Calculating and Applying KValues
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Calculating and Applying KValues
By
Abdulreda AlSaygh and Mahmood Moshfeghian
Department of Chemical Engineering University of Qatar, Doha, Qatar
And
Robert N. Maddox
School of Chemical Engineering
Oklahoma State University
Stillwater, Oklahoma, U.S.A.
ABSTRACT
Several methods for determination of Kvalues were reviewed and sample results are presented. Several case studies were presented to demonstrate their application. Based on the VLE calculations results, for light hydrocarbon systems, an equation of state should be used and for polar systems, an activity coefficient model is recommended.
Introduction
Modeling and design of many types of equipment for separating gas and liquids such as flash separators at the well head, distillation columns and even a pipeline are based on the phases present being in vaporliquid equilibrium. The criteria for thermodynamic equilibrium between vapor and liquid phases are equality of temperature in both phases, equality of pressure in both phases, and equality of fugacity of each component in both phases. The mathematical expression for the last equality in terms
of the fugacity of component i, is written as:
(1)
Equation (1) is the foundation of vaporliquid equilibrium calculations, however, we rarely use it in this form for practical applications. For calculation purposes, Equation (1) is transformed to a more commonly used expression:
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(2)
In Equation (2), K _{i} is called the vapor–liquid equilibrium constant. Equ. (2) is also called "Henry’s law" and K is frequently referred to as Henry’s constant. For the more volatile components in a mixture the Kvalues are greater than 1.0, whereas for the less volatile components they are less than 1.0.
Depending on the system under study, any one of several approaches may be taken to determine Kvalues. Obviously, experimental measurement is the most desirable; however, it is expensive and time consuming. Alternatively, there are several graphical or numerical tools that can be used for determination of Kvalues. This paper presents a history of the development of many of those graphical methods and numerical techniques.
In general Kvalues for all components in a mixture are function of the pressure, temperature, and composition of the vapor and liquid phases present. The components making up the system plus temperature, pressure, composition, and degree of polarity affect the accuracy and applicability, and hence the selection, of an approach to estimating the K values. The widely used approaches are Kvalue charts, Raoult’s law, the _{φ}_{}_{φ} approach and the _{φ}_{}_{γ} approach [15]. The last two approaches involve using an equation of state.
Methods for Determining KValues
KValue Charts
There are several forms of Kvalue charts. One of the earliest forms of the Kvalue charts for light hydrocarbons is presented in reference [1]. In these charts, Kvalues for individual components are plotted on the ordinate as a function of temperature on the abscissa with pressure as a parameter. In each chart the pressure range is from 10 psia to 1000 psia and the temperature range is from 40 ºF to 500 ºF.
Early high pressure experimental work revealed that, if a hydrocarbon system of fixed overall composition was held at constant temperature and the pressure was increased, the Kvalues of all components converged toward a common value of unity (1.0) at some high pressure. This pressure was termed the “Convergence Pressure” of the system and has been used to correlate the effect of composition on Kvalues. Plotting this way permits generalized Kvalues to be presented in a moderate number of charts.
In more recent publications [2], the Kvalues are plotted as a function of pressure on the abscissa with Convergence Pressure and temperature as parameters.
In order to use these charts, one should determine the Convergence Pressure first. The determination of convergence Pressure is a trialanderror procedure. Illustrative example calculations can be found elsewhere [6].
In 1958, for computer use, these KValue charts were curve fitted to the following equations by
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academic and industrial experts collaborating through the aegis of the Natural Gas Association of America [7].
Raoult’s Law
(3)
Raoult’s Law is based on the assumptions that the vapor phase behaves as an ideal gas and the liquid phase is an ideal solution. Under these conditions the fugacities are expressed as
(4)
(5)
Substituting from Equations (4) and (5) into Equation (1) gives
(6)
The vapor pressure may be read from a Cox chart or calculated from a suitable equation in terms of temperature. A typical Cox chart can be found in reference [8]. The Antoine [5] equation is recommended for calculating vapor pressure.
Complex vapor pressure equations presented by Wagner [5], even though more accurate, should be avoided because they should not be used to extrapolate to temperatures beyond the critical temperature of each component. Also, Raoult’s law is applicable to only to lowpressure systems (up to about 50 psia) and to systems in which the components are very similar such as benzene and toluene. This method is simple but it suffers when the temperature of the system is above the critical temperature of one or more of the components in the mixture. At temperatures above the critical point of a component, one must extrapolate the vapor pressure, which frequently results in erroneous Kvalues. In addition, this method ignores the fact that the Kvalues are composition dependent.
Correlation Method
As mentioned earlier, determination of Kvalues from charts is not suitable for computer calculations. Therefore, scientists and engineers have developed numerous curve fitted expressions for calculation of Kvalues. However, these correlations have limited application because they are specific to a certain system or applicable over a limited range of conditions. Some of these are polynomial or exponential correlations in which Kvalues are expressed in terms of pressure and temperature. One of these correlations presented by Wilson [9], is:
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(7)
This correlation is applicable to low and moderate pressure, up to about 3.5 MPa (500 psia), and the K values are assumed to be independent of composition.
φφ Approach
The _{φ}_{}_{φ} approach is based on using an Equation Of State (EOS). The fugacity of each component is determined by using an EOS. The same EOS describes both phases. The φφ approach is a powerful tool and it is relatively accurate if used appropriately. This approach is widely used in industry for light hydrocarbon and nonpolar systems. In this approach the fugacities are expressed by
Substitution of fugacities from Equations (8) and (9) in Equation (1) gives
(8)
(9)
(10)
In equation (10), fugacity coefficients must be determined from a generalized chart or calculated using an EOS. In order to calculate the fugacity coefficients for a mixture by an EOS, the mole fractions in both phases are needed in addition to pressure and temperature. Normally not all of these variables are known. Therefore, calculation of Kvalues using an EOS is a trial and error procedure. The _{φ}_{}_{φ} approach is applicable to nonpolar systems and yields good results up to about 15,000 psia.
φγ Approach
The socalled _{φ}_{}_{γ} approach is also based on using an EOS, but requires that the vapor phase non ideality be described through the fugacity coefficient, with an activity coefficient model being used to account for the nonideality of the liquid phase. This approach is widely used in industry even for polar systems exhibiting highly nonideal behavior. Using this model the fugacities are expressed by
(11)
(12)
The saturation fugacity coefficient for a component in the system,
component i at the temperature of the system but at the saturation pressure of that component.
, is calculated for pure
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Normally, an EOS is used to calculate both and (12) in Equation (1) gives
and
. Substitution of fugacities from Equations (11)
(13)
Activity coefficients are calculated by an activity coefficient model such as that of Wilson [11] or the NRTL (NonRandom Two Liquid) model [12]. The required parameters for a few binary systems are given in reference [13]. In order to calculate the Kvalues by Equation (13), the mole fractions in both phases, in addition to pressure and temperature, are needed. Normally not all of these variables are known. As is the case for the _{φ}_{}_{φ} approach, calculations are trial and error. The _{φ}_{}_{γ} approach is applicable to polar systems such as water – ethanol mixtures from low to high pressures.
γ Approach
Normally, for low pressures, we can assume that the vapor phase behaves like an ideal gas;
therefore both
and
are set equal to 1.0. Under such circumstances, Equation (13) reduces to
(14)
Equation (14) is applicable for lowpressure nonideal solutions and polar systems. Assuming the liquid phase is an ideal solution, γ _{i} becomes unity and Equation (14) is reduced further to a simple Raoult’s law.
The Impact of Computers on calculating Kvalues
The accuracy of any process simulation by computer software depends directly on the accuracy of the Kvalues used. The Kvalues are the essential ingredient for design and simulation of a separation system involving distillation columns, flash separators, etc. As computers were developed for engineering calculations, scientists and engineers strived for the development of generalized and accurate EOSs. Since the Kvalue charts are limited and simplified and calculation of Kvalues based an EOS is trial and error and, consequently tedious and time consuming for hand calculation, the computer is ideally suited for this task.
The first computer generated Kvalues were based on the ChaoSeader EOS [14]. An equation similar to Equation (13) was used for this purpose. Later Erbar and Maddox [15] developed the K&H Mod II software marketed by the Gas Processors Association for generating Kvalues and enthalpies of light hydrocarbons as well as some selected nonhydrocarbon compounds such as nitrogen, carbon dioxide and hydrogen sulfides. This program which was based on the SRK EOS was well received by industry due to its accuracy, reliability and flexibility.
Due to the development of computers and software, a complete phase envelope for a reservoir
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fluid based on EOS generated Kvalues can be plotted in a few seconds; something that would have taken months before the 1970’s. Similarly, today, a complete rigorous computer simulation of a distillation column for multicomponent systems with multistage, multi feed and multiproduct streams is calculated in only a few minutes. Accurate generation of Kvalues by an EOS enables engineers to have a more accurate, economically sound, flexible, and reliable design.
Application of KValues
Bubble Point
For a mixture, the bubble point is defined as the temperature at which the first bubble of vapor forms at a given pressure. At the bubble point, the liquid phase composition is known. At this temperature vapor and liquid phases are at equilibrium; therefore Equations (1) and (2) hold.
(15)
Depending on the situation, two kinds of bubble point calculations may be required. In one case, the pressure is known and temperature is to be calculated. In the other case the temperature is known and the bubble point pressure is to be calculated. In either case the calculation is trial and error and may be carried out by hand or computer.
Case No. 1
In order to show typical prediction accuracy for each method, the bubble point temperature and vapor phase mole fraction composition of the following natural gas mixture were calculated at pressures from 14.7 to 1700 psia using.
(a) 
Raoult’s Law Kvalues (based on pure component vapor pressures). 
(b) 
Wilson KValue Correlation (WKVC) 
(c) 
NGPA KValue Chart based on a convergence pressure of 5000 psia. 
(d) 
SRK EOS using EzThermo [16] simulation software. 
Table 1 presents the summary calculated bubble point results for pressures 14.7 to 1700 psia. Table 1 indicates that at low pressures up to 800 psia, all methods give close answers for bubble point temperature; however, as the pressure increases, the difference becomes so large.
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Table 1 Predicted bubble point temperature
Dew Point
For a mixture, the dew point is defined as the temperature at which the first drop of liquid forms at a given pressure. At the dew point, the vapor phase composition is known. At this temperature both vapor and liquid phases are at equilibrium; therefore Equations (1) and (2) hold.
(16)
Depending on the situation, two cases of dew point calculation may occur. In one case, the pressure is known and temperature is to be calculated or in the other case the temperature is known and the dew point pressure is to be calculated. In either case the calculation is trial and error and may be carried out by hand or by computer.
Case No. 2
Calculate the dew point temperatures and compositions of the first drop of liquid of natural gas mixture of Case No. 1 for pressures from 14.7 to 1870 psia using:
(a) 
Raoult’s Law Kvalue 
(b) 
Wilson KValue Correlation (WKVC) 
(c) 
NGPA KValue Chart based on convergence pressure of 5000psia 
(d) 
SRK EOS using EzThermo simulation software 
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Table 2 presents the summary calculated dew point results for pressures 14.7 to 1870 psia. The analysis of Table 2 indicates that at Raoult’s law and Wilson correlation give very close results; however, they are much different from NGPA and SRK results even at low pressures.
Table 2 Predicted dew point temperature
Flash Calculations
Separating a two phase stream into a vapor stream and a liquid stream is frequently required. Normally, the feed composition, total feed rate, temperature, and pressure are known and flow rates and composition of vapor and liquid must be calculated. The governing equations can be obtained by writing the overall and component material balances and the equilibrium relationship.
Case No. 3
Flash calculation results for the natural gas mixture of Case No. 1 at 300 psia (2058.4 kPa) and  9.7 F (250 K) for for several methods were performed and the results are presented in Table 3.
Case No. 4
A series of flash calculations for the natural gas mixture of Case No. 1 for several methods were
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performed and the results are presented in Table 4. This table indicates that the Raoult’s law and Wilson correlation give similar liquid fraction but they are different from those predicted by NGPA and SRK. Up to pressure of 800 psia, both NGPA and SRK give close answers but as pressure increases, their results deviate from each other drastically.
Table 3 Predicted Kvalues at 300 psia (2058.4kPa) and 9.7 F (250 K)
Component 
Raoult
8.2872
0.6566
0.1065
0.0189
0.0037
0.0007

WKVC 
KChart 
SRK 
Methane 
8.1934 
6.1792 
5.7629 

Ethane 
0.6377 
0.7014 
0.7168 

Propane 
0.1060 
0.1469 
0.1571 

nButane 
0.0201 
0.0331 
0.0347 

nPentane 
0.0044 
0.0078 
0.0080 

nHexane 
0.0011 
0.0022 
0.0012 
Table 4 Predicted liquid fraction formation
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Case No. 5
Yarborough and Vogel [18] reported experimental VLE measurements for a gas mixture of the following composition at several pressures and temperatures. Composition of mixture B is the experimental repeat for composition of mixture A. Flash calculations for this natural gas mixture at the following reported pressures and 200 ºF were carried out using three popular equations of state:
P, psia 
110 
255 
535 
552 
1032 
1033 
1547 
2044 
Mixture 
B 
B 
B 
A 
A 
B 
B 
A 
(a) SoaveRedlich
Kwong (SRK) EOS [10]
(b) 
PengRobinson 
(PR) 
EOS [19] 
(c) 
Nasrifar 
Moshfeghian (NM) EOS
[20]
Mole % 

Mixture A 
Mixture B 

Component 
% 
% 
Nitrogen 
0.480 
0.470 
Methane 
80.64 
80.31 
Carbon dioxide 
0.15 
0.18 
Ethane 
5.93 
5.93 
Propane 
2.98 
3.00 
nPentane 
4.30 
4.45 
nHeptane 
3.08 
3.14 
nDecane 
2.44 
2.52 
Total 
100.0 
100.0 
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A summary of the error analyses for the liquid fraction expressed as moles of liquid to moles of feed (L/ F), is presented in Table 6. The experimental liquid fraction was not reported; a simple flash calculation using experimentally determined Kvalues was performed to calculate the experimental L/F. Table 6 indicates that with the exception of the last two pressures, SRK EOS gives the most accurate liquid fraction.
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Table 6 A summary of error analyses for the liquid fraction and the moles of liquid to moles of feed (L/
A summary of the error analysis for all K values is shown in Table 7. This table indicates that SRK and PR give comparable results. A graphical comparison between predicted Kvalues and experimental K values for the NM EOS are shown in Figures 1.
Table 7 Summary of the error analysis for all Kvalues
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Consistency Test of KValues
There are several ways of testing the accuracy and validity of KValues calculated from measured experimental liquid and vapor phase mole fractions or generated by any EOS, charts or correlation. In one method, Kvalues are plotted as a function of pressure on a loglog scale as shown in Figures 1. For each isotherm, the Kvalues for each component all fall on a smooth curve if they are consistent.
Another method is to plot at the specified pressure and temperature the log of the Kvalue for each hydrocarbon component as a function of its critical point absolute temperature squared. If the K values are consistent and accurate, they will fall on a straight line. Figure 2 presents such a test for the Yarborough and Vogel data at 3035 psia and 200 ºF. This figure indicates that the Yarborough and Vogel data are of good quality.
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Conclusions:
Several methods for determination of Kvalues were reviewed. Several case studies were presented to demonstrate their application. The data used clearly show that the accuracies of these methods are not the same and care must be taken to choose the right and proper method for a given application. In Case No. 1, for bubble point pressures above 800 psia, the difference in predicted temperature is large and as the pressure increases the difference becomes larger. Case No. 2 indicates that the difference in the predicted dew point temperature is even larger. Case No. 4 shows that as the pressure increases, the amount of liquid predicted by different methods differs considerably.
In Case No. 5, two widely used EOS and a new EOS were tested. The results show that for the systems tested, all three EOS generally give relatively accurate results; however, with the exception of very high pressure, the SRK gives the most accurate VLE calculation results.
Based on the cases studied, our conclusion is that for VLE calculations of light hydrocarbon systems, an equation of state should be used and for polar systems, an activity coefficient model is recommended.
Always, the KValues should be checked for accuracy and consistency before accepting the calculation results.
References
1. Proceedings Natural Gasoline Supply Men’s Association, 20 ^{t}^{h} Annual Convention, April 2325,
1941.
2. Engineering Data Book, 10 ^{t}^{h} and 11 ^{t}^{h} Editions, Gas Processors and Suppliers Association Data Book, Tulsa, Oklahoma, (1998).
3. Prausnitz, J. M.; R. N. Lichtenthaler, E. G. de Azevedo, “Molecular Thermodynamics of Fluid
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Phase Equilibria”, 3 ^{r}^{d} Ed., Prentice Hall PTR, New Jersey, NY, 1999.
4. Maddox, R. N. and L. L. Lilly, “Gas Conditioning and Processing, Volume 3: Advanced Techniques and Applications,” John M. Campbell and Company, Norman, Oklahoma, USA,
1994.
5. Reid, R. C.; J. M. Prausnitz, and B. E. Poling, “The Properties of Gases and Liquids,” 4 ^{t}^{h} Ed., McGraw Hill, New York, 1987.
6. Engineering Data Book, 7 ^{t}^{h} Edition, Natural Gas Processors Suppliers Association, Tulsa, Oklahoma, 1957.
7. Equilibrium Ratio Data for Computers, Natural Gasoline Association of America, Tulsa, Oklahoma, (1958).
8. Natural Gasoline and the Volatile Hydrocarbons, Natural Gasoline Association of America, Tulsa, Oklahoma, (1948).
9. Wilson, G., “A modified RedlichKwong equation of state applicable to general physical data calculations,” Paper No15C, 65 ^{t}^{h} AIChE National meeting, May, (1968).
10. G. Soave, Chem. Eng. Sci. 27, 11971203, 1972.
11. Wilson, G. M., J. Am. Chem. Soc. Vol. 86, pp.127120, 1964
12. Renon, H. and J. M. Prausnitz, AIChEJ., Vol. 14, pp.135144, 1968.
13. Gmehling et al., “VaporLiquid Equilibrium Data Collection”, Chemistry Data Series, Vol.1, part 1a, 1b, 2c, and 2e, DECHEMA, Frankfurt / Main 19811988
14. Chao,
J.
Hydrocarbon Systems”, AIChE, 7, 598, 1961
K.
C.
and
D.
Seader,
“A
General
Correlation
of
VaporLiquid
Equilibria
in
15. Erbar, J.H. and R.N. Maddox, GPA K & H Mod II Program, Natural Gas Processors and Suppliers Association, Tulsa, Oklahoma, 1962
16. Moshfeghian, M. and R.N. Maddox, EzThermo Software, 2002
17. Freshwater, D. C. and K. A. Pike, J. Chem. Eng. Data, Vol. 12, pp. 179183, 1967
18. Yarborough, L. and John L. Vogel, "A New System for Obtaining Vapor and Liquid Sample Analyses to Facilate the Study of Multicomponent Mixtures at Elevated Pressures," Chem. Engr. Symposium Series, No. 81, Vol.63,
19. D.Y. Peng, D.B. Robinson, Ind. Eng. Chem. Fundam. Vol. 15, pp. 5964, 1976
20. Nasrifar, Kh. and M. Moshfeghian, “A New Cubic Equation of State for Simple Fluids: Pure and Mixtures,” J. of Fluid Phase Equilibria, 190, pp. 7388, 2001
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Symbols
the fugacity of component i in the vapor phase.
the fugacity of component i in the liquid phase.
K _{i}
y _{i} .
the vapor–liquid equilibrium constant (Kvalue)
mole fraction of one component i in the vapor phase.
x _{i}
mole fraction of component i in the liquid phase.
T absolute temperature.
P absolute pressure.
b _{i}_{j}
the fitted values coefficients in Equation (3)
the saturation pressure of a component i.
T _{c}_{i}
P _{c}_{i}
ω _{i}
the critical temperature.
the critical pressure.
the acentric factor.
the fugacity coefficients for component i in the vapor phase.
the fugacity coefficients for component i in the liquid phase.
the fugacity coefficients for pure component i at the saturation pressure.
γ _{i} the activity coefficient for component i.
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