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Calculating and Applying K-Values

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Calculating and Applying K-Values


By
Abdulreda Al-Saygh 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 K-values 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 vapor-liquid 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 vapor-liquid 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), Ki is called the vaporliquid equilibrium constant. Equ. (2) is also called "Henrys law" and K is frequently referred to as Henrys constant. For the more volatile components in a mixture the K-values 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 K-values. 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 K-values. This paper presents a history of the development of many of those graphical methods and numerical techniques. In general K-values 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 K-value charts, Raoults law, the - approach and the - approach [1-5]. The last two approaches involve using an equation of state.

Methods for Determining K-Values

K-Value Charts There are several forms of K-value charts. One of the earliest forms of the K-value charts for light hydrocarbons is presented in reference [1]. In these charts, K-values 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 F to 500 F. 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 K-values 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 K-values. Plotting this way permits generalized K-values to be presented in a moderate number of charts. In more recent publications [2], the K-values 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 trial-and-error procedure. Illustrative example calculations can be found elsewhere [6]. In 1958, for computer use, these K-Value 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].

(3)

Raoults Law Raoults 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, Raoults law is applicable to only to low-pressure 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 K-values. In addition, this method ignores the fact that the K-values are composition dependent.

Correlation Method As mentioned earlier, determination of K-values from charts is not suitable for computer calculations. Therefore, scientists and engineers have developed numerous curve fitted expressions for calculation of K-values. 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 K-values 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 Kvalues are assumed to be independent of composition.

- Approach The - 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 - approach is a powerful tool and it is relatively accurate if used appropriately. This approach is widely used in industry for light hydrocarbon and non-polar systems. In this approach the fugacities are expressed by (8) (9) Substitution of fugacities from Equations (8) and (9) in Equation (1) gives

(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 K-values using an EOS is a trial and error procedure. The - approach is applicable to non-polar systems and yields good results up to about 15,000 psia.

- Approach The so-called - approach is also based on using an EOS, but requires that the vapor phase nonideality be described through the fugacity coefficient, with an activity coefficient model being used to account for the non-ideality of the liquid phase. This approach is widely used in industry even for polar systems exhibiting highly non-ideal behavior. Using this model the fugacities are expressed by (11) (12) The saturation fugacity coefficient for a component in the system, , is calculated for pure component i at the temperature of the system but at the saturation pressure of that component.

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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 (Non-Random Two Liquid) model [12]. The required parameters for a few binary systems are given in reference [13]. In order to calculate the K-values 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 - approach, calculations are trial and error. The - approach is applicable to polar systems such as water ethanol mixtures from low to high pressures.

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 low-pressure non-ideal solutions and polar systems. Assuming the liquid phase is an ideal solution, i becomes unity and Equation (14) is reduced further to a simple Raoults law.

The Impact of Computers on calculating K-values The accuracy of any process simulation by computer software depends directly on the accuracy of the K-values used. The K-values 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 K-value charts are limited and simplified and calculation of K-values 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 K-values were based on the Chao-Seader 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 K-values and enthalpies of light hydrocarbons as well as some selected non-hydrocarbon 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 K-values can be plotted in a few seconds; something that would have taken months before the 1970s. Similarly, today, a complete rigorous computer simulation of a distillation column for multicomponent systems with multi-stage, multi feed and multi-product streams is calculated in only a few minutes. Accurate generation of K-values by an EOS enables engineers to have a more accurate, economically sound, flexible, and reliable design.

Application of K-Values

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) (b) (c) (d)

Raoults Law K-values (based on pure component vapor pressures). Wilson K-Value Correlation (WKVC) NGPA K-Value Chart based on a convergence pressure of 5000 psia. SRK EOS using EzThermo [16] simulation software.

Component Methane Ethane Propane n-Butane n-Pentane n-Hexane Total

Mole % 76.0 13.0 5.0 2.0 2.0 2.0 100.0

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 Bubble point temperature, F P, psia 14.7 100 300 600 800 1000 1200 1400 1600 1700 Raoult WKVC NGPA SRK -252.49 -252.60 -254.15 -253.84 -195.66 -196.38 -196.71 -197.23 -147.91 -147.96 -148.40 -147.10 -107.23 -107.12 -107.12 -103.76 -87.16 -86.89 -86.03 -81.65 -69.97 -69.54 -68.49 -61.96 -54.74 -54.13 -53.91 -43.08 -40.92 -40.13 -41.76 -23.24 -28.17 -27.18 -31.54 0.25 -22.13 -21.10 -26.5 16.27

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) Raoults Law K-value (b) Wilson K-Value Correlation (WKVC) (c) NGPA K-Value 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 Raoults 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

Dew point temperature, F P, psia Raoult WKVC NGPA SRK 14.7 5.90 -3.42 5.77 5.27 100 77.65 74.12 67.68 70.83 300 134.65 133.68 109.63 113.32 600 180.27 180.05 134.38 136.15 800 202.23 202.06 142.09 141.82 1000 220.77 220.44 146.19 142.90 1200 237.06 236.44 147.81 140.05 1400 251.69 250.75 147.52 133.18 1600 265.10 263.77 145.72 120.96 1700 271.44 269.87 144.32 111.51 1800 277.54 275.77 142.63 97.12 1870 281.70 279.77 141.30 59.81

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 Raoults 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 K-values at 300 psia (2058.4kPa) and -9.7 F (250 K)

K-Values at 300 psia and -9.7 F Component Methane Ethane Propane n-Butane n-Pentane n-Hexane Raoult WKVC K-Chart SRK 8.2872 0.6566 0.1065 0.0189 0.0037 0.0007 8.1934 0.6377 0.1060 0.0201 0.0044 0.0011 6.1792 0.7014 0.1469 0.0331 0.0078 0.0022 5.7629 0.7168 0.1571 0.0347 0.0080 0.0012

Table 4- Predicted liquid fraction formation Liquid fraction, L/F P, psia T, F Raoult WKVC NGPA SRK 14.7 -50 0.0417 0.0368 0.0433 0.0415 100 -50 0.0967 0.0969 0.0961 0.0955 300 -50 0.1833 0.1873 0.1743 0.1768 600 -50 0.3096 0.3131 0.2954 0.3007 800 -50 0.4131 0.4179 0.4111 0.4204 1000 -50 0.5663 0.5745 0.5862 0.6391 1200 50 0.2016 0.2044 0.1502 0.1528 1400 50 0.2381 0.2147 0.1684 0.1710 1600 50 0.2778 0.2827 0.1858 0.1795 1700 50 0.2993 0.3048 0.1943 0.1705 1800 50 0.3220 0.3283 0.2026 0.1213

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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 F were carried out using three popular equations of state:

P, psia Mixture

110 B

255 B

535 B

552 A

1032 A

1033 B

1547 B

2044 A

2543 B

3035 A

(a) Soave-RedlichKwong (SRK) EOS [10]


Component

(b) Peng-Robinson (PR) EOS [19] (c) NasrifarMoshfeghian (NM) EOS [20]

Nitrogen Methane Carbon dioxide Ethane Propane n-Pentane n-Heptane n-Decane Total

Mole % Mixture A Mixture B % % 0.480 0.470 80.64 80.31 0.15 0.18 5.93 5.93 2.98 3.00 4.30 4.45 3.08 3.14 2.44 2.52 100.0 100.0

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 K-values 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/ F) P Psia 110 255 535 552 1032 1033 1547 2044 2543 3035 AAPE Mix. B B B A A B B A B B Exp 0.0271 0.0451 0.0665 0.0631 0.0854 0.0899 0.1072 0.1110 0.1006 0.0214 SRK 0.0250 0.0438 0.0647 0.0629 0.0853 0.0891 0.1086 0.1174 0.1298 0.0905 PR 0.0242 0.0430 0.0633 0.0615 0.0823 0.0860 0.1027 0.1071 0.1102 0.0390 NM SRK PR NM 0.0243 7.75 10.70 10.33 0.0421 2.88 4.66 6.65 0.0607 2.71 4.81 8.72 0.0589 0.32 2.54 6.66 0.0760 0.12 3.63 11.01 0.0795 0.89 4.34 11.57 0.0908 -1.31 4.20 15.30 0.0897 -5.77 3.51 19.19 0.0867 -29.03 -9.54 13.82 0.0393 -322.90 -82.24 -83.64 37.37 13.02 18.69 Liquid Fraction, L/F at 200 F Percent Error in (L/F)

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 K-values and experimental Kvalues for the NM EOS are shown in Figures 1.

Table 7- Summary of the error analysis for all K-values


P

Psia 110 255 535 552 1032 1033 1547 2044

Mix. Average Absolute Percent Error in All K-Values SRK PR NM B 20.77 21.23 22.77 B 16.72 17.74 20.16 B 9.46 8.48 11.76 A 7.65 9.06 11.39 A 5.55 8.59 12.36 B 7.79 7.49 10.70 B 6.23 11.35 10.39 A 3.82 5.61 6.59

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2543 3035 AAPE

B B

7.42 5.37 9.07

5.59 2.48 9.76

9.39 11.39 12.76

Consistency Test of K-Values There are several ways of testing the accuracy and validity of K-Values calculated from measured experimental liquid and vapor phase mole fractions or generated by any EOS, charts or correlation. In one method, K-values are plotted as a function of pressure on a log-log scale as shown in Figures 1. For each isotherm, the K-values 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 K-value for each hydrocarbon component as a function of its critical point absolute temperature squared. If the Kvalues 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 F. This figure indicates that the Yarborough and Vogel data are of good quality.

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Conclusions: Several methods for determination of K-values 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 K-Values should be checked for accuracy and consistency before accepting the calculation results.

References

1. Proceedings Natural Gasoline Supply Mens Association, 20th Annual Convention, April 23-25, 1941. 2. Engineering Data Book, 10th and 11th 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, 3rd 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, 4th Ed., McGraw Hill, New York, 1987. 6. 7. 8. Engineering Data Book, 7th Edition, Natural Gas Processors Suppliers Association, Tulsa, Oklahoma, 1957. Equilibrium Ratio Data for Computers, Natural Gasoline Association of America, Tulsa, Oklahoma, (1958). Natural Gasoline and the Volatile Hydrocarbons, Natural Gasoline Association of America, Tulsa, Oklahoma, (1948).

9. Wilson, G., A modified Redlich-Kwong equation of state applicable to general physical data calculations, Paper No15C, 65th AIChE National meeting, May, (1968). 10. G. Soave, Chem. Eng. Sci. 27, 1197-1203, 1972. 11. Wilson, G. M., J. Am. Chem. Soc. Vol. 86, pp.127-120, 1964 12. Renon, H. and J. M. Prausnitz, AIChEJ., Vol. 14, pp.135-144, 1968. 13. Gmehling et al., Vapor-Liquid Equilibrium Data Collection, Chemistry Data Series, Vol.1, part 1a, 1b, 2c, and 2e, DECHEMA, Frankfurt / Main 1981-1988 14. Chao, K. C. and J. D. Seader, A General Correlation of Vapor-Liquid Equilibria in Hydrocarbon Systems, AIChE, 7, 598, 1961 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. 179-183, 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. 59-64, 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. 73-88, 2001

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Symbols the fugacity of component i in the vapor phase. the fugacity of component i in the liquid phase. Ki yi. xi T P bij the vaporliquid equilibrium constant (K-value) mole fraction of one component i in the vapor phase. mole fraction of component i in the liquid phase. absolute temperature. absolute pressure. the fitted values coefficients in Equation (3) the saturation pressure of a component i. Tci Pci 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. i the activity coefficient for component i.

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