3.712 5.409 2.536 2.832 4.380 1.867 2.712 1.419 3.182 2.945 4.415 3.929 1.640 5.133 10.060 4.818 3.713 2.008 1.286 0.673 0.8240 7.193 4.976 2.583 4.778 4.486 4.553 9.741 8.809 8.116 5.544 6.013 5.744 1.527

Orig.

y(100) Mod. 0.990 2.026 3.144 1.723 1.947 1.479 0.898 0.797 1.182 1.810 1.852 1.108 1.520 1.477 1.984 1.411 1.045 1.122 1.239 1.344 1.867 1.354 1.255 0.499 0.941 3.537 2.201 2.995 0.318 0.294 0.457 1.045 0.547 1.491 1.437 3.140 2.365 1.615 5.145 3.782 2.200 5.630 5.023 1.166 0.614

1.000 2.052 3.073 2.457 1.939 1.429 0.671 0.900 1.174 1.912 1.920 1.147 2.040 1.397 1.970 2.467 1.263 1.090 0.586 1.299 1.501 1.130 1.079 0.526 0.771 3.660 2.189 2.940 0.312 0.287 0.514 1.021 1.239 2.699 2.217 4.131 3.532 2.872 5.423 3.928 2.083 6.452 6.084 1.450 0.979

ethanol-tetrachloromethane ethanol-chloroform ethanol-pentane

ethanol-2,2,4-trimethyl pentane

273.15 298.15 323.15

ethanol-cyclohexane

278.15 308.15 338.15

ethanol-benzene ethanol-1-propanol

298.15 323.15 323.15 343.15 353.15

ethanol-2-butanone ethanol-methyl formate ethanol-methyl acetate

328.15 298.15 323.15 343.15 353.15

ethanol-ethyl acetate

313.15 328.15 343.15

ethanol-methyl propionate water-methanol

298.15 303.05 333.15 363.15

water-ethanol

313.15 328.15 343.15

water-1-propanol

303.15 333.15 363.15

water-2-propanol

298.15 308.16 353.15 523.15

Chin. J. Ch. E. 15(1) 102 (2007)

106 Table 2 (Continued) System water-acetaldehyde

Chin. J. Ch. E. (Vol. 15, No.1)

T, K 283.15 293.15 303.15 298.15 373.15 473.15 523.15 323.15 333.15 343.15

No. data points 7 7 7 15 22 25 11 10 10 10

water-acetone

water-methyl acetate

p/p(100) Orig. Mod. 25.156 23.807 15.427 13.773 9.842 8.371 9.774 8.912 4.568 4.363 3.952 3.033 3.684 2.587 6.681 6.676 4.068 3.365 15.175 14.277

y(100) Orig. Mod. 1.537 1.316 1.890 1.618 1.261 0.935 4.216 3.181 1.282 0.766 1.140 1.179 0.646 0.732 4.022 3.033 3.086 2.063 1.869 1.181

Orig.: Original SRK equation of state. Mod.: Modified SRK equation of state. Experimental data taken from Refs.[16,17]. Experimental data taken from the data files of Orbey and Sandle[9]. Table 3 Comparison of binary vapor-liquid phase equilibria results calculated by original SRK and modified SRK (isobar data) p, kPa 101.325 101.325 98.659 69.461 45.330 30.664 methanol-ethanol methanol-tetrahydrofuran 101.325 98.659 79.993 51.196 31.331 methanol-diethyl ether methanol-acetone methanol-2-butanone methanol-methyl acetate 93.326 101.325 101.325 101.325 79.993 53.329 26.664 methanol-ethyl acetate ethanol-tetrachloro- methane ethanol-chloroform ethanol-benzene 101.325 99.325 101.325 101.325 53.329 23.998 ethanol-2-propanol ethanol-acetone ethanol-2-butanone ethanol-methyl acetate 101.325 101.325 101.325 101.325 No. data points 37 24 22 30 27 24 10 10 12 15 16 21 14 14 9 15 15 14 21 11 20 15 11 11 15 10 10 10 T, K Orig.

System methanol-tetrachloro-methane methanol-chloroform methanol-benzene

y(100) Mod. 1.957 1.068 1.437 1.566 1.722 1.713 0.399 0.707 0.665 0.795 0.789 1.277 0.621 0.975 0.751 0.996 1.274 0.830 1.123 0.905 0.619 0.698 0.472 0.291 0.226 0.604 0.302 0.971 Orig. 2.715 1.112 1.199 1.087 1.509 1.998 0.720 0.764 0.933 1.003 1.294 1.144 0.760 0.677 1.236 1.548 1.693 2.744 0.748 3.365 1.412 1.413 1.138 0.615 0.408 1.312 0.996 2.577 Mod. 2.732 1.094 1.304 1.169 1.546 1.819 0.726 0.804 0.972 0.922 1.118 0.722 0.714 0.718 1.149 1.418 1.483 2.372 0.779 3.122 1.342 1.477 1.109 0.724 0.485 1.306 0.864 2.600

2.217 1.381 1.719 2.054 2.454 2.647 0.547 0.939 1.020 1.405 1.595 1.483 0.809 1.078 0.946 1.333 1.826 1.529 1.234 0.981 0.747 0.652 0.287 0.700 0.320 0.644 0.416 1.012

February, 2007

A Modification of in SRK Equation of State and Vapor-Liquid Equilibria Prediction Table 3 (Continued) System ethanol-ethyl acetate water-methanol p, kPa No. data points 15 12 14 18 23 16 15 15 15 T, K Orig.

107

y(100) Mod.

Orig.

Mod. 0.837 0.467` 0.547 0.704 0.731 1.207 1.606 0.808 1.146

101.325 101.325 46.663 26.664 water-ethanol 333.306 101.325 50.663 water-acetone 101.325 66.661 Experimental data taken from Refs.[16,17]. Orig.: Original SRK equation of state. Mod.: Modified SRK equation of state.

0.533 1.193 1.530 2.474 0.709 1.392 1.505 1.449 1.316

0.459 0.887 0.777 1.366 0.665 1.045 0.871 1.034 0.771

0.874 1.469 1.496 1.099 0.973 2.311 2.801 1.588 1.492

pcal pexp p (100) = 100 pexp p

(11) (12) (13)

y (100) = 100 ycal yexp N T = Tcal Texp N

The experimental data taken from Vapor-Liquid Equilibrium Data Collection[16,17] recommended by the editor were used. The prediction equilibrium pressures and temperatures improved obviously, when the modified was used as shown in the Tables. The prediction of equilibrium vapor mole fractions were improved obviously for systems containing water, but for systems containing alcohols were not obvious. In addition, Figs.411 showed some experimental and calculated phase equilibria for different systems. All the figures show the results of modified SRK equation of state were more approach to the experimental points through the total composition range. The improvement may be attributed to the deviations of saturated pressure of pure substances were decreased.

Figure 5 Phase equilibrium prediction of ethanol-tetrachloromethane binary system by original SRK equation of state and modified SRK equation of state (isothermal) 318.15K; 338.15K; original SRK; - - - - modified SRK

Figure 6 Phase equilibrium prediction of ethanol-2,2,4-trimethyl pentane binary system by original SRK equation of state and modified SRK equation of state (isothermal) 298.15K; 323.15K; original SRK; - - - - modified SRK

Figure 4 Phase equilibrium prediction of methanol-benzene binary system by original SRK equation of state and modified SRK equation of state (isothermal) 293.15K; 453.15K; original SRK; - - - - modified SRK

CONCLUSIONS With the thorough analysis of SRK equation of state, a new correction factor of parameter a in SRK

equation of state was presented in this article. Compared with the original one, SRK equation of state with the modified gives better phase equilibria calculating results for both pure substances and mixtures. The new method can be used in phase equilibrium calculation without adding any complexity. It is easy to actualize the new method in programs and software with original SRK equation of state. The mixture phase equilibria were calculated by the SRK equation of state combined with MHV1 mixing rule and UNIFAC model. No binary interaction
Chin. J. Ch. E. 15(1) 102 (2007)

108

Chin. J. Ch. E. (Vol. 15, No.1)

Figure 7 Phase equilibrium prediction of ethanol-methyl propionate binary system by original SRK equation of state and modified SRK equation of state (isothermal) 298.15K; original SRK; - - - - modified SRK

Figure 11 Phase equilibrium prediction of acetone-water binary system by original SRK and modified SRK equation of state (isobar) 101.325kPa; 66.661kPa; original SRK; - - - - modified SRK

and GE models, better result may be achieved.

NOMENCLATURE
a(T) ac b f GE N p pc q1 R T Tc Tr v x y (T) l v SRK equation parameter value a(T) at T=Tc SRK equation parameter fugacity excess Gibbs energy number of data points pressure critical pressure parameter in MHV1 mixing rule gas constant absolute temperature critical temperature reduced temperature volume mole fraction in liquid mole fraction in gas correction factor fugacity coefficient acentric factor

Figure 8 Phase equilibrium prediction of ethanol-water binary system by original SRK equation of state and modified SRK equation of state (isothermal) 313.15K; 328.15K; 343.15K; original SRK; - - - - modified SRK

Superscripts Subscripts
Figure 9 Phase equilibrium prediction of 2-propanol-water binary system by original SRK equation of state and modified SRK equation of state (isothermal) 298.15K; 308.16K; 523.15K; original SRK; - - - - modified SRK cal exp i

liquid phase vapor phase calculated value experiment value i component

REFERENCES
1 2 3

4 5 6 7

Figure 10 Phase equilibrium prediction of methanol-water binary system by original SRK equation of state and modified SRK equation of state (isobar) 101.325kPa; 26.664kPa; original SRK; - - - - modified SRK

parameter was needed. This method can be used for phase equilibrium prediction. With other mixing rules
February, 2007

Soave, G., Equilibrium constants from a modified Redlich-Kwong equation of state, Ind. Chem. Eng. Sci., 27(6), 11971203(1972). Peng, D.U., Robinson, D.B., A new two-constant equation of state, Ind. Eng. Chem. Fundam., 15(1), 59 64(1976). Huron, M.J., Vidal, J., New mixing rules in simple equations of state for representing vapour-liquid equilibria of strongly non-ideal mixtures, Fluid Phase Equilibr., 3, 255271(1979). Michelsen, M.L., A method for incorporating excess Gibbs energy models in equations of state, Fluid Phase Equilibr., 60, 4758(1990) Michelsen, M.L., A modified Huron-Vidal mixing rule for cubic equation of state, Fluid Phase Equilibr., 60, 213219(1990). Holderbaum, T., Gmehling J., PSRK: A group contribution of state based on UNIFAC, Fluid Phase Equilibr., 70, 251256(1991). Wong, D.S.H., Sandler, S.I., A theoretically correct mixing rule for cubic equations of state, AIChE J., 38(5), 671680(1992). Boukoubalas, C., Spiliotis, N., Coutsikos, P., Prediction

A Modification of in SRK Equation of State and Vapor-Liquid Equilibria Prediction of vapor-liquid equilibrium with the LCVM model: A linear combination of the Vidal and Michelsen mixing rules coupled with the original UNIFAC and the t-mPR equation of state, Fluid Phase Equilibr., 92, 75 106(1994). Orbey, H., Sandler, S.I., Modeling Vapor-Liquid Equilibria-Cubic Equations of State and Their Mixing Rules, Cambridge University Press, Cambridge (1998). Graboski, M.S., Daubert, T.E., A modified soave equation of state for phase equilibrium calculation. 1. Hydrocarbon systems, Ind. Eng. Chem. Process Des. Dev., 17(4), 443448(1978). Mathias, P.M., Copeman, T.W., Extension of the Peng-Robinson equation of state to complex mixture: Evaluation of the various forms of the local composition concept, Fluid Phase Equilibr., 13, 91108(1983). 12 13 14 15

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9 10

16

11

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Ma, P.S., Chemical and Engineering Thermodynamics, Chemical Industry Press, Beijing (2005). Stephenson, R.M., Handbook of the Thermodynamics of Organic Compounds, Elsevier, New York (1987). Boublick, T., Freid, V., Hala, E., The Vapor Pressures of Pure Substances, 2nd ed., Elsevier, New York (1984). Fredenslund, A., Jones, R.L., Prausnitz, J.M., Group contribution estimation of activity coefficients in non-ideal liquid mixtures, AIChE J., 21, 1086 1099(1975). Gmehling, J., Onken, U., Vapor-Liquid Equilibrium Data Collection .1. Aqueous-Organic Systems, DECHEMA, Frankfurt (1977). Gmehling, J., Onken, U., Vapor-Liquid Equilibrium Data Collection .2. Organic Hydroxy Compounds:Alcohols, DECHEMA, Frankfurt (1977).

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