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SIMULATOR
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 ()
*
Corresponding author
function (Wilson, 1964, 1966; Soave, 1972). One of the important features in
applying a cubic equation of state is that the 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.
This feature is important because the accurate prediction of pure component
vapor pressures is prerequisite for accurate vapor-liquid calculations.
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. Cubic equations of state, with the usual van der Waals
one-fluid mixing rule, can be used for the description of phase behavior of
nonpolar and slightly polar systems (i.e., hydrocarbons and inorganic gases).
On the other hand, 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. Therefore, if a CEOS is
equipped with a flexible function and an advanced mixing rule, then the CEOS
is applicable to important systems encountered in industry practice.
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, liquid activity coefficients cannnot
be determined and Henry's constants are required), to handle both vapor and
liquid phases in large ranges of temperature and pressure, to adequately handle
high pressure systems, to predict a critical point of mixtures, to properly
calculate K-values near or at the critical point, and to generate all thermodynamic
properties, such as enthalpy, in a consistent way.
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. 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. The equation of state starts gaining popularity in the computation
of equilibrium K-values since Soave modified the Redlich-Kwong cubic
equation of state (SRK CEOS) in 1972. Wilson (1964) however, was the first to
introduce a general form of the temperature dependence of the "a" parameter in
the Redlich-Kwong equation of state:
P=
RT
a
v b
v ( v + b)
(1)
with
a ( T ) = ( T ) a ( Tc )
(2)
The constants a(T c) and b for SRK CEOS are obtained from the critical
constraints. Wilson later (1966) expressed (T) as a function of the reduced
temperature, Tr = T/Tc, and the acentric factor for the Redlich-Kwong CEOS,
but was not successful. The (T) function that gained widespread popularity
was proposed by Soave (1972) as an equation of the form:
=[ 1 + m ( 1 T r 0.5 ) ] 2
(3)
The m parameter was obtained by forcing the equation to reproduce the vapor
pressure for nonpolar hydrocarbon compounds at Tr = 0.7 and was correlated
as a function of for the SRK CEOS:
m = 0.480 + 1.574 0.175 2
(4)
RT
a
v b
v ( v + b) + b( v b)
(5)
CEOS
WITH
FREE
WATER
DECANT
Refinery systems often contain both water and hydrocarbons. Mixtures with
water and hydrocarbons will form two liquid phases, one is water-rich phase and
the other is hydrocarbon-rich phase. The free water option is a simplication of
the thermodynamics treatment for water-hydroacrbon systems. For the free
water or decant option, water is considered as forming an immiscible phase with
the hydrocarbon-rich liquid phase The free water option is a convenient,
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. It is adequate for most hydrocarbon calculations such as refinery
columns with steam stripping and natural gasoline plants. The following
example shows how to use the decant option for refinery columns in the waterhydrocarbon calculations:
TITLE PROBLEM=DECANT, USER=SIMSCI
PRINT INPUT=FULL
COMP DATA
LIBID 1, H2O / 2, H2 / 3, N2 / 4, CO2 / 5,H2S/6, C1 / 7, ETHENE / *
8, C2 / 9, PROPENE / 10, 1BUTENE / 11, BTC2 / 12, IBTE / *
13, 13BD / 14, NC4 / 15, IC4 / 16, NC5
THERMO DATA
METHOD SYSTEM = SRK, SET = SET01, DEFAULT
WATER DECANT = ON
The free water technology is a semi-rigorous three phase (VLLE) calculations.
The vapor is first saturated with water at its vapor pressure. Water is then
dissolved in the hydrocarbon liquid up to its solubility limit, and any remaining
water is decanted as a free water phase. The K-value of water in the
hydrocarbon-rich liquid phase can then be computed from water partial
pressure, pw, the solubility of water in the hydrocarbon-rich liquid phase, xw, and
system pressure, P, 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).
The GPSA Figure 15-14, which relates the partial pressure of water vapor in
natural gas to temperature and pressure, is recommended for natural gas
mixtures above 2000 psia and Antoine saturated water vapor pressure is proper
for most problems.
The water solubility in the hydrocarbon-rich liquid phase can be computed by
either the method developed by SimSci, Figure 9A1.2 in the API Technical Data
Book (1982), which relates the solubility of water in kerosene to temperature, or
the cubic equation of state.
The K-value of water in the hydrocarbon-rich liquid phase is computed in the
way just mentioned above. On the other hand, the properties of pure water
phase including vapor pressure, enthalpy, entropy and density are predicted
either from saturated condition, which is the default and adequate for most
problems, or from steam table (i.e. the Keenan and Keyes equation of state,
1969). The Keenan and Keyes equation of state is recommended for
superheated water vapor.
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, USER=SIMSCI
PRINT INPUT=FULL
5
COMP DATA
LIBID 1, H2O/2, H2S/3, N2/4, CO2/5, C1/6, C2/7, C3/8, IC4/*
9, NC4/10,IC5/11, NC5/12, NC6
PETRO 13, CUT1,100,715.0,94.44/14, CUT2,164,820.3,204.44/*
15, CUT3,310,921.8,376.66
ASSAY CHAR=SIMSCI
THERMODYNAMIC DATA
METHOD SYSTEM=SRK,SET=SET01,DEFAULT
WATER DECANT=ON,GPSA,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, however, not all these equations have the
necessary binary interaction parameters to do the proper split. When the
standard SRK or PR CEOS are selected for three phase calculations, the free
water (decant) option must be deactivated. The example given below shows
how to use SRK CEOS for three-phase (VLLE) calculations:
TITLE PROBLEM=VLLE, USER=SIMSCI
PRINT INPUT=FULL
COMP DATA
LIBID 1, H2 / 2, N2 / 3, CO / 4, CO2 / 5, C1 / 6, ETHENE / 7, C2 / *
8, PROPENE / 9, 1BUTENE / 10, BTC2 / 11, IBTE / 12, 13BD / *
13, NC5 / 14, H2O / 15, IC4 / 16, 3BT1 / 17, O2
THERMO DATA
METHOD SYSTEM(VLLE) = SRK, SET = SET01, DEFAULT
WATER DECANT = OFF
SRK CEOS WITH KABADI-DANNER MIXING RULE
Although for most refining and natural gas calculations, the free water option is
adequate to represent water-hydrocarbon phase behavior, however, the free
water phase contains no dissolved hydrocarbons or light gases. When
hydrocarbon or light gas solubility in the water phase is an important
consideration for the problem being analyzed, e.g., an enviromental question, the
free water option is not adequate and a rigorous three phase calculation must be
performed for hydrocarbon-water systems.
6
Kabadi and Danner (1985) proposed a two-parameter mixing rule for the SRK
equation of state. The rigorous three phase calculation can be performed for
hydrocarbon-water systems by using the Soave-Redlich-Kwong-Kabadi-Danner
(SRKKD) equation. The example given below shows how to use SRKKD for
three-phase (VLLE) calculations:
TITLE PROBLEM=SRKKD, USER=SIMSCI
PRINT INPUT=FULL
COMP DATA
LIBID 1, H2 / 2, N2 / 3, CO / 4, CO2 / 5, C1 / 6, ETHENE / 7, C2 / *
8, PROPENE / 9, 1BUTENE / 10, BTC2 / 11, IBTE / 12, 13BD / *
13, NC5 / 14, H2O / 15, IC4 / 16, 3BT1 / 17, O2
THERMO DATA
METHOD SYSTEM(VLLE) = SRKKD, SET = SET01, DEFAULT
Note that the SRKKD mixing rule leads to inconsistencies when a component is
split into two or more identical fractions. This method was also found to give
large errors for the aqueous phase.
ALPHA () 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 function. In fact, vapor pressures of both nonpolar and polar
components can be very accurately represented by any cubic equation of state if
the temperature dependent function is sufficiently flexible.
Numerous functions have been proposed for this purposed. They contain
usually 1 to 3 empirical parameters to be derived from vapor pressures of
individual compounds. Among them, a two-parameter function proposed by
Twu (1988) and a three-parameter function proposed by Twu et al.(1991) are
recognized as the most flexible ones with correct extrapolation to high reduced
temperatures. These two functions, which become SimSci functions, are:
= Tr 2 ( M 1) e L ( 1 Tr
2M
(7)
= Tr N ( M 1) e L ( 1 Tr
N M
(8)
x x aij
(9)
i j
where
aij = ( aiaj ) (1 / 2 ) (1 kij )
(10)
xb
(11)
i i
The quadratic mixing rule is the most widely used for equations of state. The
standard method for introducing a binary interaction parameter, kij, into this
classical mixing rule is to correct the assumed geometric mean rule for the "aij"
parameter in the eqn.(10). 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 used for standard SRK and PR cubic equations
of state. The SYSTEM=SRK in previous examples are standard SRK equation
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. While this is a good approximation for hydrocarbon mixtures, it
cannot be applied to systems containing strongly polar or associating
components.
Therefore, in the 1970's and 1980's, equations of state were used virtually only
for nonpolar hydrocarbons and slightly polar components. 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.
Chemical systems consisting of components with varying chemical nature can
exhibit highly non-ideal phase behavior and thus are difficult to predict.
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. For predicting such highly non-ideal systems, the advanced mixing
rules in addition to the advanced function are required for the equations of
state. Over the past decade, the equations of state have significantly progress in
the development of the most appropriate functions and advanced asymmetric
mixing rules for systems containing strongly polar components. An appropriate
temperature dependent function is required to represent accurately the vapor
pressure of pure components and a proper mixing rule is essential to correctly
predict vapor-liquid and/or vapor-liquid-liquid phase behavior of highly nonideal chemical systems.
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., 1992). 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 1 or 2 , respectively. While
it is a good approximation for hydrocarbon mixtures to assume that k12 = k21,
this assumption cannot be applied to highly asymmetric systems containing
strongly polar or associating components.
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, for example, the water-rich and hydrocarbon-rich phases. The mixing
rule proposed by Kabadi and Danner (1985) is an example of using two binary
parameters, although it is not quite successful in the aqueous phase.
Another particular example of using two binary interaction parameters was
proposed by Panagiotopoulos and Reid (1986). They have proposed modified
classical quadratic mixing rules that use composition-dependent binary
interaction parameters.
aij = ( aiaj ) ( 1 / 2) [(1 kij ) + ( kij kji ) x i ]
(12)
(13)
11
12
THERMO DATA
METHOD SYSTEM(VLLE)=HEXAMER
TITLE PROBLEM=REFRIGERANT, USER=SIMSCI
PRINT INPUT=FULL
COMP DATA
LIBID 1,HF/2,TFETH,,R134A, 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, efficient computation time and reliability in the K-value calculations,
the accuracy of predicting liquid density and liquid enthalpy are not quite high
even for nonpolar hydrocarbons. On the other hand, the non-cubic equation of
state such as the Benedict-Webb-Rubin-Starling (BWRS) equation of state
(Starling, 1973) is capable of representing for both liquid and vapor phases the
density, enthalpy, and entropy, in addition to vapor pressure for hydrocarbons
in the cryogenic liquid region in addition to higher temperature regions.
However, unlike the constants (a and b) of cubic equation of state, which are
constrained to satisfy the critical point conditions, the constants (total is 11) of
Benedict-Webb-Rubin-Starling equation are not satisfied with the critical
contraints. Therefore, the K-value calculations from BWRS for hydrocarbons
near the critical point may not be as reliable as that from CEOS.
The BWRS is quite often employed to calculate K-value, enthalpy, entropy,
and density for hydrocarbon and industrial important gas systems in the
cryogenic liquid region in addition to higher temperature regions. One of the
typical examples is given below:
TITLE PROBLEM=BWRS, USER=SIMSCI
PRINT INPUT=FULL
COMP DATA
LIBID 1,H2/2,ETLN/3,IC4/4,HXE1,BANK=SIMSCI
THERMO DATA
13
METHOD SYSTEM=BWRS
KVALUE BANK=SIMSCI
In general, 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. It may also
require considerably more computing times. The following example applies
BWRS equation of state to pure hydrocarbon for the prediction of properties at
any temperature and pressure:
TITLE PROBLEM=BWRS, USER=SIMSCI
DIME ENGLISH, PRES=PSIG
COMP DATA
LIBID 1,ETLN,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, PR, ans vdW cubic equations of state. SimSci has compiled a data bank
of parameters for all the components in the SimSci component library using
the functions given by eqn.(7) and (8) for SRK, PR, and vdW CEOS. The
following is an example showing how to retrieve component-dependent
parameters from SimSci databank and to input you own parameters for SRK
CEOS:
TITLE PROJECT=TRAINING, PROBLEM=ALPHA, USER=SIMSCI
PRINT INPUT=FULL
COMPONENT DATA
LIBID 1,NITROGEN/2,CO2/3,METHANE/4,ETHANE/ *
5,PROPANE/6,IBUTANE/7,BUTANE/8,IPENTANE/ *
9,PENTANE/10,HEXANE/11,HEPTANE, BANK=PROCESS
THERMODYNAMIC DATA
METHOD SYSTEM=SRK,SET=SET01,DEFAULT
KVALUE ALPHA=SIMSCI, BANK=PROCESS
14
SA06 11,0.340339,0.844963,2.38332
15
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. The
proprietary MW correlation was then used to estimate the binary parameter for
this binary which parameters were not found in the databank.
SRK INTERACTION PARAMETERS
KIJ = A(I,J) + B(I,J)/T + C(I,J)/T**2
I J
--- --1 2
1 3
1 4
2 3
2 4
3 4
A(I,J)
B(I,J)
---------- ---------0.0830 0.00
-0.0800 0.00
0.5000 0.00
0.0680 0.00
0.0600 0.00
0.0141 0.00
C(I,J)
---------0.00
0.00
0.00
0.00
0.00
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
function; the other is the mixing rule. A flexible 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. Having these two elements, the key application guideline of
a CEOS primarily depends upon the availability of binary interaction parameters
for the system.
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, CO2, H2, etc.
16
17
Panagiotopoulos, A.Z. and Reid, R.C., 1986. "A New Mixing Rule for Cubic
Equations of State for Highly Polar Asymmetric Systems." ACS Symp. Ser.
300, American Chemical Society, Washington, DC, pp. 571-582.
Peng, D.Y. and Robinson, D.B., 1976. "A New Two-constant Equation of
State", Ind. Eng. Chem. Fundam., 15:58-64.
Redlich, O. and Kwong, N.S., 1949. "On the Thermodynamics of Solutions. V:
An Equation of State. Fugacities of Gaseous Solutions", Chem. Rev. 44:233244.
Soave, G., 1972. "Equilibrium Constants from a Modified Redlich-Kwong
Equation of State", Chem. Eng. Sci., 27:1197-1203.
Starling K.E., 1973. Fluid Thermodynamic Properties for Light Petroleum
Systems, Gulf Publ. Co., Houston, TX.
Twu, C.H., 1988. "A Modified Redlich-Kwong Equation of State for Highly
Polar, supercritical Systems," International Symposium on Thermodynamics
in Chemical Engineering and Industry, May 30-June 2, 1988.
Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E., 1991. "A Cubic
Equation of State with a New Alpha Function and a New Mixing Rule", Fluid
Phase Equilibria, 69:33-50.
Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E., 1992. "A Cubic
Equation of State: Relation Between Binary Interaction Parameters and Infinite
Dilution Activity Coefficients,", Fluid Phase Equilibria, 72:25-39.
Twu, C.H., Coon, J.E., and Cunningham, J.R., 1993. "An Equation of State: for
Hydrogen Fluoride,", Fluid Phase Equilibria, 86:47-62.
van der Waals, J.D., 1873. Over de Constinuiteit van den gas-en
Vloeistoftoestand, Doctoral Dissertation, Leiden, Holland.
Wilson, G.M., 1964. "Vapor-liqumid Equilibria Correlated by Means of a
Modified Redlich-Kwong Equation of State", Adv. Cryog. Eng., 9:168-176.
Wilson, G.M., 1966. "Calculation of Enthalpy Data from a Modified RedlichKwong Equation of State", Adv. Cryog. Eng., 11:392-400.
18