SPe24112 Analytical Theory of Combined Condensing/Vaporizing Gas Drives Analytical solutions for dispersion-free flow of two-phase, four-component mixtures confirm the existence of condensing/vaporizing gas drives and reveal how they behave. R. T. Johns, B. Dindoruk, and F. M. Orr, Jr., Stanford University SUMMARY ‘Analytical solutions are presented that confirm the existence of ‘4 combined condensing and vaporizing displacement mechanism in enriched gas drives. The solutions are derived for dispersion- free, one-dimensional displacements in four-component hydrocar- bon systems. A simple geometric construction is used to find 1 key tie line in the solution, the “crossover” tie line. This tie line is shown to control the development of miscibility in con- Ke, > Keg > Keg forall compositions inside the two-phase region. Only Cif, has a K-value greater than unity at this temperature and pressure. Johns!® shows that solutions of displacements in aystems in which Kovalues are strictly ordered are well posed. We concentrate here on the mechanisms of dis: placement rather than on solution uniqueness and continuity Fig. 1 and Table 2 give the analytical solution for a three- component oil labeled ©) displaced by enriched mixtures of CHa and Cs (labeled I, Ip, Ig, 1g, Ig). Fig. 2 shows the correspond- ing composition and saturation profiles for the immiscible dis- placements by injection gas Ty, Ig and Ig. Consider the typical solution illustrated for the displacement by injection gas Ig. The solution lies on three key tie lines: (1) the tie line whose extension passes through the injection gas composition (called the injection 428 tie line), (2) the tie line whose extension passes through the «il composition (called the initial cil tie line), and (3) a key tie line known as the crossover tie line. ‘The analytical solution in- cludes: (1) a trailing nontangent shock from the injection gas composition Ip to Fo along the injection gas tie line, (2) a region 8 Fig. 1: Composition route for displacements of oil © by CH4/Cs gas mixtures at 2000 psia, 200 *F. Geometric construction of crossover tie line is shown for injection gas Ip. of constant state at F, (8) a self-sharpening tangent shock from Fg to Eg on the crossover tie line, (4) a continuous variation from Eg to the equal eigenvalue point Dz, with velocities given by the tie-line eigenvalue, (5) a continuous variation (see Appendix A) along the nontie-line path from Dz to Bg on the initial oil tie line, with velocities given by the nontie-line eigenvalue, (6) a region of constant state at Bg, (7) and @ nontangent shock from Bg to ‘the oil composition ©. The Fz — Eg shock occurs because the nontie-line eigenvalue increases from Bg to Fa, and a continuous variation there would violate the velocity constraint. A continu- cous variation along the Dg — Bg nontieline path, however, is allowed because the nontie-line eigenvalue increases from Dg to Ba, Fig. 2 shows that the components in the oil are separated chromatographically according to their volatilities. CH, with the highest volatility, is displaced fist followed by a small Cy bank. Ce disappears next at the selfsharpening shock from Ea to Fp. Cig with the lowest volatility is completely evaporated at the slow moving trailing shock from F to Ig. In this example, the nontie-line path intersects the constant-composition plane for (CH, twice, and thus, the CH, concentration decreases and then increases from Bg to Da (this effect ia more pronounced from Bg to Dg). Because the nontie-line eigenvalue does not vary signif cantly from Bg to Dg, those compositions are nearly the same, as the profiles of Fig. 2 show. Fig. 3 gives a comparison of the analytical solution for injec- tion gas Ty with finite difference solution (fully explicit with single-point upstream weighting) using 1000 grid blocks and a time step size of 0.0001. As Fig. 3 shows, numerical dispersion smooths the shock fronts in the displacement. The nontiedine path is smoothed the most because it is nonsharpening. Other- wise, excellent agreement is obtained, SOLUTION CONSTRUCTION ‘The analytical solution can be computed easily once the crossover tie line is found. Orr et a1? demonstrated a simple construction to find the crosover tie ine when a three-component oil (C H/C, /Cyo) was displaced by pure COs. In that system the SPE Advanced Technology Series, Vo. 1, No. 2Breasae vaca oo Fig. 2: Composition and saturation profiles for the routes shown in Fig, 1 at 2000 psia, 200 °F. = hele Gas Saturation ot Mole Fractions 8° Bimensicnfess Volbaty (xs) Fig. 5: Compasison of analytical and numerical profiles with zp = 0.001 and Atp = 0.0001 for solution with gas Ip, SPE Advanced Technology Series, Vo. 1, No. 2 ‘crossover tie line was reached only by shocks and could be found easily. For the more complex case of enriched gas injection, however, ‘that simple geometric construction can be generalized. For ex- ample, in Fig. 1, nontangent and selfsharpening shocks occur at the trailing end of the displacement (neat the injection gas com- position). In Appendix B we prove that for a series of succeasive shocks from one tie line to another, the extensions of these two tie lines must intersect, regardless of the number of components present. Thus, in the CH/Cs/Ce/Cie example, the extension of the injection gas tie-line must intersect the crossover tie-line extension. The intersection point (labeled Xq) lies outside the quaternary diagram, as is illustrated in Fig. 1 for the displace rent by injection gas Ig. We also show in Appendix B that the generalized crossover tie line construction makes finding compositions E and F straight- forward, Point E can be found by constructing a tangent shock along the crossover tie line from the intersection point X. The velocity of this shock is EXW FP ono Because this is tangent shock, the velocity of composition Bis she axe Aevrsme 6) pave "= a5," Furthermore, we prove in Appendix B that a with equal velocities occurs. That is, Axe AXE Are MP eat o Thos, compotion F canbe found by constructing shock from X to F such that its velocity is equal to AF.19 Therefore, the solution procedure forthe CHa/C/Ce/Oue di placement isa two patt proces. Fret, the key he lines and com Potions must be found bythe fllowing sep: ind the tie lines that extend through the injection gas and oil compositions. The negative lash procedure described by Whitson and Michelsen? can be used to find these tie lines. To do so, integrate along a line path from the cil tie line and compute succes- sive tie lines. The crossover tie line is the tie line along the nontie-line path that intersects the 3. Construct a tangent shock from X along the crossover tie line to locate composition E. The velocity of this shock, AP, is equal to the velocity, A*®, of the selfsharpening shock from F to E. 4. Find composition F by constructing # nontangent shock from X along the injection gas tie line such that the shock velocity is equal to AF Once the key te lines and compositions are found, the location of each overall composition is found from its wave velocity. The velocity of the trailing shock from injection gas composition Ito point F is given by the shock jump relations, Eq. 4. (In some instances, a tangent shock can be constructed from the injection gas composition along the injection gas tie line. This occurs only when point F is beyond the tangent point. In such cases, a small continuous variation along the injection gas tie line is possible. For example, as Fig. shows, a small continuous variation occurs from Fy to G) in the displacement by injection gas Ty.) The velocity of compositions that vary continuously along the crossover tie Tine from E to the equal eigenvalue composition D is given by the tiene eigenvalue, A = @fy/dS,. The velocities of compositions °CH on o te coasarg ones Fig. 4: Ternary representation of C/V daplacement of oil © by ep that vary continuously along the nontie-line path from D to B are given by the nontie-line eigenvalue. The path is obtained by taking small steps in composition space. The velocity of the shock from B to O is obtained from the shock jump relations, Eq. 4 (A continuous variation along the oil tie line may occur if point B lies before the tangent point ftom the oil tie line to ©.) CONDENSING/VAPORIZING MECHANISM. ‘The displacements shown in Fig. 1 have features of both con- densing and vaporizing mechanisms. In the CH4/Cs/Cs/Cis ex- ample, condensing behavior occurs at the leading edge of the dis- placements followed by a trailing vaporizing drive. ‘The combined condensing and vaporizing mechanism is best il lustrated by constructing two limiting ternary solutions from the ‘quaternary displacements of Fig. 1. Fig. 4 shows two ternary solu- tions constructed by removing (along a dilution line) components from the oil or injection gas. In Fig. 4a, Ce has been removed from the oil O (shown as 0’) to illustrate the condensing portion, ‘of the solution. The ternary solution includes a continuous varia tion along the nontiedine path from B' to D/ with Cs condensing into the liquid phase, The nontie-ine path can be taken because the nontie-line eigenvalue increases from the injection gas tie line to the initial oll tie line (see Appendix A). A small continuous variation along the initial oil te line occurs from A’ to B’. The vaporizing portion of the solution is illustrated in Fig. 4b and in Fig. 1 by removing C3 from the injection gas Ig (shown as Ty) [A self-sharpening shock occurs along the nontieline path in this ‘This, the four-component solution can be decoupled approx imately into two successive ternary solutions which exhibit con- ddensing and vaporizing behavior. Fig. § illustrates this behavior further for the nearly miscible displacement by injection gas Tg Tn that case, the component K-values and phase densities both nearly converge at the crossover tie line. Thus, in the condensing portion of the displacement, the liquid phase density decreases as, heavier components ate replaced by lighter components (Cs and Ge), while in the trailing vaporizing portion, the liquid density increases as the lighter components in the oil are extracted. ‘This result is similar to that presented by Zick® in his Fig. 12 w ‘Dimensionless Veloety (rola) Fig. 5: Fluid properties for nearly miscible C/V displacement of, cil O by gas Ig Fig. 6 further illustrates the C/V mechanism. It demonstrates that the analytical solution for the composition path lies on ver tical and horizontal ruled surfaces (a ruled surface is generated by a sequence of lines) within the quaternary diagram. The ruled surfaces are composed of tic lines that intersect the composition path and may be thought of as cross-sections of the quaternary diagram (they are nearly planar). The condensing displacement ‘occurs on the vertical ruled surface (composed of tie lines along, the nontieline path), while the vaporizing displacement occurs along the horizontal ruled surface (composed of tie lines which intersect the crossover tie-line extension). Hence, the crossover tie line can be defined as the intersection of the vertical and hor- ‘zontal ruled surfaces. ‘MINIMUM ENRICHMENT FOR MISCIBILITY Multicontact miscibility in C/V displacements is obtained when the crostover te line becomes a critical te line. Fig. 1 Iusteates this for the CHs/Cs/Ce/Cie system in which the in- jection gas is enriched with Cs. As the gas is enriched to Tg, the crossover tie line moves closer to the critical locus, and the shocks and waves approach unit velocity (see Fig. 2). That i, the two- phase transition zone shrinks, and flow approaches a piston-like displacement. 1€Cs enrichment is increased to the minimum en- richment for miscibility (MME at Ig), all shocks and waves have unit velocity (see Appendix C for proof). “Thus, it isthe crossover tie line and not the injection gas tie line that determines miscibility here. For example, in Fig. 1, the crossover tie line approaches the critical locus at a mixtare of 61.5% CH, and 38.5% Cs (Iq), while the injection gas tie line is al ie line at an enrichment of 47.0% CH, and 53% Cs (Ig). ‘Thus, if the injection gas ti line were used to determine misci- Uilty in C/V displacements, the calculated MME would contain significantly more Cy From experimental and simulation results Zick® observed that “In between (the condensing and vaporizing zones) isthe sharp, two-phase transition zone, the two phases of which are almost, but not quite miscible.” Fig. 5 shows the distribution of K-values Jn the transition for injection gas Tg. Fig. 5 clearly illustrates that the Kevalues in the middle of the transition zone are close SPE Advanced Technology Series, Vol. 1. No. 2Cue (oy Hordonar Rules Sues Vaportng) o (a) "Vera Rules Suree (Condensing) Fig. 6: Mustration of ruled surfaces of tie lines upon which the displacement is either condensing or vaporizing. to unity, and hence, the two-phase fluids are nearly miscible. As the crossover tie ine approaches the critical locus, the K-values approach unity. Thus, an important result of this paper is to demonstrate conclusively the existence of combined condensing and vaporizing displacement behavior in which multicontact mis- ibility is controlled by the approach of the crossover tie line to the plait point locus as the enrichment or pressure is increased. PSEUDOTERNARY DIAGRAMS Several authors have shown that projections on pseudoternary diagrams of tie lines intersected by the composition path of a displacement can exhibit a neck in the two-phase region for mul- ticomponent systems.5:89.11 Figs. 7 and 8 show these same fe tures for pseudoternary diagrams constructed by replotting the ruled-surface tie lines for injection gas enrichments 1y, Ta, Tg, and Iq. Fig. 7 is constructed by lumping Cy and Cie, while Bis constructed by lumping Cs and Ce. ‘The pseudoternary phase diagrams in Fig, 7 reproduce the fea- tures of phase diagrams obtained by Zick and Stalkup from nu- ‘merical simulations. Fig. 8, however, gives a different view of the same displacements and shows similar features to pseudoternary diagrams given by Lee ef alll In the condensing portion of the displacement, the tie-line lengths become smaller as the solution route approaches the crostover tie line (along the vertical ruled surface as shown in Fig. 6a). Because the crossover tie line is clos- fest to the critical locus, itis the shortest length tie line obtained in the displacement. The vaporizing portion of the displacement begins at the crossover tie line, and ti-line lengths increase until the injection gas te line is reached (along the horizontal ruled sur- facesin Fig. 6b). Because the crossover tieline length decreases as the displacement approaches miscibility, the neck region becomes thinner for nearly miscible floods. For example, the immiscible displacement with injection gas Ig shows less curvature in the two-phase region, while displacements closer to the MME (ie. Ig) give thinner necks in the two-phase region. If the injection 188 entichment is increased further to the MME Iq, the neck be- comes a single point, as the crossover tie line becomes a critical tic line. Because composition paths in numerical simulations are influenced by numerical dispersion, however, the crossover tie line SSPE Advanced Techoology Series, Vol. 1. No.2 CH CH CeCe) Cy (CeO) co |e nooton Gas 'eIniecton Gas. Bonar reine vont fede woul Cy (Cet Cre) Cy (MME) Inocton Gas IaInlocton Gas Fig. 7: Peeudoternary diagrams constructed from the ruled sur faces like those in Fig. § by lumping Cp and Cie CH, . A (CatCe) Crp (Ca+Ge) is ncton Gon Teneton Gan cn, | —oe st Cw (Ca#Ce) 6 (Cate) Iscton Gas {Aeon Gas Fig. & Pseudoternary dingrams constructed from the ruled su faces like those in Fig. 6 by lumping Cs and Ce.Fig. 9: Composition route for displacements of oil O by CHa/C2 ‘ga8 mixtures at 2000 psia, 200 °F. Geometric construction of crossover tie line is shown for injection gas Tq. obtained numerically would still have a small finite length at the MME. (CH4/C2/Cg/Cig DISPLACEMENTS. In the next example, we replace Cs in the injection gas with Cz and hold the temperature, pressure, and initial ol composition constant, In this system, the two-phase region is larger due to the greater volatility of C over that of Cs. Hence, the displacement by CHa/Ca gus mixtures should be les efficient than those with CH4JCs gas injection. Figs. 9 and 10 and Table 3 show the analytical solutions for displacements with gas enrichments I, Ty, Tg, Lg, Ig, and Ig. ‘Because the volatility of ethane is greater than unity (Ke, > 1.0), some features of the displacements differ. In particular, the continuous variation along the nontie-line path on the vertical led surface is replaced by a selsharpening shock. The K-value rule (derived in Appendix A) applied to the ternary CHl,/Ca/Cie face verifies that a shock must occur along the nontie-line path Hence, sis proved in Appendix B, the crossover tie-line extension rust intersect both the oil and injection gas tieline extensions, and the crossover tie line can be found easly. The intersection with the oil tie line (X) and the injection gas tie line (X4) is shown in Fig. 9 for the displacement with injection gas Iq. ‘The solution consists primarily of shocks with only & small continuous variation along the crossover tie line. Just as before, the solution can be found from a two-step process in which the key tielines, points B, C, D, E, and F, and the velocities of the overall compositions are calculated. The solution procedure differs from the CH,/Cs/Ce/Cre ayster only in that points B and D are ied from shock balances rather than by integration along a 1 path shown in Figs. 9 and 10, less efficient (more immiscible) than the displacements of the CH4/Cs/Co/Cie system. That is, the leading shocks are faster and the trailing shocks are slower. Also, the crossover tie line is farther from the critical locus. Hence, the minimum enrichment needed for miscibility is higher (approximately 29% CH and 71% C2). Just as before, it would take significantly more C (at Ig) 2 ‘Saturation or Mole Fractions Gas ao ‘Bmensicntess Velscity xo) Fig. 10: Composition and saturation profiles for the routes shown in Fig. 9 to make the injection gas tie line a critical tie line, and thus, the ‘crossover criterion (MME at Ip) is less restrictive. DISCUSSION ‘The examples shown illustrate that when a fourth component is added, it is possible to have a displacement with features of both condensing and vaporizing gas drives. Also, a third key tie line of the solution route, the crossover tie line, was shown to control the development of miscibility in these systems. Dis- placement mechanisms other than a combined condensing and vaporizing one, however, can exist in four-component drives. It is easy to conceive of oil and injection compositions that could ‘ive purely vaporizing, purely condensing, oF combined vaporiz- ing (leading) and condensing gas (trailing) drives.19.14 For these ‘other mechanisms, the injection or oil tie line will control the development of miscibility, not the crossover tie line.19.}4 Thus, in four component systems, there are four possible mechanisms of displacement. The variety of displacement types may help to explain the contradictory conclusions reached by Novosad and Costain®, Tiffin et al10 and Lee et alt In any case, the four- ‘component analytical theory allows unambiguous calculation of the conditions required for multicontact miscibility, regardless of ‘he combination of mechanisms. For the systems considered here, optimum displacement efficiency occurs when the injection ges is sufficiently entiched that the crossover tie line becomes tangent, to the critical locus. ‘That enrichment level can be found quite ‘easily using the geometric construction for the crossover tie line (Appendix B).. Te seems likely that many real oil displacements will have fex- tures of both condensing and vaporizing displacements. For ex- ample, many authors have assumed that carbon-dioxide floods are always purely vaporizing (especially at high temperature) ‘The COs/CH4/Ci/Cio example given by Orr et all2, however, can now be clearly identified as a C/V displacement. ‘The fact that the crossover tie line controls development of miscibility in C/V displacements has important implications for mixing-ell algorithms?1.22.2 used to estimate MMP's and MME's. Those methods determine the MMP or MME as the pressure or en- richment at which either the initial or injection composition lies on the extension of a critical tie line. Jensen and Michelsen?4, SPE Advanced Technology Series, Vol 1, No, 2however, used the COs/CH«/Ca/Cio system as an example of a system for which such methods give incorrect results. The solu- tions presented here and by Orr et al. show why. The mixing-cell algorithms do not identify the crossover and hence they sive incorrect MMPs and MME’s for C/V drives in which the ‘crossover tie line controls the development of miscibility. We ar- {gue, therefore, that such methods should not be used unless itis known a priori that the displacement mechanism is purely vapor- ining or condensing, ‘The solutions given here are for one-dimensional, dispersion- {ree fow. Displacements in reservoir rocks are anything but one- dimensional, however, and they are certainly not dispersion free. In addition, ‘there are many more than four components present in reservoir fluid systems. Hence, there are many more issues to be explored as a deeper understanding of gas injection processes is developed, and some progress has already been made. The ‘effects of dispersion and multicomponent flow are considered by Johnset al28, and extension of the four-component theory to sys tems with more than four components described by Johns!® and Dindoruk.14 The interaction of heterogeneity, gravity segregation, viscous crossflow and phase behavior is examined by Pande.27 No matter how complex the flow situation, however, the underlying physical mechanism that makes possible high local displacement efficiency is the chromatographic interaction of phase behavior and flow, and hence, the theory given here forms the basis for understanding the full range of physical mechanisms that control displacement performance in enriched gas drives. CONCLUSIONS We have shown through analytical calculations for four- component systems that: 1. In certain four-component enriched gas floods, the mecha- nism of displacement is a leading condensing drive followed by a trailing vaporizing one. 2. In C/V gas drives, miscibility is obtained when the injection gas is sufficiently enriched to drive the crossover tie line to the critical plait point locus. ‘Thus, the crossover tie line, not the injection gas tie line determines miscibility in such systems. 3, When the crosover tie line is reached only by self- sharpening shocks, it can be found easily from a geometric, construction. In such cases, the crossover tie ine is the only tie line that intersects both the initial and injection te lines. 4. The neck region of pseudoternary diagrams is directly related to the combined displacement mechanism. The crossover tie line is the shortest tie line in the neck region of the ternary diagram. 5. A simple rule based upon component K-values allows an a rior’ prediction of the type of wave (self-sharpening shock ‘oF continuous variation) along the nontie-line path. NOMENCLATURE overall volume fraction of component i volume fraction of component i in phase j ‘overall fractional low of component i fractional flow of phase j equilibrium component K-values molecular weight critical pressure, psia sas saturation residual ofl saturation SPE Advanced Technology Series, Vol. 1, No. 2 critical temperatare, °F dimensionless time, pore volumes throughput dimensionless distance mole fraction of component jin phase j tole fraction of component ‘in the liquid phase role fraction of component é in the vapor phase critical specific volume, f€ b-mol b= molar density of component j, Ib-mol/ft? My = viscosity of phase j, ep A dimensionless shock wave velocity De = eigenvalue associated with composition variation along 2 tie line cigenvalue associated with composition variation along a nontie-line path centric factor binary interaction parameters arc length along a nontie-line path, ft ACKNOWLEDGEMENT ‘The research described here was supported by U.S. DOE grant No. DE-FG21-89MC26253 and by the SUPRI-C Miscible Flood- lates, ‘That support is gratefully acknowl REFERENCES 1. Hutchinson, C.A. Jr. and Braun, P.H.: “Phase Relations of Miscible’ Displacement in Oil Recovery,” A.J.Ch.E. J. (March 1961) 64-72. 2. Rathmell, J.J. Stalkup. FI. and Hassinger, R.C.: “A Lab- oratory Investigation of Miscible Displacement by Carbon Dioxide,” paper SPE 3483 presented at the 197] SPE An- ual Meeting, New Orleans, Oct. 4-8. 3. Helferich, F.G.: “Theory of Multicomponent, Multiphase Displacement in Porous Media,” SPEJ (Feb. 1981) 51-62. 4, Dumoré, J.M. Hagoort, J. and Risseeuw, AS. “An Anz lytical Model for One-Dimensional, Three.Component Con- densing and Vaporizing Gas Drives,” SPEJ (April 1984) 169-179, 5. Zick, A.A: “A Combined Condensing/Vaporizing Mecha- nism in the Displacement of Oil by Enriched Gas,” paper SPE 15493 presented at the 1986 SPE Annual Technical Conference and Exhibition, New Orleans, Oct. 58. 6. Stalkup, FL: “Using Phase Surfaces to Describe Condens- ing Gas Drive Experiments,” SPEJ (May 1965) 184-188. 7. Stalkup, Fil: Miscible Displacement, Monograph Series, SPE, Richardson, TX (1983) 8. 8, Stalkup, FLL: “Displacement Behavior of the Condens- ing/Vapotizing Gaa Drive Process,” paper SPE 16715 pre- sented at the 1987 SPE Annual Technical Conference and Exhibition, Dallas, Sept. 27-30 9. Novosad, Z. and Costain, T.: ‘New Interpretation of Re- covery Mechanisms in Enriched Gas Drives,” J. Canadian Pet, Tech, (March-April 1988) 27, No, 2, 54-60. 10, Tiffin, D.L., Sebastian, H.M., and Bergman, DF. “Dis placement Mechanism and Water Shielding Phenomena for ‘a Rich-Gas/Crude-Oil System,” SPERE (May 1991) 193- 199, 11, Lee, $-T, Lo, H. and Dharmawardhana, B.T.: “Analysis of Mass Transfer Mechanisms Occurring in Rich Gas Displace- ment Process,” paper SPE 18062 presented at the 1988 SPE, “Annual Technical Conference and Exhibition, Houston, TX, October 25. 1B12, Orr, FM, Jr, Johns, R-T. and Dindorak, B, in Four-Component Vaporizing Gas Drives,” 1993). 18, Monroe, W.W., Silva, M.K., Larsen, LL. and Orr, F. Jez “Composition Paths in Four-Component Systems: EE fect of Dissolved Methane on 1D CO; Flood Performance,” SPERE (August 1990) 423-432, M4. Dindoruk, B.: ‘Analytical Theory of Multiphase, Mul component Displacement in Porous Media", PhD disserta- tion, Stanford University, Stanford, CA (1992) 15. Lohrenz, J., Bray, B.C. and Clark, C.R: “The Viscosity of Pure Substances in Dense Gaseous and Liquid Phases,” JPT (4964) 1171-1176. 16. Peng, D.Y. and Robinson, D.B: “A New Two-Constant Equation of State,” Ind. Eng. Chem. Fund. (1976) 18, 59- 64 AT. Larson, R.G.: “The Influence of Phase Behavior on Susfac- tant Flooding,” SPEJ (Dec. 1979) 411-422. 18. Ceré, A. and Zanot ‘Miscibility SPERE (May F.: “Sharpening Behavior and Dis- persion in a Chemical Flooding,” Proc., Third European Conference on Improved Oil 16-18. Recovery, Rome (1985) April “Analytical Theory of Multicomponent Gas ‘Two-Phase Mass Transfer”, PhD dissertation, Stanford University, Stanford, CA (1992). 20. Whitson, C. and Michelsen, M.: “The Negative Flash” Fluid Phase Equilibria 88 Part Il (December 1989) 51-72. 21. Hagoort, J. and Dumoré, J.M.: “Determination of Mini- mum Miscibility Pressures with an Equation of State Pro- sram,” Proc., Third European Conference on Improved Oil Recovery, Rome (1985) April 16-18, 61-66. 2. Kuo, S.8.: “Prediction of Miscibility for the Enriched-Gas Drive Process,” paper SPE 14152 presented at the 1985 SPE Annual Technical Conference and Exhibition, Las Vegas, Sept. 22-25. 23. Luks, K.D., Turek, EA. and Baker, L.Es “Calculation of Minimum Miscibility Pressure,” SPERE (Nov. 1987) 501~ 508. 24. Jensen, F. and Michelsen M.L: “Calculation of First Con- tact and Multiple Contact Minimum Miscibility Pressures,” Jn Situ (January 1990) 14, No. 1, 1-17. 25. Johansen, T. and Winther, R.: “Mathematical and Nu- merical Analysis of a Hyperbolic System Modeling Solvent Flooding,” Proc., Second European Conference on the Mathematics of Oil Recovery, Arles (1990) Sept. 11-14, 26, Johns, R.T., Payers, F.J., and Orr, F.M., Jn: "Effect of Gas Enrichment and Dispersion on Nearly Miscible Dis- placements in Condensing/Vaporizing Drives,” paper SPE 24938 presented at the 1992 SPE Annual Technical Confer- ence and Exhibition, Washington, D.C., Oct 47. 21. Pande, K.K, “Effects of Gravity and Viscous Crossflow on Hydrocarbon Miscible Flood Performance in Heterogeneous Reservoirs,” paper SPE 24935 presented at the 1992 SPE ‘Annual Technical Conference and Exhibition, Washington, D.C, Oct 47, APPENDIX A. K-VALUE RULE FOR, SELF-SHARPENING WAVES Eq, 1 ean be transformed to a new set of dependent variables, and y28. For ternary systems, €).[% BIE - [E)-[9 Alle] an) where the eigenvalues are cay identified as oh _ of Ath we ae ue Bt, ann ad the fention hin Mn Ze ee (a-a ‘The function a isthe tiene slope (a = (ya ~ x2)/(ys ~ 23)) and bis the tieline intercept (6 = (y:22~ z1¥2)/(v1 ~ 24)), and € 4 parameter (arc length) that varies monotonically along the sontie-line path ‘The eigenvector associated with the nontieline eigenvalue is aC, yg dn Aw ea ee ‘The derivative of the nontielne eigenvalue along the nontc- line path is (A~4) du 1 [ahi dh aca, dh e an|[#+# dole 2 Because 4 = Ane (proved using the chain rule), Bq. A-5 be (A-5) Dae _ dh (1 Anw) & Gah ‘The expression for the nontie-line eigenvalue can be substituted into this equation to obtain Bar. _ah(F = Cy ag (Cr Fhy Hence, in the region where Fy > C, (the region of interest), the nontiene eigenvalue decreases along the nontcdine path if 2 is positive. Thus, the sign of dh/c€ determines how the nontiefine tigenvalue vaies along the nonti-ine path. To show how sel-sharpening behavior depends on component volatility, we asrume that equilibrium Kevelues, Ky = n/t do not change with composition variations, After signfcant algebrat9, we find that the derivative dh/d is proportional to ‘new function H, (a-9 (A-7) (Ky = Ka)( Ka = Ks)] de UR Kai Ke) | aE If > 0, the nontie-line eigenvalue decreases along the nontie-line path, while if JF < 0, the nontieline eigenvalue increases along the nontieline path. For the case when K-values are independent of composition, the derivative dza/d¢ is either positive or nega- tive depending on the direction taken along the nonte-line path. ‘To apply this result to the PREOS, however, typical K-values rast be chosen. For example, in Fig. 4b, Ki = Kom > 1.0, Ky = Ko < 10 and Ky = Koy << 1.0, and therefore, dz/dg <0 from Ey to Fy. Hence, it in negative, and a shock is needed because the nonteline eigenvalue increases from By to Fy. Direct computation with the PREOS shows that this raat holds for all nontieline paths (a-) SPE Advanced Technology 5. Vol. 1, No.APPENDIX B, GENERALIZED CROSSOVER TIE LINE CONSTRUCTION Consider the displacement route shown in Fig. 1 for injection of a CH, and Cy gas mixture. For ne components, the jump relations for the F — E and X — E shock are EPO RE gxe_ FX- FE - ee ee] (e-1) Because compositions X and F contain no Cy, Of, = FE, = c, snd from Eq, B-1, we (B-2) ‘so, the X + E shock must be tangent tothe fractional fow surface at Ein order to satiny appropriate entropy and velocty Constraints (proof of this statement is given by Johns!®). Thus, Composition E ean be found fom tangent construction along the crossover tie ine in which AX® = AP = d/?/45,, ‘Eq. B-1 can be rearranged to eliminate F,*. That is, FRA FP _ MEE CP) 4M HCK-C8) g_ yy ORF OF =F Because AX® = A?®, Eq, B-3 becomes BEOEP _ xp ogre oqXP oat @-» oF CF Hence, strangle of equal velocity shocks from X ~+ F, F — E, and X — E exists, where composition X is the intersection of the cxossover tieline and the injection gas te-ine extensions. Fur- thermore, point F ean be found by a geometric construction of ‘shock fiom the injection gas te lie to point X such that the resulting shock velocity is equal to A. For the displacements of Fig. 9 in which the solution contains only selesharpening shocks, this same proof applies to the B —+ D shock. Thus, in Fig. 9, the crossover te line must intersect both the injection gas (at X') and ol eline extensions (at X°). Com- potition D is found fom a tangent construction to X° while composition E is found from a tangent construction to X APPENDIX C, DEVELOPMENT OF MISCIBILITY We prove here that the crossover tie line controls the develop- ment of miscibility in C/V displacements. Consider the injection ‘gas at the MME (Ig) shown in Fig. 1 for which the crossover tie line coincides with a critical tieline extension. In that case, Fi= Oy and Eq, Bet reduces to oP aie APF al alt (-1) ‘Thus, all shocks have unit velocity. Using the I F and I> E shock jump relations, we also obtain that FF) = CF and FP = CF. Hence, points F’and E lie on the binodal surface Furthermore, compositions D and E must merge to a critical point when the crossover tie line is critical tie line. Hence, the continuous variation along the nontie-line path from D to B follows the equivelocity surface in the two-phase region on which the nontie-line eigenvalue is unity. A unit shock velocity from B — O occurs because B is an equal velocity point. ‘Thus, the gas flood is multicontact miscible with piston- like displacement when the crossover tie line is a critical tie line. A similar proof exists for the system of Fig. 9 except a unit velocity shock occurs from D to B. SSPE Advanced Technology Series, Vol. 1, No. 2 Authors Russ Johns is a consultant with Colenco Power Consulting Inc. in Baden Switzerland, His work includes analytical well-test studies of extremely low-permeabilty reservoirs for application to nuciear waste disposal. He holds PhD and MS degrees in petroleum en- ineering from Stanford and a BS degree in electrical engineering from Northwestern. Birol Dindoruk is a research engineer at the Reservoir Engineering Research Inst. in Palo Alto, CA. His research interests include the mathematics of cil recovery, phate! behavior and numerical simulation. He holds 2 BS degree from Istanbul Technical U., an MS degree from the U. of Alabama, and 2 PhD degree from Stanford, all n petroleum engineering. Lynn| Orr is professor and chairman of petroleum engineering at Sten-| ord. He holds BS and PhD degrees in chemical engineeting from Stanford and the University of Minnesota. His research interests include experimental and theoretical descriptions of gas injection! processes in heterogeneous reservoirs. (SPB 24112) ‘Table 1: Component Properties for Quaternary Examples. [Component] Me Pe Tr. ve wo (psi) | (°F) |(f b-mol) CH Teme 67 7H.65] 1.5809 [OTTO Gi ao. —[ror.8 | 9009 | 2.3768 [0.0090 Gas ot [ors 8 an5.a5 |. 294 [0.1590 35.18 [450.6 [45.83 [ 5.0009 [0.2000 Cio 226-8] 205.7 [0-1 | 18.000 fo. (Componeat] % (@oemol/t) CH] Cr Te CH] 0.3075 — [.an0o]o-0960 | —Vxn00e —o.0259 Tz [ —a.st14—[o.0000[0,0000| = —[o.0109 0.8299 o.a000] =| “on000 —fo.n109 Ce | 0.4464 [0.0950] 0.0100] — 0.0100 [0.0000 Tie} 0.1750 [0.0350] 0.0100] —0.0700 [0.0000‘Table 2: Composition Routes for the CH4/Cs/Ce/Cig System at 2000 psia, 200 °F. ‘Composition ras [Dimensionless] Composition | __(Mole Fraction) Saturation | Wave Label CH] Cz Ce | Cie |(Vol. Fraction)| Velocity iO 2000] 0008 |e a000 S000 | — 0.0000 = Di Josue. a0o0|o 7000] o.10s1| —0-rem9—| 70 FE fovea oaooofp.taas[o-rarz] —0saat—| 02803 Fi [0.8993 |0.0000 [0.0000 0.1007 O77I0 02893, G——os056 00000000 | o-0544 | 0.7843 —| — 0.0061 Taj ts000 o-oo fo. aoao[o.ca00 | 1.0000 —[—0.005r Xr 1.0364 [0.0000 |0.0000]-0.0364] = = Ba [0.5881 [0.0000 [0.2144] 0.1975 0.2813 [0.8471-1.6913 De—osrasorasrfo.raes| oreo] —eaae0—] ozs Ee fossouocese|o-iia7| over] —esase | 03089 Fz Jost23 [11080-0000] 0.076] 0.7874 0.009603 Taj. Fo: 3000[0-To 0000] o.0006 | —¥:0000—| 0.0086 Xa Ios a 00%8 .c000)-0037t| = Fe J-s0e5 oan00fo.asAO| OS | —OTaTO [OSTA ORT De foaso8 ores o.oeaT|o.0200| —o-sa7o—| astro Ee ——Io-issefoaia2 ana [0.0082 | —o.senz—| —o-7050 Fears fsa fo-ooo0 Loca | —o-soa0 —|o.1387-0.7000, Taj Tossa jo.as00 |e anooL e000] 0009 —| 0382 %5_—_Jortar|o-256]0.0000|0.0997| ——- : ing. (MATE) [0.0150 0.0850 ]0.0000] 0.0000 | 1.0000 T0000 (Inj. fz ]o.at00|o.s000]0-0000] 0.0000 [1.0000 T.0000 Table 3: Composition Routes for the CH4/C2/Cs/Cis System at 2000 psia, 200 °F. ‘Composition fas [Dimensionless] ‘Composition (Mole Fraction) Saturation | Wave Label [CM_[ Cr | Co [ Cie |(Wol. Fraction)] Velocity ‘OirO | 0.7000 |o.0000]o.4000] 0.4000 | 0.0000 = Taj. Ty ‘Same as solution in Table? Br D.so14 [o.0000]0.2128[ 0.1058] 0.2809 [1 0T@s-1 6007 Di 0.5880 |0.0977)0.1684[ 0.1455 | 0.3941 T0785 Es 0.6596 |0.0978|0.1345 [0.1083 | 0.5414 0.3248 Fe ‘0.8108 [0.0994]0.0000 [0.0898 | 0.7758 [0,0081-0.5248 Ga 0.8121 [0.0994 0.0000 [0.0885 | 0.7783 0.0073 Taj._Tz—[ 0.9000 [0.1000 [0.0000 0.0000-| 1.0000 ‘O07 xT 0.9380 0.1002 [0.0000 0.0387, = = XP ___ [10.4950] 0.0000 [5.5150] 5.9801 = = Be ‘said [0.0000 |0.2463]0.7993| 01670 [1.06041 3050 Ds 0.3567 [0.4792 [0.1046] 0.0665 | 0.4685, T0894 Es 0.5734 [0.4763 [0.0981 0.0562 | 0.5401 0.5653 Fi 10-4616 |0.4934[0.0000|0.0450| 0.8286 [0.0815-0.5685 Taj- Te [0.5000 0.6000 0.0000 0.0000.| 1.0000 0.0515 xT 0.5413 {0.5070 [0.0000 [0.0483] 5 5 XY 27479 [0.0000], 5683] 1.6746 = = De 0.4067 |o.0000]0.7e8i [0.0452 | 0.1266 [1 0a08-1.0100 De 10.2608 [0.6145 [0.0850] 0.0907 | 0.5252 T0458 7 (0.2651 [0.616% [0.0872] 0.0366 | 0.5703 0.7487 Fe 0.3300 [0.6428 0.0000 0.0268 | 0.8701 [0 1664-0.7057 Taj. Tz__[ 0.3800 [0.6500 0.0000 [0.0000 | 1.0000 0.1664 XT 10.3896 [0.6648 [0.0000 [0.0544] 5 xv E3179 {0.0000 [1.1231 [11886 5 nj (A ATEY] 0-29000-7100.0000[ 0.0000] 1.0000 [Inj Te [0.0900 [-aT00].0000] 0000] 1.0000 (sre 20112 SPE Advanced Technology Series, Vol. 1, No. 2