SELECTION OF EQUATIONS OF STATE MODELS FOR PROCESS SIMULATOR

Chorng H. Twu* , John E. Coon, Melinda G. Kusch, and Allan H. Harvey
Simulation Sciences, Inc., 601 South Valencia Avenue, Brea, CA 92621 (USA) (Workbook meeting 7/26/94; Outline from MGK 7/28/94, Revised form 8/3/94)

INTRODUCTION There are two traditional classes of thermodynamic models for phase equilibrium calculations: one is liquid activity coefficient and the other is equation-of-state models. Activity coefficient models can be used to describe mixtures of any complexity, but only as a liquid well below its critical temperature. What is an equation of state ? Any mathematical relation between volume, pressure, temperature, and composition is called the equation of state and most forms of the equation of state are of the pressure-explicit type. Many equations of state have been proposed, but most all of them are essentially empirical in nature. The virial equation of state has a sound theoretical foundation and is free of arbitrary assumption. However, the virial equation is appropriate only for the description of properties of gases at low to moderate densities. The virial equaions of state are polynomials in density. The simplest useful polynomial equation of state is cubic, for such an expression is capable of yielding the ideal gas equation as volume goes to infinite and of representing both liquid-like and vapor-like molar volumes at low temperatures. This latter feature is necessary for the application of an equation of state to the calculation of vapor-liquid equilibria. A cubic equation of state (CEOS) usually contains 2 or 3 parameters. These parameters in the CEOS are constrained to satisfy the critical point conditions. As a result, the cubic equations of state provide an exact duplication of the critical temperature and critical pressure which is the end point of the vapor pressure curve. These constraints also lay out a foundation for the alpha ( α)
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. using asymmetric mixing rules allows cubic equations of state to be used for a broad range of nonideal mixtures which previously could only be described by activity coefficient models.e. 1966. 1972). such as enthalpy. and to generate all thermodynamic properties. The success of correlating vapor-liquid equilibrium data using a cubic equation of state also depends on the mixing rules upon which the accuracy of predicting mixture properties relies. 1964. to adequately handle high pressure systems. to predict a critical point of mixtures.function (Wilson. can be used for the description of phase behavior of nonpolar and slightly polar systems (i. Soave. hydrocarbons and inorganic gases). in a consistent way. Redlich and Kwong (1949) proposed the first vdW modification that was used extensively for engineering calculations for vapor phase properties of mixtures containing nonpolar components. EQUATION-OF-STATE ADVANTAGES The equation-of-state has an inherent advantage over the traditional liquid activity coefficient methods in that it is able to directly handle supercritical components which do not form liquid (hence. with the usual van der Waals one-fluid mixing rule. Cubic equations of state. liquid activity coefficients cannnot be determined and Henry's constants are required). then the CEOS is applicable to important systems encountered in industry practice. One of the important features in applying a cubic equation of state is that the α function in the cubic equation of state can be adjusted to provide an accurate description of the vapor pressure of any nonpolar and polar components from the triple point to the critical point. to properly calculate K-values near or at the critical point. Therefore. This feature is important because the accurate prediction of pure component vapor pressures is prerequisite for accurate vapor-liquid calculations. On the other hand. SOAVE-REDLICH-KWONG EQUATION OF STATE The first CEOS that represented both vapor and liquid phases was proposed by van der Waals (1873) over a century ago. to handle both vapor and liquid phases in large ranges of temperature and pressure. The equation of state starts gaining popularity in the computation of equilibrium K-values since Soave modified the Redlich-Kwong cubic 2 . if a CEOS is equipped with a flexible α function and an advanced mixing rule.

was the first to introduce a general form of the temperature dependence of the "a" parameter in the Redlich-Kwong equation of state: P= with a ( T ) = α ( T ) a ( Tc ) RT a − v −b v ( v + b) (1) (2) The constants a(T c) and b for SRK CEOS are obtained from the critical constraints. PENG-ROBINSON EQUATION OF STATE Peng and Robinson (1976) proposed the the following CEOS. 3 .574 ω − 0. The α(T) function that gained widespread popularity was proposed by Soave (1972) as an equation of the form: α =[ 1 + m ( 1 − T r 0. For example the liquid density calculation is better for n-hexane.(3) and (4) represented a significant progress in the application of a CEOS.175ω 2 (4) Soave's development of eqns. Tr = T/Tc.480 + 1.7 and was correlated as a function of ω for the SRK CEOS: m = 0.5 ) ] 2 (3) The m parameter was obtained by forcing the equation to reproduce the vapor pressure for nonpolar hydrocarbon compounds at Tr = 0. Wilson later (1966) expressed α(T) as a function of the reduced temperature. Wilson (1964) however. but was not successful.(1) in the volume function: P= RT a − v −b v ( v + b) + b( v − b) (5) The PR CEOS improves the calculation of liquid density for mid-range hydrocarbons relative to the RK CEOS. and the acentric factor ω for the Redlich-Kwong CEOS. which is slightly different from eqn. but worse for methane.equation of state (SRK CEOS) in 1972.

Water is then 4 . NC4 / 15. IC4 / 16. efficient method to simulate the three phase behavior exhibited by hydrocarbonwater systems when the solubility of hydrocarbons in the water liquid phase can be neglected. ETHENE / * 8. The following example shows how to use the decant option for refinery columns in the waterhydrocarbon calculations: TITLE PROBLEM=DECANT. the Soave approach was subsequently used in the work by Peng and Robinson (1976). The free water option is a simplication of the thermodynamics treatment for water-hydroacrbon systems. C1 / 7. USER=SIMSCI PRINT INPUT=FULL COMP DATA LIBID 1. For the free water or decant option. It is adequate for most hydrocarbon calculations such as refinery columns with steam stripping and natural gasoline plants. The vapor is first saturated with water at its vapor pressure. H2O / 2. This helped the Peng-Robinson cubic equation of state (PR CEOS) to also become one of the most widely used equations of state in industry for correlating the vapor-liquid equilibria of systems containing nonpolar and slightly polar components SRK OR PR METHODOLOGY CEOS WITH FREE WATER DECANT Refinery systems often contain both water and hydrocarbons.Although the Soave's α function is found to be incorrect at high reduced temperatures as it does not always decrease monotonically with increasing temperature. IBTE / * 13.H2S/6. N2 / 4. PROPENE / 10. water is considered as forming an immiscible phase with the hydrocarbon-rich liquid phase The free water option is a convenient. Mixtures with water and hydrocarbons will form two liquid phases. C2 / 9. 1BUTENE / 11. BTC2 / 12. SET = SET01. H2 / 3. CO2 / 5. one is water-rich phase and the other is hydrocarbon-rich phase. 13BD / 14. NC5 THERMO DATA METHOD SYSTEM = SRK. DEFAULT WATER DECANT = ON The free water technology is a semi-rigorous three phase (VLLE) calculations.

entropy and density are predicted either from saturated condition.dissolved in the hydrocarbon liquid up to its solubility limit. xw. which relates the partial pressure of water vapor in natural gas to temperature and pressure. The following example indicates that the K-value of water in the hydrocarbonrich liquid phase is calculated from GPSA and SimSci methods and the properties of pure water liquid phase are calculated from the Keenan and Keyes equation of state : TITLE PROBLEM=DECANT. and any remaining water is decanted as a free water phase. or the cubic equation of state. The GPSA Figure 15-14. the Keenan and Keyes equation of state. the solubility of water in the hydrocarbon-rich liquid phase. and system pressure. the properties of pure water phase including vapor pressure. On the other hand.2 in the API Technical Data Book (1982). The water solubility in the hydrocarbon-rich liquid phase can be computed by either the method developed by SimSci. is recommended for natural gas mixtures above 2000 psia and Antoine saturated water vapor pressure is proper for most problems. enthalpy. using the following equation: Kw = x pw wP (6) The water partial pressure is calculated from either Antoine vapor pressure equation with coefficients properly stored for different temperature ranges or Figure 15-14 in the GPSA Data Book (1976).e. The K-value of water in the hydrocarbon-rich liquid phase is computed in the way just mentioned above. pw. which relates the solubility of water in kerosene to temperature. The Keenan and Keyes equation of state is recommended for superheated water vapor. USER=SIMSCI PRINT INPUT=FULL 5 . P. Figure 9A1. The K-value of water in the hydrocarbon-rich liquid phase can then be computed from water partial pressure. 1969). or from steam table (i. which is the default and adequate for most problems.

N2 / 3. not all these equations have the necessary binary interaction parameters to do the proper split.IC5/11. When hydrocarbon or light gas solubility in the water phase is an important consideration for the problem being analyzed. O2 THERMO DATA METHOD SYSTEM(VLLE) = SRK. N2/4.94.3.COMP DATA LIBID 1. C3/8. the free water option is not adequate and a rigorous three phase calculation must be performed for hydrocarbon-water systems. USER=SIMSCI PRINT INPUT=FULL COMP DATA LIBID 1. e. H2O/2. H2S/3. CO2/5. ETHENE / 7.. CO / 4. 1BUTENE / 10.164.66 ASSAY CHAR=SIMSCI THERMODYNAMIC DATA METHOD SYSTEM=SRK. CUT1. the free water option is adequate to represent water-hydrocarbon phase behavior. an enviromental question. NC5/12.376. the free water (decant) option must be deactivated. CUT2. 6 . C2 / * 8.204. however. H2O / 15.DEFAULT WATER DECANT=ON. NC4/10. 3BT1 / 17. IBTE / 12.310. H2 / 2. When the standard SRK or PR CEOS are selected for three phase calculations.SET=SET01. PROPENE / 9.100. C1/6. C2/7. SET = SET01. CO2 / 5. The example given below shows how to use SRK CEOS for three-phase (VLLE) calculations: TITLE PROBLEM=VLLE.820.44/* 15.921. the free water phase contains no dissolved hydrocarbons or light gases.GPSA. 13BD / * 13.44/14. however. NC6 PETRO 13. IC4 / 16.SOLUBILITY=SIMSCI.* PROPERTY=STEAM Note that all of the SRK and PR equations of state in PRO/II are capable of predicting three phase behavior.715. DEFAULT WATER DECANT = OFF SRK CEOS WITH KABADI-DANNER MIXING RULE Although for most refining and natural gas calculations.g.8. NC5 / 14. C1 / 6.0. BTC2 / 11. CUT3. IC4/* 9.

3BT1 / 17. CO2 / 5. DEFAULT Note that the SRKKD mixing rule leads to inconsistencies when a component is split into two or more identical fractions. USER=SIMSCI PRINT INPUT=FULL COMP DATA LIBID 1. CO / 4. The rigorous three phase calculation can be performed for hydrocarbon-water systems by using the Soave-Redlich-Kwong-Kabadi-Danner (SRKKD) equation. They contain usually 1 to 3 empirical parameters to be derived from vapor pressures of individual compounds.Kabadi and Danner (1985) proposed a two-parameter mixing rule for the SRK equation of state. IC4 / 16. PROPENE / 9. 13BD / * 13. O2 THERMO DATA METHOD SYSTEM(VLLE) = SRKKD. N2 / 3. 1BUTENE / 10. ETHENE / 7. IBTE / 12. H2O / 15. Numerous α functions have been proposed for this purposed. Among them.(1991) are recognized as the most flexible ones with correct extrapolation to high reduced temperatures. C2 / * 8. vapor pressures of both nonpolar and polar components can be very accurately represented by any cubic equation of state if the temperature dependent α function is sufficiently flexible. a two-parameter α function proposed by Twu (1988) and a three-parameter α function proposed by Twu et al. In fact. ALPHA (α) FORMULATION The accurate prediction of pure component vapor pressures is required for accurate vapor-liquid calculations and the ability of predicting vapor pressure from any CEOS is controlled by the selection of an appropriate temperature dependent α function. C1 / 6. The example given below shows how to use SRKKD for three-phase (VLLE) calculations: TITLE PROBLEM=SRKKD. H2 / 2. NC5 / 14. These two α functions. are: α = Tr 2 ( M −1) e L ( 1− Tr 2M ) (7) 7 . BTC2 / 11. SET = SET01. which become SimSci α functions. This method was also found to give large errors for the aqueous phase.

IPENTANE/ * 9. BANK=PROCESS THERMODYNAMIC DATA METHOD SYSTEM=SRK.IBUTANE/7. ans vdW cubic equations of state.HEXANE/11.CO2/3. PR. ALPHA=SIMSCI must be specified for SRK or PR CEOS in the input file as shown below: TITLE PROBLEM=ALPHA. the other is the mixing rules upon which the accuracy of predicting mixture properties relies.ETHANE/ * 5.BUTANE/8. such as glycols. USER=SIMSCI PRINT INPUT=FULL COMPONENT DATA LIBID 1. The mixing rules originally proposed for a CEOS are derived from van der Waals one-fluid approximation: a= ∑ ∑ x x aij i j (9) where aij = ( aiaj ) (1 / 2 ) (1 − kij ) The Kay’s mixing rule was applied to the constant b: b= (10) ∑xb i i (11) 8 .PENTANE/10.DEFAULT KVALUE ALPHA=SIMSCI.NITROGEN/2.α = Tr N ( M −1) e L ( 1− Tr N M ) (8) where the integer 2 in eqn.SET=SET01.HEPTANE. BANK=PROCESS CLASSICAL QUADRATIC MIXING RULES The success of correlating vapor-liquid equilibrium data using a cubic equation of state primarily depends on two things: one is the α function.METHANE/4.PROPANE/6. PRO/II allows the user to utilize a choice of 12 different alpha formulations for SRK. To use component-dependent α function in the calculations. which is described in the previous section.(6) has been replaced by a parameter N to improve vapor pressure prediction for highly polar substances with high normal boiling point temperatures.

(10). The standard method for introducing a binary interaction parameter. Over the past decade. While this is a good approximation for hydrocarbon mixtures. Since the equationof-state method does not effectively model strongly polar/polar and/or polar/nonpolar systems. liquid activity coefficient methods are typically ultilized for such kind of chemical systems. equations of state were used virtually only for nonpolar hydrocarbons and slightly polar components. An appropriate temperature dependent α function is required to represent accurately the vapor pressure of pure components and a proper mixing rule is essential to correctly 9 . kij. Therefore. into this classical mixing rule is to correct the assumed geometric mean rule for the "aij" parameter in the eqn. The SYSTEM=SRK in previous examples are standard SRK equation of state. The cubic equations of state with classical quadratic mixing rules are capable of accurately representing vapor-liquid equilibria for non-polar hydrocarbon systems with only one adjustable binary parameter.The quadratic mixing rule is the most widely used for equations of state. ADVANCED MIXING RULES Equations of state with the classical mixing rules are applicable only to the computation of phase equilibria in mixtures of nonpolar and weakly polar systems. For predicting such highly non-ideal systems. in the 1970's and 1980's. it cannot be applied to systems containing strongly polar or associating components. the advanced mixing rules in addition to the advanced α function are required for the equations of state. Interactions are strong between different chemical types. and the standard SRK or PR CEOS do not work well for prediction of such highly non-ideal phase behavior. The quadratic mixing rule is used for standard SRK and PR cubic equations of state. Chemical systems consisting of components with varying chemical nature can exhibit highly non-ideal phase behavior and thus are difficult to predict. the equations of state have significantly progress in the development of the most appropriate α functions and advanced asymmetric mixing rules for systems containing strongly polar components.

it should not be extended to multicomponent mixtures because it is not invariant when a component is split into two or more identical fractions (Michesen and Kistenmacher. While it is a good approximation for hydrocarbon mixtures to assume that k12 = k21. They have proposed modified classical quadratic mixing rules that use composition-dependent binary interaction parameters. SimSci has modified the Panagiotopoulos-Reid mixing rule to reduce the dilution effect to a minimum for better prediction of phase behavior of 10 (12) . however. The derivation of the infinite dilution activity coefficients from the equation of state indicates that k12 or k21 is directly related to the infinite dilution activity coefficients γ 1 ∞ or γ 2 ∞ . and can make use of available binary interaction parameters for SRK CEOS. respectively. The inability of classical quadratic mixing rules to represent the phase behavior of strongly nonideal mixtures can be explained in terms of infinite dilution activity coefficients (Twu et al. The mixing rule proposed by Kabadi and Danner (1985) is an example of using two binary parameters. 1992). Another particular example of using two binary interaction parameters was proposed by Panagiotopoulos and Reid (1986). the classical quadratic mixing rule is recovered. although it is not quite successful in the aqueous phase. Because the Panagiotopoulos-Reid mixing rule is very powerful and yet very simple. 1990). aij = ( aiaj ) ( 1 / 2) [(1 − kij ) + ( kij − kji ) x i ] If kij = kji. this assumption cannot be applied to highly asymmetric systems containing strongly polar or associating components. for example. The Panagiotopoulos-Reid mixing rule provides an excellent representation of the phase equilibria of highly non-ideal binary mixtures.predict vapor-liquid and/or vapor-liquid-liquid phase behavior of highly nonideal chemical systems. Unfortunately.. The failure of classical quadratic mixing rules for strongly nonideal mixtures can therefore be overcome by using two binary parameters and accurate results can be obtained for such mixtures when different values of binary parameters are used for. the water-rich and hydrocarbon-rich phases.

The SRKM mixing rule is given below: aij = ( aiaj ) (1 / 2 )[(1 − kij ) + ( k ij − kji )( xi / ( x i + xi )) cij ] (13) As mentioned previously. which was not found in SIMSCI databank. NC6 THERMODYNAMIC DATA METHOD SYSTEM(VLLE)=SRKM. CO2/5. the SRKM method is recommended. the variance problem still exists. NC4/9. should be input through SRKS keyword to improve the calculation results. L2KEY=1 KVALUE BANK=SIMSCI Although the SRKM mixing rule reduces the dilution effect. These methods also have been found to be quite accurate for cryogenic processes such as nitrogen rejection plants and air separation plants. The mixing rule proposed by Twu et al. N2/4. SRKS mixing rule and SimSci α function are applied to a highly non-ideal system in following example. The binary interaction parameters between ethanol and benzene. C3/ * 8. C1/6.* L1KEY=10. but also to reproduce the activity coefficients in the infinite dilution region as well as to model phase behavior throughout the finite range of concentration. SET=01. MEOH/3. methanol and water. The follwoing example shows that the SRKM mixing rule is applied to natural gas mixtures with methanol and water: TITLE PROBLEM=SRKM.multicomponent mixtures. 11 . (1991) have proposed a mixing rule not only to overcome the flaw for multicomponent mixtures as exhibited by the Panagiotopoulos-Reid mixing rule. H2O/2. typical natural gas processing plants are best represented with the SRK and PR equations of state. NC5/10. (1991) was called SRKS mixing rule. Twu et al.g. DEFAULT. USER=SIMSCI PRINT INPUT=FULL COMP DATA LIBID 1. C2/7. This modified Panagiotopoulos-Reid mixing rule is named as SRKM mixing rule. When accurate calculations are needed for natural gas mixtures with e.

(1991) was used in the hexamer equation of state.IC4. Hexamer equation of state provides a new method for calculating the properties of HF mixtures. 1993). and enthalpy departure of HF mixtures exhibit significant deviations from ideal behavior. heat of vaporization. -42.00971. 0.H2O THERMO DATA METHOD SYSTEM(VLLE)=SRKS. -322. vapor compressibility factor.68601. * 0. Hydrogen fluoride strongly associated by hydrogen bonding and strong evidence indicates that the vapor exists primarily as monomer and hexamer.ETOH/2.9063. 2. PRO/II has a large bank of binary interaction parameters for hexamer equation of state for HF alkylation process and manufacture of refrigerants.NC4/4. 0.C3/3. 1. -3. It is used in the HF alkylation process and in the manufacture of refrigerants and other halogenated compounds. -0. USER=SIMSCI PRINT INPUT=FULL COMP DATA LIBID 1. L2KEY=3 KVALUE ALPHA=SIMSCI SRKS 1. BANK=PROCESS 12 . A monomer-hexamer chemical equilibrium model is built into the cubic equation of state to account for association of hydrogen fluoride (Twu et al. Failure to take this chemical association into account can lead to serious errors in vapor-liquid and vapor-liquid-liquid equilibrium and energy balance calculations.TITLE PROBLEM=SRKS.275771. Alkylation processes and the manufacture of refrigerants simulated by the use of hexamer equation of state are given by the following two examples: TITLE PROBLEM=ALKYLATION.HF/2. The SRKS mixing rule proposed by Twu et al. LIKEY=2.BNZN/3. USER=SIMSCI PRINT INPUT=FULL COMP DATA LIBI 1.428.998951 HEXAMER EQUATION OF STATE Hydrogen fluoride is an important chemical in the chemical industry.. The calculated fugacity coefficient.

R134A. On the other hand. and entropy.THERMO DATA METHOD SYSTEM(VLLE)=HEXAMER TITLE PROBLEM=REFRIGERANT. unlike the constants (a and b) of cubic equation of state. BANK=SIMSCI THERMO DATA METHOD SYSTEM(VLLE)=HEXAMER BENEDICT-WEBB-RUBIN-STARLING EQUATION OF STATE Although the cubic equations of state proved to be especially useful in their simplicity. which are constrained to satisfy the critical point conditions. USER=SIMSCI PRINT INPUT=FULL COMP DATA LIBID 1. The BWRS is quite often employed to calculate K-value. Therefore. However. enthalpy.BANK=SIMSCI THERMO DATA 13 . the accuracy of predicting liquid density and liquid enthalpy are not quite high even for nonpolar hydrocarbons.HXE1. One of the typical examples is given below: TITLE PROBLEM=BWRS.H2/2.. enthalpy.TFETH. and density for hydrocarbon and industrial important gas systems in the cryogenic liquid region in addition to higher temperature regions. the non-cubic equation of state such as the Benedict-Webb-Rubin-Starling (BWRS) equation of state (Starling. in addition to vapor pressure for hydrocarbons in the cryogenic liquid region in addition to higher temperature regions.IC4/4.ETLN/3. efficient computation time and reliability in the K-value calculations. 1973) is capable of representing for both liquid and vapor phases the density. the K-value calculations from BWRS for hydrocarbons near the critical point may not be as reliable as that from CEOS. USER=SIMSCI PRINT INPUT=FULL COMP DATA LIBID 1. entropy.HF/2. the constants (total is 11) of Benedict-Webb-Rubin-Starling equation are not satisfied with the critical contraints.

(7) and (8) for SRK. PROBLEM=ALPHA.IPENTANE/ * 9.PENTANE/10. PR. the BWRS equation of state is better for representing pure fluid properties and less attractive for mixtures because it does not offer any advantages over cubic equations of state in K-value calculations.HEPTANE. USER=SIMSCI PRINT INPUT=FULL COMPONENT DATA LIBID 1. BANK=PROCESS 14 .CO2/3. PR. SimSci has compiled a data bank of α parameters for all the components in the SimSci component library using the α functions given by eqn. The following example applies BWRS equation of state to pure hydrocarbon for the prediction of properties at any temperature and pressure: TITLE PROBLEM=BWRS.SET=SET01.ETHANE/ * 5. It may also require considerably more computing times. BANK=PROCESS THERMODYNAMIC DATA METHOD SYSTEM=SRK.METHOD SYSTEM=BWRS KVALUE BANK=SIMSCI In general. and vdW CEOS. ans vdW cubic equations of state.IBUTANE/7. PRES=PSIG COMP DATA LIBID 1.METHANE/4.BANK=SIMSCI THERMO DATA METHOD SYSTEM=BWRS DATABANK: ALPHA PRO/II allows the user to utilize a choice of 12 different alpha formulations for SRK.BUTANE/8.ETLN. The following is an example showing how to retrieve component-dependent α parameters from SimSci databank and to input you own α parameters for SRK CEOS: TITLE PROJECT=TRAINING.HEXANE/11.PROPANE/6.NITROGEN/2.DEFAULT KVALUE ALPHA=SIMSCI. USER=SIMSCI DIME ENGLISH.

PR. equations which fit a wide range of hydrocarbon applications and in most of cases does not require additional input binary interaction parameters from the user. It is good practice to inspect the reprint of binary interaction parameters and verify that parameters are present for key binary components which accurate calculations are needed. be improved by supplying binary interaction parameters to the BWRS mixing rules (Starling. the Soave-Redlich-Kwong and Peng-Robinson equations of state are the proven methods for most hydrocarbon applications involving mixtures of non-polar hydrocarbons and non-hydrocarbon gases (e. in eqn. SRKM. CO2. The accuracy of the K-value calculation from BWRS can.). H2/2. NC6/4.10). The following example shows all the binary interaction parameters and their sources can be retrieved from SIMSCI databank by using the INPUT=FULL in the input file: TITLE PROBLEM=KIJ.340339. 1973). for these cubic equations of state.0. BNZN 15 . as usually. For hydrocarbon systems. The binary interaction parameter. kij.844963. However. PRO/II has a data bank of binary interaction parameters supplied in DECHEMA (1982) for the Benedict-Webb-Rubin-Starling equation.SA06 11. etc.2. H2S/3. which behave in an orderly fashion.38332 DATABANKS: BINARY INTERACTION PARAMETERS The data bank of binary interaction parameters is essential in modelling flowsheet.g. to tune the classical quadratic mixing rule for the equation of state.0. H2S. are usually obtained from the regression of PTXY data. USER=SIMSCI PRINT INPUT=FULL COMPONENT DATA LIBI 1. (kij. and SRKS. N2. PRO/II already contains a large data bank of binary interaction parameters for SRK. the accuracy of the K-value calculations can often be improved by supplying binary interaction parameters.

00 0. Having these two elements.THER DATA METHODS SYSTEM=SRK KVALUE BANK=SIMSCI The follwoing reprint from the simulation run indicates that all the binary interaction parameters but one were found in SIMSCI databank.J) B(I.00 0.5000 0. 16 . CO2.J) ---------. the key application guideline of a CEOS primarily depends upon the availability of binary interaction parameters for the system. A flexible α function and an advanced mixing rule allow cubic equation of state to be used for a broad range of nonideal mixtures which previously could only be described by activity coefficient models.0600 0. the other is the mixing rule.J) + B(I.00 0. H2. SRK INTERACTION PARAMETERS KIJ = A(I. The proprietary MW correlation was then used to estimate the binary parameter for this binary which parameters were not found in the databank.0141 0.0800 0.00 UNITS --------DEG K DEG K DEG K DEG K DEG K DEG K FROM ------------------SIMSCI BANK SIMSCI BANK SIMSCI BANK SIMSCI BANK MW CORRELATION SIMSCI BANK APPLICATION GUIDELINES We have discussed that the success of correlating vapor-liquid equilibrium data using a cubic equation of state primarily depends on two things: one is the α function.0680 0.00 -0.00 0.00 0.00 0.00 0.--1 2 1 3 1 4 2 3 2 4 3 4 A(I.J)/T**2 I J --.00 0.00 0.J) ---------0. Soave-Redlich-Kwong and Peng-Robinson equations of state are recommended for most hydrocarbon applications involving mixtures of nonpolar hydrocarbons and inorganic gases such as H2S.0830 0.00 C(I. etc.J)/T + C(I.---------0.

and Danner. Hill. Although SRKKD is recommended in API Technical Data Book (1982) for water and light hydrocarbons mixtures. and Moore. 537-541. "A Modified Soave-Redlich-Kwong Equation of State for Water-Hydrocarbon Phase Equilibria". The success of applying either SRKM or SRKS equation of state to nonideal systems is to verify that parameters are present for key binary components.H.. Chem. Oklahoma.G. 1990.. Tulsa. SRKM is recommended for polar/polar and/or polar/nonpolar systems which the standard SRK or PR equation of state cannot handle. John Wiley & Sons Inc.g. "On Composition-dependent Interaction Coefficients. 1976. 1985. Des. Keenan. hydrocarbons and inorganic gases). R. H.. J. The SRK-Kabadi-Danner mixing rule is composition dependent." Fluid Phase Equilibria. VI. Michelsen... U. J. REFERENCES API Technical Data Book-Petroleum Refining. Eng.L. 1982. P... M. J. American Petroleum Inst. and Kistenmacher. Vol..M. R. SRKS is recommended for HF alkylation process and the manufacture of refrigerants and other halogenated compounds. Oelirich. Kabadi.. L. published by DECHEMA. 24(3). Doring.. Ind. “Steam Tables”. F. NY. 1982. the calculated results may not be reliable due to the inconsistency problem in its mixing rule. H.BWRS is an excellent equation of state for predicting properties of pure hydrocarbons and gases at any temperature and pressure and is suitable for the application to non-polar hydrocarbon and industrial gas mixtures. Plocker.. Chemistry Data Series. Keyes. “Vapor-liquid Equilibria for Mixtures of Low Boiling Substances”.P. It was developed specifically for water and well-defined light hydrocarbon systems. dev. 17 . 59:229-230.G. GPSA Engineering Data Book. 1969. Germany.. Knapp. Proc.N.. SRKS is also suitable for polar/polar and/or polar/nonpolar systems. V.G... Gas Processors Suppliers Association. New York. and Prausnitz. SRKM is reduced to the standard SRK CEOS for nonpolar mixtures (e.

Rev. 44:233244. J. 72:25-39. supercritical Systems.. Bluck. Bluck. Twu. Wilson. 1988. 1991. Ser. C. "A Cubic Equation of State: Relation Between Binary Interaction Parameters and Infinite Dilution Activity Coefficients.R. Sci. Cryog.R. DC...Panagiotopoulos.. D. 1964. Wilson.".H.. J. 1873.B.C. 18 . and Coon.H. D. J. Adv. G.H. Fluid Phase Equilibria... Gulf Publ. TX. Ind. "Calculation of Enthalpy Data from a Modified RedlichKwong Equation of State". C. pp. Twu. "An Equation of State: for Hydrogen Fluoride.. May 30-June 2." International Symposium on Thermodynamics in Chemical Engineering and Industry. Eng.E. Holland. “Fluid Thermodynamic Properties for Light Petroleum Systems”." ACS Symp. D. 1988. Adv.M. J. Leiden. Cunningham. Fundam. Twu. "Vapor-liqumid Equilibria Correlated by Means of a Modified Redlich-Kwong Equation of State". "A New Two-constant Equation of State". Washington.".Y. Eng. 15:58-64. 1966. 1972.. C.. and Cunningham..R. 1992. Chem. Redlich. J. Doctoral Dissertation...H. Houston. 571-582. Coon. D. C. 1976.E.. Starling K. 1949. 27:1197-1203. Chem. Soave. 11:392-400. 1973. American Chemical Society. "Equilibrium Constants from a Modified Redlich-Kwong Equation of State".E. O. A.. van der Waals. and Reid. 1986. Co. 86:47-62.. and Coon. 9:168-176. “Over de Constinuiteit van den gas-en Vloeistoftoestand”. Cunningham. Chem. "A Modified Redlich-Kwong Equation of State for Highly Polar.E.. V: An Equation of State... J. J. and Kwong. Fluid Phase Equilibria..Z. "A Cubic Equation of State with a New Alpha Function and a New Mixing Rule".. 1993. G. Eng. G. "A New Mixing Rule for Cubic Equations of State for Highly Polar Asymmetric Systems.M. Twu.. N.. Fugacities of Gaseous Solutions". 300.. Cryog. and Robinson. Fluid Phase Equilibria. Eng. "On the Thermodynamics of Solutions. 69:33-50. Peng..S.D. R.

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