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Fluid Phase Equilibria 117 (1996) 225-232

**A Consistent Procedure for Pseudo-Component Delumping
**

Claude Leibovici*'a, Erling H. Stenbyb and Kim Knudsenb aElf Aquitaine Production, F-64018 Pau Cedex, France. bIVC-SEP, Department of Chemical Engineering, Technical University of Denmark, DK-2800 Lyngby, Denmark.

ABSTRACT If the mixture parameters of an equation of state can be expressed as a linear combination of pure component parameters and the phase molar compositions, then the component fugacities can also be expressed as a linear combination of pure component parameters with coefficients only depending on mixture properties. As a result Henry's constant is then available without any computation for any solute, as soon as the parameters describing the solvent have been calculated. A further extension of the same approach to phases in equilibrium leads to the same type of relation for the equilibrium constants. Thereby infinite dilution K-values can be obtained exactly without any further computation. Based on these results a consistent procedure for the estimation of equilibrium constants in the more classical cases of finite dilution has been developed. It can be applied when moderate binary interaction parameters are used. A potential application of such a procedure is the delumping of pseudo-components, i.e. the prediction of the detailed composition of the phases resulting from a flash calculation just performed on a lumped mixture. The method is described in details and a number of examples are provided in this paper. The method has been tested on two and four parameter cubic equations of state. Particular attention has been given to the conditions of temperature and pressure where the lumping process changes the number of phases.

1. INTRODUCTION It can be easily shown that, for any equation of state P = f(T,V) involving n parameters, the fugacity coefficient of component i in a mixture of N components can be expressed as simple as

]

In

xi

f'P

=

Co+ ~_, Ck " Pi,k k= 1

k=n

(1)

provided that the mixture parameters [or any of their power transforms] can be expressed as linear combinations of the pure component parameters, the weighting factors being the component mole fractions (x~)

*

Corresponding author

0378-3812/96/$15.00 © 1996 Elsevier Science B.V. All rights reserved 0378-3812(95)02957-5

SSDI

] where = AC o + ~ k=l AC k Pi. the infinite dilution K value can be exactly obtained for any component without any extra computation. 5 to 7 pseudo components are handled. it is requested to estimate. 1976) the values of p. this problem does not seem to have received any satisfactory answer. But. 2. To illustrate the problem we address here. under the assumptions outlined above. as simply as possible. this could only be considered as a first order approximation. it is well established that the equilibrium constants are only weakly dependent on composition. under the previous assumptions. the phase content of a component which has been lumped with other components. the Ck coefficients have been determined. any flash problem can be handled as a set of (n+ 1) equations and unknowns whatever N could be. at the current temperature and pressure conditions.p. / Fluid Phase Equilibria 117 (1996) 225.c/ (5) Again. Up to now. But this can be brought one step further: at equilibrium the isofugacity criterion (3) has to be fulfilled for all components. In general the Ck coefficients of equation (1) are complex functions of temperature. The basis of this work has been the simplified flash procedure proposed by Michelsen (1985).226 C. in some cases.2 are ~a i and bi. we shall let the original stream contain N . Moreover..232 j=l xj. This lumping can be very severe for compositional reservoir simulation where. THE DELUMPING PROBLEM Lumping many components together is a very typical task in oil and gas industry since all of the handled mixtures contain an about infinite number of components. in a system at equilibrium. contrarily to what happens with classical algorithms. and the logarithm of equilibrium constant can therefore be written as k=n Ln[K. (2) /--For the two-parameter PR EOS (Peng and Robinson.~ and Pi. The major interest of such an approach is that the CPU time is very weakly dependent on the number of components. this means that.k (4) = c? . For most applications. This implies that the mixture can be adequately represented without using any binary interaction parameters. for the mixtures which could be modelled without any binary or higher interaction parameters. pressure. typically. for the considered solvent. and phase parameters. who showed that. this can be obtained exactly without extra computation provided that. A possible immediate application of such formalism is the calculation of Henry's constant of any component in a specific mixture. respectively. Leibovici et al. This means that the above procedure can also be applied to have an approximation of K values outside the infinite dilution area.

~ . and x are feed. vapor. AC t and A C 2 are: &Co = In [ P [ RT a~" v~-b-. if any of the n parameters involved in the equation of state is rewritten for the original system . respectively.. a mandatory condition is that the parameters associated to the feed stream be preserved since the balance equation related to each of the n parameters ( ~ and b for the PR EOS) of the equation of state is Pk. In order to achieve this..y + (1 -.. This will work even better if the lumping does not affect. Leibovici et al.. in the case where no interaction coefficients are used.) b--~] vV +(1 + _ q ~ . For the PR EOS with no binary interaction coefficients the analytical expressions for AC0. Then. In order to obtain the (n+ 1) ACt-values (three for a two parameter EOS) the number of components in the lumped system has to be at least (n+ 1). then the ACk coefficients are the same for the lumped scheme and the original one.~ (9) where /3 is the vapor fraction and subscripts z.) ~ ] - bY 2Vt2" b "2 R T If binary interaction coefficients were used to describe the lumped system.----] ~ vl-b I J (6) AC x = - In v ~ _ + ( l _ + q ~ ' ) b~] vV +(1 vl+(1 ~-)b\J +_ q~-) bl / X[-2 b~ R T (7) ~ In ~/T b l R T AC 2 - Z t . If the lumped stream is flashed at given T and P conditions.z = [3 Pk.1 bt Z~. y. then the coefficients ACk are known analytically and the K-values of all components [M + 1. / Fluid Phase Equilibria 117 (1996) 225-232 227 components and let the lumping process reduce it to its first M components plus one pseudo-component which corresponds to the lumping of all components ranking between (M+ 1) and N.b t2 R T a~ - (1 . N. is there any manner to predict the vapor and liquid phase compositions for the original fluid with no extra computation? The method proposed above can be used for this purpose.1 + at In In Vl v'+ + (1 + V/2-)b l] (8) 2qt2. M +2 ./3)" lOk. N] which were lumped together can be easily obtained from equation (4).C. then the coefficients ACk can be approximated by any standard least square fit method and requested K-values can be predicted. If this is the case. the phase parameters and the phase split.1. or only slightly. and liquid.

to give the correct number of phases at a given temperature and pressure the concept of negative flash (Whitson and Michelsen.. The purpose of these examples is to see how well the phase compositions calculated for a fully specified mixture agree with those calculated for a lumped mixture where the equilibrium phases are delumped into the fully specified mixture with the proposed method. In the case of some k .p.E j=l xj. 4) Calculate Ki from equation (4) for all components in the full system. If not. / Fluid Phase Equilibria 117 (1996) 225-232 j=N j =M j=N p. RESULTS In order to evaluate the new procedure a number of test examples have been designed. use regression.--. y ~ 0 . p . 2) Perform a flash calculation with the lumped system in order to obtain the equilibrium constants of the pseudo components. 3. = E j~l xj Pj.E j=l xj .k = j = M + I r j=N j=M+I (12) E which corresponds exactly to the procedure proposed by Leibovici (1993) for a consistent estimation of pseudocomponent properties. As indicated in the theory section the delumping can be performed analytically if the binary interaction coefficients are equal to zero. In Example 1 a mixture of the normal alkanes from C~ to Ct2 is used (Mixture 1).. For a given composition a region will exist in which a flash calculation for the fully specified and the lumped mixture will not result in the same number of phases. Leibovici et al. and afterwards the vapor and liquid mole fractions are directly given.k + ~ j=M+I xj . the value of the vapor fraction is calculated. (10) and for the lumped system j=M+I j=M pk-. The mole fractions as well as the equilibrium constants are used for this comparison. n+l ~ M < N where n is the number of EOS parameters.228 C. In practice the procedure contains the following steps: I) Lump a mixture of N components into M components.* (11) a formal identification leads to j=N Dlumped. In the case of all k 0=0. use equations (6-8). a regression procedure can be applied. The Soave (1972) . This is illustrated in Figure 1.pj.--E j=l Xj • pj. 3) Determine the ACi values from the lumped system with M components. This is also tested in an example. 5) Using the ~ ' s from step 4) in the Rachford-Rice equation. In order. for the delumping process. + Xtun~ea Plumpea. A particular problem occurs due to the fact that the lumping process will change the phase envelope of the mixture. 1990) is used for the lumped system.

01 n-C10H22 0.0182 0.0188 0.0005 0.C Leibovici et aL / Fluid Phase Equilibria I 17 (1996) 225-232 229 modification of the Redlich-Kwong equation of state is used with all binary interaction coefficients equal to zero. and i-Cs.0156 0.0067 0.0301 0. P = 150 bar.0105 0.0853 0.0007 0.2543 0.0960 0.1148 0.0235 0. The equilibrium phase for the lumped mixture are delumped using the proposed method.0375 0. Two pseudo components are defined consisting of n-C4 plus i-C4 and n-Cs plus i-Cs. expressed as the vapor and liquid phase mole fraction as well as the equilibrium constant. i-C4. (1983) was used.0070 0. frac.70 0. The results are shown in Figure 2 as a plot of the logarithm of the equilibrium constant for the lumped-delumped mixture versus the logarithm of the equilibrium constant for the fully specified mixture.8682 1.0384 0.0318 0.01 n-CHH24 0.8689 0.0007 0.0182 0. A flash calculation is performed at 300 K and 50 bar for the full and the lumped mixtures.2516 0.1527 0.0003 0.0173 0. frac.5325 0. Flash of total system Total Compo.0008 1.0003 0.0195 0.0241 0.0017 0.0018 0.0161 0. = 0. The components were C~. SRK-EOS.0303 0.4310 0. Flash of full and lumped system. The composition is shown in Table 2. A flash calculation is performed at 300 K and 150 bar with the fully specified and the lumped mixture. Overall composition.0005 0.2516 0. n-Cs.0181 0.0602 0.0197 0.0026 0. frac.10 0.0027 0.0192 0.component sition C.0850 0.0698 0.0300 0.7430 0.0120 0.0977 0.6317 0.01 n-C6Hl4 0.0590 0.01 n-CsHls 0.6317 0.0189 0. C3. n-C4.4999 Ki x~ Yi Flash of lumped system Vap.0696 0.5333 0.0319 0. a and b.6324 0.02 Vap.0011 0.0319 0.0196 0.7398 0.0697 0. of this pseudo component are calculated as described by Leibovici (1993).0172 0.0017 0.0081 0.01 n-C9I-I20 0. The EOS parameters. Table 1 Mixture 1.8701 1.0195 0.4978 K~ x~ y~ 0.4950 Ki xi y~ Flash of delumped system Vap.0849 0.0011 0.0026 0.06 The mixture is lumped by creating a pseudo component containing the components from C7 to C~2.0002 0. The results.H4 C2H6 C3Hs n-C4Hi0 0. = 0.4310 0.5319 0.1147 0. In this example the cubic EOS proposed by Adachi et al.2153 0. all kij = 0.0198 0.0080 0. The overall composition is given in Table 1.01 n-CI2H~6 0.0008 0. T = 300 K.1549 0.0080 0.0173 0.0101 0.1191 0.0197 0.0002 0.4342 0. = 0. are shown in Table 1.0193 0.0960 0.01 n-CTHl6 0.1149 0.7398 0.1187 n-CsH12 0. Result of delumping after flash of lumped system. .05 0. As Example 2 a mixture containing isomers of alkanes was selected (Mixture 2).0026 0.1527 0. C2.

7870 0.1339 y~ 0.0 l l l l l l l l l l l l [ l l l l l t l l l l l ~ l . Overall composition. l l l l l l l l I I I .L POINTS - ln(Kl) from flash versus ln(Ki) from the delumping ~ 150 1 ' 1 1 I I I ' ] ' I 0.7875 0.0460 Flash of delumped system Vap.1335 0.l -3. = 0. T = 300 K.1303 0.1811 K~ 3.1256 0.1458 0.2328 0.1816 K~ 3.1 Vap. = 0.230 C Leibovici et al.3814 0.1125 0. For Mixture 2 the equilibrium constants for the delumped system are shown versus those for the full system.232 300: ~250 I 1.0460 0.7869 0.0100 0.0248 0. Phase envelope of Mixture 1 as a full and a lumped system.1049 0. P = 50 bar. Mixture 2.5 ln(Kula.1125 0.50 CRITIC/.1049 0. frac.1339 Y~ 0.h) Figure 1.3662 xi 0.0248 0.50 4 / 0 200 400 600 : :'~ ~* cY~lculated resuls t [ TEMPERATURE (K) I 3.0747 0. all kij = 0.1 0. ALS-EOS.2617 0.1904 0.1315 0.1125 0.0436 Flash of lumped system Vap.3663 0.1315 0.1457 0.0675 0.1 0.2674 0. -I .5 0.1903 0.1049 0.0192 0.0747 0.1302 0.1815 Component Ct C2 C3 i-C4 n-C4 i-C5 n-C5 Ki 3. frac.0611 Xi 0. Result of Example 2. [ t . Flash of total system Total composition 0.0082 0.0 1.0611 x~ 0.1256 0.1665 0.2327 0.0082 . / Fluid Phase Equilibria 117 (1996) 225.3814 0. = 0.3 0. Table 2.2329 0.9326 0.1 0. Flash of full and lumped system. Result of delumping after flash of lumped system. frac.9329 0.1 0. Figure 2.1 0.00 -~ • 1.3662 0.9326 0.0460 0.0100 0..3820 0.00 .0181 0.0192 0.1336 0.1255 Yi 0.

01 atm and a further reduction in pressure was of little interest. In Figure 4 the root mean square of the absolute deviation of the mole fraction in each phase is shown as function of the vapor fraction. All binary interaction coefficients were set equal to zero.40 Vapour 0. i i i i 300 350 400 450 0. Leibovici et al.00 0. flash calculations were carried out for Mixture 3 at the temperature 300 K and various pressures.00 Figure 3. The root mean square of the absolute deviation in mole fraction between the delumped and the full system as function of the vapor fraction. Figure 4. 1976). i i ' i . Result of Example 3.20 TEMPERATURE (K) 0.0009 0'30. For Mixture 1 the phase envelopes calculated with the PR-EOS of the full and the lumped system are shown. For Mixture 3.95.0000 0.0012 0.0003 200 I 250 .80 1.2308).0015 "•2601 ~ 240// /// 2201 // //eI / --* o lumped system crit(cal point delumped systems 0. . 280 - 0. i i i i J J ~ . In Table 3 it can be seen that the lumped system results in a negative value of/3 (vapor fraction) but that the delumping procedure results in a small positive vapor fraction. In Figure 3 the selected (T. Thereby the method could be tested for different values of the vapor fraction. The maximum vapor fraction is just below 0.60 fraction 0. In Example 4. The ALS-OS was used with the k Uvalues of Aasberg-Petersen and Stenby (1991).C. Mixture 3 contains the same alkanes in the same ratios as in Mixture 1 with addition of a significant amount of carbon dioxide (Xco2=0. Result of Example 4.P) is seen to be located in the area where the fully specified and lumped systems give different numbers of phases.0006 0. /Fluid Phase Equilibria 117 (I 996) 225-232 231 Example 3 was made with Mixture 1 and the PR-EOS (Peng and Robinson. At this vapor fraction the pressure was 0.

: "A consistent procedure for the estimation of properties associated to lumped systems". PR-EOS. Leibovici. 1990. CONCLUSION A consistent delumping procedure has been developed for phase equilibrium calculations with cubic equations of state. Negative flash applied. Sci. Soave. P = 217.232 C. where n is the number of independent equation of state parameters. Fluid Phase Equilibria.L. REFERENCES Aasberg-Petersen. K. p. Chem. Fundam. H. Y.L. p. Lu.H. D. and delumped system.B. 184-188. Eng..-Y. lumped. 248-254. The minimum number of components necessary is n + 1. M.C. 53. . T = 300 K. and Michelsen. 1197-1203. 25.H. G. Flash of system vapor fraction total 0. Calculations close to the saturation point are improved by using the negative flash concept. Michelsen.00325 5. If non-zero interaction coefficients are introduced a simple regression procedure is required. 59-64. If all binary interaction coefficients are set equal to zero the whole delumping calculation can be made by analytical expressions. 1972. and Sugie. p.: "Prediction of thermodynamic properties of oils and gas condensate mixtures". ACKNOWLEDGEMENT The authors want to thank Elf Aquitaine Production and the Danish Technical Research Council for financial support of this work.6 bar.: "The negative flash". 1993. Fluid Phase Equilibria. Table 3. p.. Chem. The vapor fraction for the full. 189-197. p.: "A new two-constant equation of state".: "A four-parameter equation of state'. 27.: "Simplified flash calculations for cubic equations of state". The results of the first investigations are very promising. Chem. M.: "Equilibrium constants from a modified Redlich-Kwong equation of state".00374 delumped 0. Leibovici et al. B. C. Ind. Eng. p.-Y. 11. Res. Eng. Adachi. Peng. 1985. 87. 51-72. 29-48. Ind. 15. Fluid Phase Equilibria. all kij = 0. 1983. / Fluid Phase Equilibria 117 (1996) 225-232 4. and Stenby E.. Example 3 and Mixture 1. Fluid Phase Equilibria.. 1976. 30. p. C. Whitson. 1991.03795 lumped -0. and Robinson D.

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