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    22 695

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    of 4
    ON THE FUNCTIONAL FORM OF THE EQUATION OF STATE FOR PREDICTION OF MIXTURE CRITICAL PROPERTIES Himostt INOMATA, Kunio ARAI AND SHOzABURO SAITO Key Words: ‘A previous paper” showed that improvement of the accuracy of BWR-type equations of state for pure components reduced the deviation between the predicted and experimental critical properties, of mixtures consisting of similar components. For asymmetric mixtures, however, the deviation tended to increase with the critical temperature ratio Ta[T..® of the components of the mixture. To examine the tendency demonstrated for the BWRctype equations in the previous paper, in the present work we calculated the critical properties of binary mixtures with extended BWR equations over a wide range of critical temperature ratio. The calculated results are compared with those obtained “I is paper, denotes theta temperature of the iter component. WoL. 22 No, 6 1809 Department of Molecuar Chemistry & Engineering Tohoku University ‘Aoba, Arama, Sendai 980 Critical Properties, Equation of State, BWR Type Equation with the Soave-Redlich-Kwong (SRK) equation of state, which is one of the currently used cubic equations. 1. Equations of state Five extended BWR equations were used in this study: an optimized 8-constant BWR equation (BWR), an optimized [1-constant BWR equa- tion (BWRS)”, a generalized 15-constant equation (BWRSN)”, and two optimized 15-constant equations (BWRS-TV, BWRSN-TP). They are expressed in common as follows RT9(ByRT ~ Ag ColT? + Dol T? — Evi Tp? + ORT=a—d/T—efT*=f/T?)p° + ulatd/T+e/T*+ f/T?)p° +(c/T?+g/T* +h/T?)p (1 + yp?) exp(—yp*) (I), 605 Table 1 Estimation error for critical properties of binary mixtures [%AAD} ‘eitcal pressure, Pox) ‘System BWR BWRS GBWRSNBWRSN-TV BWRSN-TP SRK smethane-ethane 1.60 295 210 206 096 “propane 196 302 627 158 2n “butane 22 420 924 33 539 heptane 283 a9 3274 29116 408 ethane -propane Ls9 923 3m 175 butane Lae an 383 136 aeptane am m2 64s, 267 propane:mbutane os 14s 37 O10 ceptane 16 160 1596 138 Le butane-r-heptane 127 219 16s 13 039 ‘etitcal temperature, Tin) system BWR BWRS —GBWRSNBWRSN-TV BWRSN-TP SRK rethane-ethane 160 019 ost 034 020 ous oss propane Lo 102 307 119 13 136 13s butane 223 333 376 038 090 060, Las Sreheptane 2a 221 236 42 428, 424 212 thane propane tat 139 232 056 oat 030. 019 Snatane 139 ois 34 oad 0.09 039 0.60 “heptane un 23 297 325 199 203 139 ropane:n-butane Lis 00 020 032 0.02 0.02 010 heptane 146 079 38 13 030 058 082, butane-heptane lar 026 307 090) 043 0.04 04s, ©All data used in this paper for eritical properties are given in reference 4 where Do, Eo, dse.f.d' 0 for BWR and for The constants of the BWRSN-TV and the BWRSN- ‘TP equations were determined in this work so as to satisfy the following critical criteria and to fit the volumetric data of each pure substance. (0Pi6p), 2 (Pip?) @) ‘The BWRSN-TV equation satisfies the above criteria at T= 7? and p=v$°, and the BWRSN-TP equation at T=? and P= P!*" like a cubic equation of state For other BWR equations, Eqs. (2) and (3) were not considered in determining equation constants, ‘The SRK equation” is expressed by Eq. (4). BWRS RT|(v~b) ~ajv(v+b) @ where a and 6 are equation constants evaluated for each pure component from critical properties and an acentrie factor. The same mixing rules as in the previous work?) were adopted for BWR-type equations and the following rules for the SRK equation. a=SExx faa)? Oo b= Tab where x; and x; are mole fractions of i and j components respectively. The same calculation pro- cedure as in the previous paper was used to calcu- late the critical properties. Calculations were per- formed for 10 binary hydrocarbon systems con- taining methane, ethene, propane, n-butane, and n-heptane. The binary interaction parameter is not considered in this paper. 2. Results and Discussion ‘Average deviations between calculated and experi- ‘mental results for critical pressure (P.,) and critical temperature (Tq) are listed in Table 1. The average deviations for both Py and Tey inerease as the T;a/To. value of the mixtures increases. For detailed comparison, the deviations are plotted against the value of T.a/Ta, in Fig. 1. The deviations for Poy become larger and more sensitive to the T,x/T,, value than do those for Tiy- The SRK. equation presents better results over the whole range than does the BWR equations. Among BWR-iype equations, the BWR equation with 8 constants is fairly good in the prediction of Poy. With respect to the possible reasons. for this superiority of cubic equations over BWR-type equations of state, Kurnik® suggested that the SRK equation might give better predictions of vapor-liquid equilibria (VLE) for asymmetric mixtures than BWRctype equations because of the good representa- JOURNAL OF CHEMICAL ENGINEERING OF JAPAN GBWRSN i BWRSN-TV z Teles Fig. 1. Average absolute deviations in the prediction of critical properties tion of the critical point of pure component. To examine this suggestion, VLE of ethane-n-heptane binary mixture-(T,2/T,, = 1.77) and the PVT relation- ship of each pure component were calculated with the SRK and the BWRSN-TP equations, both of which satisfy the critical criteria (Eqs. (2) and (3)) at the same condition (T=T! and P= PS), The SRK equation predicts VLE better than the BWRSN-TP equation, as shown in Fig. 2, while the saturated properties of pure components are well represented by the BWRSN-TP equation because it was developed bby using the data of such properties. As is well known, the SRK eqquation shows a typical van der Waals loop in the PVT relationship. However, the BWRSN-TP equation presents complex isotherms, exhibiting multiple maxima and minima in the unstable region at low temperatures. Other BWR-type equations have similar PVT isotherms, as shown in Fig. 3. To date, this PVT behavior in the unstable region has not been sufficiently studied because there are no experimental thermodynamic data inthis region and such behavior seems to have a negligible effect on calculation of the thermodynamic properties of pure substances. However, computer simulation has shown that the PVT relationship of a Lennard-Jones fluid shows a van der Waals loop”. In addition, isotherms in the unstable region as well as in the stable region are commonly integrated for the evaluation of fugacity. Therefore, the complex isotherms of BWRc(ype equations in Fig. 3 probably have some influnce on the prediction of the thermodynamic properties of mixtures, especially of the critical properties, because the derivatives of PVT (€P/dp, VoL. 22 No. 6 18 Pressure (MPa) t \ wok WR If 104 ' nHeptane \ lie Density (mol/t) Fig. 2. Vaporliqud equilibria for the ethane-n-heptane system 00 05 10 Fig. 3. Isothermal pressuredensity curves of BWR-type fsations of sate for heptane at 7,=08 0 Pjdp?) are used to evaluate the governing equations of the critical point. In short, isothermal behavior in the unstable as well as the stable regions should be taken into consideration for the development of an equation of state which can accurately predict the thermodynamic properties of both pure components and mixtures. Nomenclature Ae, Bos Co: Dos Bo 4, 6 def g, 9,7 constants of equations of state w Pe pressure iMPa} 687 IK) ltmat~}} H [mmol R as constant K-* mot") r temperature . = molat volume x molar fraction e density ‘

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