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SOcioty of

Potrolwm Engirmore U.S. Depmtm.nt of Enwgy

SPEMX3E

12634

**Critical Properties Estimation From an Equation of State
**

by C.H. Whitson, Consultant

Member SPE-AIME

Copyright

1984 Society

of Petroleum

Engineers

of Al ME

This paper was presented at the SPE/DOE Fourth Symposium on Enhanced Oil Recovery held in Tulsa, OK, April 15-18, 1984. The material is subject to correction by the author. Permission to copy is restricted to an abstract of not more than 300 words. Write SPE, 6200 North Central Expressway, Drawer 6470S, Dallas, Texaa 75206 USA. Telex 730S89 SPEDAL.

AESTRACT This paper describes a new method for calculating critical properties of petroleum fractions used as input to a cubic equation of state (EOS). The method differs from existing nethods in that it forces the EOS to match measured values of boiling point and molar volume (molecular weight divided by specific gravity) for each petroleum fraction. PVT predictions are made with the proposed method using the Peng/Robinson EOS for selected reservoir fluids reported in the literature. Saturation pressure and saturated density are With calculated the EOS and compared with experimentally determined values. Heptanee-plus are characterized using the (C7+) fractions proposed method and results indicate that both and phase behavior are volumetric L=preved= Reservoir fluids used in the study repreeent a wide range of compositions with PVT properties -.noinm f~Qg 38-120 ‘JC. reportea at temperzt”tires =..5...0 . A new method is -suggested for matching experimental saturation pressure with an EOS. Using the proposed method for calculating critical properties, the boiling point of the heaviest petroleum fraction is adjusted until mixture A near-linear saturation pressure is matched. hfi;limo r-mint =_____ of the relation exists betiiesr, ““~--..~ heaviest fraction and saturation pressure. It is suggested that this method has more physical meaning than the common practice of adjusting methane binary interaction coefficients. Proposed methods can be used with any cubic EOS. Critical properties are presented graphically for the Peng/Robinson and Soave/Redlich/Kwong equationa. A generalized form of the two-constant cubic EOS is proposed, and necessary expressions for p“nase aiid ‘val”umetr ea~c!&~ations are given. G i“ diagramed The iS critical-property method schematically to facilitate programming. It can be easily incorporated into existing PVT softwarealready baaed on an EOS. INTRODUCTION Cubic equations of state are used to calculate behavior of volumetric and phase petroleum reservoir fluids. Input data required by an equation of state (EOS) usually includes critical pressure, critical temperature, and acentric factor of each component in the mixture. For pure compounds these properties are known. Critical properties must be estimated for the petroleum fractions making up heptanes-plus. Having defined critical properties for all the components in a mixture the EOS can be used to predict PVT properties. for proposes a new method This paper petroleum calculating critical properties of fractions. The method requires normal boilifig for petroleum point and molar volume each fraction. The EOS chosen is forced to fit the boiling point and moiar voiume by adjusting pressure and critical temperature. critical Acentric factor is estimated by an empirical correlation using boiling point and molar volume; this correlation is general and does not depend on the EOS. reviews the most common empirical Whitson ~ri~ica~ used for estimating correlations properties of petroleum fractions. He studies the effect of C7+ characterization on EOS predictions none of existing and concludes that the PVT consistently better gives correlations predictions. Observations from this earlier work led to the idea that an alternative approach could be used for defining critical properties of individual petroleum fractions based on the EOS used for mixture calculations.

16

**References and illustrations at end of paper.
**

!JY

.,.

(1) C = c*p/RT D = dOp/RT = = = ~Opr/Tr ~Opr/Tr Qd=pr/Tr . is usually introduced as a shorthand for pv/RT . The first cubic equation of state was proposed by van der Waals in 18732and results from Eq. Also. numerical constants which will be defined using the VDW critical criteria and the assumption that ~ is proportional to ~b. b.*.***... ~~~ ~~~~~~d k’~~h experimental PVT data and results indicate that the proposed method gives improved VLE and phase densities. the traditional method of adjuating binary interaction coefficients to fit saturation pressure is replaced by a new method of adjusting the boiling point of the C7+ residue (heaviest petroleum fraction). Zc. universal and the critical compressibility factor. Eq. ...~~t ~tibi~ ~q=~ti~=e SPE 12634 .. Since the critical property method is based on manipulation of a cubic EOS.. the first section reviews the basic calculation procedures for solving an EOS for a single component..**. and d. ~@~~ where p is densi~y expressed volume (e.. They include fluid compositions and detailed C7+ pressures phase description. and pr = p/Pc. c.8....... 1 states that pressure results from the interaction of repulsive forces.. ~. (3) Equation of State Thoery Martin shows that almost all cubic equations can be generalized by a four-constant EOS. 4 the EOS constants are now Qa. saturation and densities.. where A is a numerical constant.PC) and it does not change sign at the inflection These two graphical point. though the method is equally applicable to other two-constantj3cubic equations such as the Soave-Rediich-Kwong Eos. Constants a. PVT data for reservoir fluids have been taken from the literature (Refs... reauces to aiiY t-wo-co~si. Neither composition or appear to the temperature variation affect reliability of the proposed method.. The Peng/Robinson 10 (PR) EOS has been used exclusively in this study... Q= = A=%.z~(~+~-1) + (A+CD-C-D) LJ” 1 +{-B3 + B2(C+D-1) . van der Waals chose two thermodynamic criteria for defining EOS constants.. T = temperature.2 CRITICAL PROPERTIES ESTIMATION FROM AN EQUATION OF STATE in ~nls work -r-m -. (4d) where p = pressure.. or p=RT/(v-b)-a/v .... and attractive forces. where Tr = T/Tc definitions which develop an EOS. and D are expressed as A = a“p/R2T2 = a“~”Pr/Tr2 .. a/(v-b+c)(v-b-ki). The fluids have a wide range in compositions and measured PVT data are reported at several temperatures.and ~d.... b. . RT/(v-b)... kgfm ). 1 the undefined EOS constants were a.. require that first and second derivativea of vo1ume equal zero: pressure wi$h (apfav) = (a p/a~f~psc~attoTc and PC.e. On the critical temperature isotherm the slope equals zero at (VC. -------LUD pZ~UILLLUIL..********* (4b) . (2) q ~ . In Fig. 1 if b=c=d. For Eqs...9)... Z.. The Z-explicit form of Eq. v = molar volume. To solve an EOS in terms of volume the compressibility factor. stated mathematically.. (4a) .******** (4c) p=RT_ (v. C. Eqs. c. 3..... observations are equivalent to the VDW’S criteria stated mathematically above.. temperature are measured quantities defining the state of the system..e. the general EOS . and R = universal gas constant.... The method i~l not recommended for the modified Redli~$-Kwong EOS propos~$ by Zudkevich and Joffe (see also Yarborough )...B(A+CD-C-ilj. 4 are ease the mathematics used to In Eq..**. i. A the generalized form of two-constant cubic equation is given to make the method readily applicable to any EOS... B. Expressing an EOS in terms of pressure is ackward for practical purposes because volume is usually while pressure and the unknown. 1 as mssa per unit is Z3 + Z2{-3B + (C+D-1)} + 2 [2R2 .. . They have since been named van der Waals (VDW) critical criteria which. Z = pv/RT v = ZRT/p ...g. .b) a (v-b+c)(v-bti) B = b“p/RT . 1 pressure is plotted versus volume for a pure compound at several temperatures.. Clc. The pressure-explicit form of the equation is written. By specifying a numerical QQnstant: A. and d define the EOS and they can be defining determined (1) thermodynamic by conditions or (2) fitting the equation to experimental data..i.**.... where a new set of EOS constants A..= G LUJ .

.... fv=fL.. temperature.. 4 are used to calculate A... ~ ~~ ~Q~.and threeconstant equations.. the term aisa correction to EOS constant $la to ensue accurate predictions of VLE pure compounds.J~d fQr z+ If only one solution exists then fugacity is not of interest.37464 + 1...574uJ.. and D.. At equilibrium conditions the vapor (which iS represented by the volume solution at the right) is aa content being a vapor as the liquid (which is represented by the voiume at the left? is content being a liquid......... By specifying i and Zc the EOS is defined.... for single and multicomponent systems... 6b and 6c.. Eqs. ....% Peng/Robinson (PR) Eqa. 10 is solved for fugacity of each phase and if fv = fL then the pressure and temperature define an equilibrium point on the vapor pressure curve.. (9) m = 0.. (lo) Fugacity of a single component system is calculated by first specifying the critical pressure.307401... (5a) q Zc = 1/3 . Defining the state with pressure and temperature...17(jw2 ..... This equilibrium condition is alao satisfied when cnmponent fugacitiea for vapor and liquid equal one another .. Without introducing the formal definition of fugacity it can be visualized by referring to Fig... W... Zc is the universal criticai compressibility factor which is assumed to be the same for all compounds. 1 it iS necessary to express fugacity.. f. In(f/p) = -ln(Z-B) + L+ Z-B LE+EI D-C Z-B+D Z-B-I-C ReturnLng to Eq... WHITSON Soave/Redlich/Kwong (SRK) k=l(or2) 3 The conditions defining Q constants are then ap/av = o a2pfav2 = o Z=zc .e.........> and can be written in shorthand as ~..........0.... 6a is chosen for ~. a is temperature dependent and acentric factor.. If three solutions are found then the smallest Z is defined as liquid and the largest Z ia defined aa vapor. Eq... I RK EOS : A=lor2andZc=l/3 (7) PR EOS : ~ = 2 T fiand Zc = 0.... For a single-component system the fugacity of a given phaae is. Eq. G= 1 +m(l-~) ...... The subcritical isotherm labeled Tb has a cubic form. The Pressure which divides the loop into two sections with equal area (shaded) is the vapnr pressure for the temperature defining the isotherm. 1.......... B..~b2(k2-3~+3Zc) + ~b(~-3~Z~+3Z~2) ..SPE 12634 CURTIS H.. (5b) G= = constant where A= ......26992w2 ~d = flb(j-a)-3ZC+1 .. is typically used to correlate variation in temperature dependence for compounds of varying species............. (5C) constant ....54226u ...... (6a) To complete the development of Eq. is = o.. ........ The last constraint.. C..... Results of algebraic manipulation shows that 0 constants are defined by: ~b3 ....i... 61 . (6c) The smallest root of Eq...... (5d) m = o. 5a-5c apply at the critical point defined by T :)$ P... 4a.. while flcis defined by Eq. ...0. 5d.. A = 2-E (or 2+ti) ~c = g*3fi7&g~. 5d... for example the RK and PR equations. fl&and Qa follow from Eqs..Zc 3 .. chosen so that the generai EOS can be easily simplified to the most common two.............. and Eq.. critical and acentric factor... (8) l+m(l-~) n= = A*....480 + 1.. (6b) S2a= ~b2(k2-3~+3) + ~(3AZc-X-6Zc+3) + (3ZC2-3ZC+I) .. Both the SRK and PR EOS’s use the correction resulting in the factor for %~ complete definitions of their respective equations: + A ~n(Z-B+D) —— Z-WC C-D ....

.. 3 shows acentric factor plotted versus normai ‘boiiing point Eer pa~dfi~S and Approximate linear relations can be written ~~(XMtiC&.477 + 0. y.127 becomes 142.0 for aromatics... EOS Critical Property Estimation traditional method for estimating critical ~f petroleum fractions is illustrated in Fig. The procedure is outlined in Figs. . 1-. .00218 Tb(K) .. Eqa. M. and D represent mixture where Aij=~.. Acentric factor is estimated by an empirical correlation.........e. constant 91.. This is done by adjusting Tc and Pc until a satisfactory match is achieved. (11) A. that the estimate of u is sufficient for the proposed method since normal boiling point itself is matched exactly by the EOS. (12d) where Z1 iS mole fraction of the phase and kij are binary interaction coefficients...... Fugacity calculation for mixtures are complicated and they will not be covered here since the method for dererning critical properties based on an EOS only requires fugacity calculation for single-component systems.. and Eq.. The prcper~ies One might ask why the EOS is not used to check. which by specify Tc. The first step ia to determine or estimate normal boiling point. I Bi ln(fi/ziP) = -ln(Z-B) +_+_ Z-B Bi-Di e+—} D-C Z-B+D A Ci-Bi ~ Z-B+C ‘A = -0. Estimated values Tc. Usually it y for Siieh is f3Ufficient to specify Tb and correlations.. (12b) Ii Zi Ci . ... A B c D= = = = Ii ~j Zi Zj Aij (l-kij) •**~*** (12a) the measured for Since data petroleum fractions are Tb and F1/Y it would be helpful to express u in terms of these two data...... C.. normal) pressure..1... (13b) = -0.... u... P~~* Temperature ia aasumed. 2A.. Tb . specific gravity.. If fugacities do not equal then a new temperature ia assumed. and D are calculated.. It seems reasonable that if the EOS does in fact match meaaured Tb and ii/Y data then mixture behavior also will be predicted with reasonable accuracy. preaaure... Composition. B. M/Y) match the measured vduea.. 3 is solved for If only one Z solution is found then the z.. if the EOS-calculated boiling point and specific gravity (i. The trial and error procedure is begun by first guessing values of Tc and pc..*.. solutions are found then the lowest value ia designated as liquid and the largest value as vapor.042 ~+ 0... Having defined w it is now necessary to use y the EOS to match meaaured ~aiu~~ of Tb ~p-~ u... molar volume..= Che data temperature. for an individual petroleum fraction..... 2B and 2C... PCS % definition is atmospheric (i.e... Using the Riazi-Daubert correlation for molecular weight as a function of Tb and Y it haa been possible to derive the following relation. Mixture phase behavior and volumetric celculationa are performed as necessary... Empirical correlation are chosen to estimate critical critical temperature.. of each fraction. Kw = 91. (12C) Ii Zi Di .. Pc.. If three temperature is not equal to Tb.4 CRITICAL PROPERTIES ESTIMATION FROM AN EQUATION OF STATE For a single component fugacity is given by. ...csrau.....! . Reasonable estimates are given ~~ the and Daubert ~impie ~Helatians of Riazi (see Whitson ). p=. and molecular weight... ~il ----“. -0..127 (M/Y)0”49593 Tb(K) (15) If Tb is given in Rsnkine. B..00218 becomes 0. and u for petroleum fractions are input into the EOS together with known values for pure compounds.. Combined. ( 4) If Tb is given in Rankine then constant 0.. The proposed method requires the selected EOS to =tch Tb and H/Y by adjusting T= and PC.... C.7 fir paraffins and 10.-a a~~ WCSlly defining the state of the system.000983. the following approximate relation for u can be derived. ~. 14 and 15 estimate acentric It is asaumed factor knowing only Tb and M/Y.. in a mixture the SPE 12634 Fig..587 + 0.of 12. averages calculated using the following mixing rules: u= -1. Tc..00218°Tb(K) ... ~ p. and acentric factor.0 + 0. EOS constants A.. (13a) + 21jzjAij +A(Di-ci)l (C-D) (C-D)d ~n(z-B+D) Z-B-I-C Assuming an averaee Watson characterize={ ion factor.. Fugacities are calculated for each phase and if they are equal then the assumed temperature equals Tb. To calculate Tb with an EOS it ia neceaaary to and pressure....00218°Tb(K) .75584 Ii Zi Bi .

14 and 15). Predicted equilibrium gas composition from the bubble point VLE calculation using EOS critical properties resulted in methane content of 91. then dew point is predicted exactly (equal to the bubble point. et al. cgIc~~Eted Iiqa&d densities and yields are compared with experimental data in Table 2. A simple Newtwon or chord method ia sufficient to determine Tc.8409.e. When both E(Tb) and E(M/Y) equal zero then the Tc and Pc The double trialvalues have been determined. molecular weights. and critical properties calculated with the proposed method the PR EOS predicts a dew point at 201 ‘F of 4044 paia. Tc is varied until E(Tb) = O. Using critical properties based on the PR EOS a bubble point is predicted at 3829 psia. et al. and temperature. 3865 psia). The critical pressure.gacities are equal at the specified Tb (and If they are not equal then an error Pat)” function is calculated. Peng/Robinson predictions correspond to those listed in Table 1. C. or 2. including male fractions. If equilibrium vapor composition resulting from the bubble point flash is used to represent the gas cap fluid.1-%. C35. It is obvious that dew point pressure is dependent on the properties used to describe the petroleum fractions. i. PR-3. 4a . is defined as the difference in measured and calculated Fi/Y.001 mol-%. and PR-4 use suggested by and Katz methane binaries Firoozabadi. . or 0. Cavett’s correlations are used for Tc and Pc while it ia assumed that the Edmister correlation is used for u. retaining only components to C22. Tsc. and specific gravities (corresponding to cuts with boiling pointa of normal paraffin).0377 *pc(MFa). Binaries are not used when EOS-based critical properties are used (PR-1). Tc/Tb. Constants A. content of the gas cap fluid is 91.7867. properties are similar.” a dew point is predicted at 3706 psia.3% lower than the measured pressure. This shows the sensitivity in dew point prediction due to a round-off error in composition of less than 0. where PR-2. Using the gaa compositions reported by Hoffman. ia not correct. coefficients Predicted saturated oil density is 0. ZRT/p). Having matched Tb. If the exact composition to C35 ia used. E(Tb). 3 is solved for the smallest Z factor.. w (defined by Eqa. compared with the experimental value of 0.47 MPa) at 201 ‘F (93. M/T is calculated with the EOS using Tc (from previous step). Table 1 illustrates how critical properties calculated from different correlations affect predicted dew point pressure. and a methane binary of 0. The gas-cap fluid reported by Hoffman. Crump. Interaction have not been used.e.70 having 1. SCN is analyzed in SCN fractions up to C22. pressure. This is worse than the prediction given by Katz and Firoozabadi (+0. reported in MPa and the conversion to psia is pc(paia)=145.318 mol-% with an average mo. An error function. with an average C7+ molecular weight of 198. Holding p= constant. PVT Predictiorisusing EOS Critical Properties Hoffman. M/Y equala molar volume (i. et al. are calculated and Eq.9% high. it ia given as the ratio of Critical pressure is T= to Tb. PC> is adjusted and the procedure for matching Tb is repeated.54 mol-% with an average molecular weight of 141. but not the same for the Methane reservoir oil and equilibrium gaa. (equal to standard (equal to pressure). Estimated bubble-point oil density is not reported by Katz and Firoozabadi.7 and specific gravity of 0. some 5.00 and specific gravity of 0. and-error procedure is relatively simple to program. p= (held constant in the previous step).25 and specific gravity of 0. With the generalized EOS presented in this paper it ia eaay to determine critical properties of petroleum fractions for any two. and D standard temperature). Reported bubble point pressure is 3840 psia (26.6672.7854. defined as the difference in fugacities of vapor and liquid phases.SPE 12634 CURTIS H.17 for the heaviest The methane-C35 binary waa used fraction.or three-constant EOS.8%) using methane binaries for fractions calculated from an empirical C7+ correlation.84 mol-%. B. Extended analysia of heptanesplus ia given to C35 for the oil.3% high.6867 gfcc. Figs. psc. 5 Instead of using this procedure to solve for Tb it is sufficient to check if vapor and liquid f.4d present the results graphically. possibly suggesting that the use of paraffin molecular weights by Hoffman. C7+ molecular weight of 128. E(M/Y).35 mol-% and heptanes-plus constitutes 1.. Methane content is 52 mol-% and C7+ is 36. Tables of PR and SW critical properties for extended ranges of Tb and M/Y can be obtained from the author. C7+ specific gravity is in good agreement with the experimental value but molecular weight shows more deviation. to match the measured bubble point pressure. WHITSON Katz and Firoozabadi match the measured bubble point using the PR EOS with increasing interaction coefficients between methane and C7+ fractions. Instead of reporting critical temperature directly. Hocott 3 and present compositional and PVT data for a reservoir oil and its gas cap fluid.89 ‘C).

et al. .= iS Y. Binary interaction coefficients are not used.Jes StrOSg temperature dependence. From results presented in this section it can be concluded that the present method of defining critical properties based on an EOS is reasonably accurate for predictions of saturation pressure and mixture densities. EOS Predictions of the Olds. Interestingly. with a maximum error of 13. Saturated liquid densities are predicted more accurately than vapor densities. All systems studied by Olds. as indicated for An increase in Tb a North Sea fluid in Fig. This can be an important factor in thermal recovery and surface process appiicatioiis. M+.c~. Extensive experimental results are given for six recombined systems. Physically. though the proposed method gives excellent results as well. 5. and 5. Dew points for very lean condensates are difficult to measure experimentally and therefore it ia reasonable to question measurements of the 14440-GOR mixture. Practically. Properties of the separator gas and liquid are given in the original work and recombined reservoir mixtures have been calculated using reported gasfoil ratios.d~~p. and 9) for methane at supercritical temperatures.g ~h~ —-—. Saturated iiquid and vapor defi~itie~ Zie overpredicted.i. experimental saturation pressure is mat ched by an EOS using binary interaction coefficients between methane and C7+ fractiona.tvs leanest pre~au. A first estimate Of Tb+ for the heavieat fraction =n be made using molecular weight. are oils with reported bubble point pressures and saturated oil densities.45% including the leanest mixture.30% with a Deviation also increases maximum error of 6. Watson gravity. despite good prediction of liquid densities. and Lacey data presented in 1949 are reviewed in Table 4. results in an increase of saturation pressure. Maximum error is 10%.. Temperature dependence may result in part from incorrect extrapolation of correction factor. SPE 12634 Saturated liquid densities are predicted with an absolute average deviation of 3. Next we consider the data presented by Olds.—. and molecular weight for each fraction. mixture (GOR=14440 scffatb). critical properties) by introducing large binaries.8 where Tb hSS UnitS Kdvin. It can be shown that VLE calculations are dominated by A. Considering the range of temperatures and compositions. Matching Experimental Saturation Pressure Traditionally. For all GOR mixtures deviation in bubble-point pressure increasea with increasing temperature. A direct ~eis~iar.3%. Whitson gives several examples Indicating that interaction ~aefficiez~~ h2. The general trend of overprediction is cwoaite of that which is usually observed with the PR EOS (using empirical property correlations). 8. -w{.7%. each measured at three temperatures (100.14% with maximum error of 8. as a indicated by the choice to introduce a.g. and lack of any adjustment or use of binary interaction coefficients.JJO “. The PR EOS iS used to calculate critical properties. liquid yields for predictions based on calculated gas composition from the bubblepoint calculation are very poor.. and Lacey in 1945. Measurements are made at three temperatures for each mixture of differing GOR. Absolute average deviation is 5. (see Eqa. The method is not inferior to empirical correlations and has the advantage of being consistent with the EOS used. with temperature for all GOR mixtures. Tb+=(R+-Y+) /1. As can be seen from the mixing rules (Eqs. It also appears that VLE predictions are good.” . Sage.61%. and specific Y+O me characterization factor is estimated from and boiling point ts found directl~ from the definition of ~ . however. 12). Hexanes-plus is fractionated into seven CU’CS with approximately equal weight fractions (-10%). a. the use of binaries to match pressures is saturation very efficient. Absolute average deviation for saturation -----/. EOS predictions are presented in Table 3 for saturation pressure. For accurate predictions using the proposed method it is necessary to have detailed analysis of the C7+ fraction. and 250 oF). vapor and liquid densities.. not easily given physical meaning and there is a tendency to overcompensate for bad input data (e. Binary interaction coefficients are set equal to zero in all cases. Interaction coefficients are.6 CRITICAL PROPERTIES ESTIMATION FROM AN EQUATION OF STATE Results indicate that the Cavett/Edmister (PR-3) combination performs best. 4a. 190. boiling point is easily defined and has obvious limfts.+ ip. fraction and saturation pressure..<77 .-. binaries only affect EOS constant A.*S he~ween Tb of the heaviest =’. specific gravity. Sage. the predictions are very good. biibb~t2-~CiIlt Absoiute average deviation f~i pressure is 5. Critical properties of the petroleum fractiona are calculated using the PR EOS.e. The present method suggests that boiling point of the heaviest petroleum fraction is the most uncertain C7+ data and that it alone can be adjusted to match saturation pressure. The transition from bubble. correction factor for modifying vapor pressures of pure compounds.to dew-point is also predicted correctly.1%. preferably distillation data including boiling point..

: “Physical Data for Distillation Calculations .c$d = constants in the general form of the cubic EOS A. 12. .H.-Y.81-97. M. Sage. 2. Results indicate that saturation pressure and saturated predictions are reasonably density accurate without using binary interaction ~~eff~~i~~.-. D. Cavett..Vapor-Liquid Equilibrium. 17. 26-29. This procedure has a more direct physical understanding .1-10. Tb(”R)l/3/Y m= correlating parameter for a M= molecular weight P= absolute pressure Pr = reduced pressure.b. San Francisco (1962)351-366. W. —— 16. Riazi. n.: “On the Thermodynamics of Solutions.S. Olds. T.Pet. Pr = PIPC Pc = critical pressure Pv = vapor pressure R= universal gas constant T= absolute temperature Tb = normal boiling point Tc = critical temperature Tr = reduced temperature. 15. and Lacey. 5. 233-244. Hoffmann.-.AIME(1953)198..Ind. Lee. Using factor.510. Proc.F.~.Pet.-n uq. Watson. NOMENCLATURE a.: Pet. m“s.N.En@Chem. accounting for oil type (i. .H. G. and Lacey. Olds. E.H..g i binary interaction tF. (Marc~l..— 683-693.M. p= density w= acentric factor. Nelson.: “Volumetric and Phase Behavior of Oil and Gas from Paloma Field.H. is empirical.Chem. “. Peng. A = (talc.I..1980)..” Proc. Leiden..1. 1983) Plus Fractions.J. Soave..L.: “Characterizing Hydrocarbon Soc. D.: Doctoral Dissertation. Sage. u = -log(pv/pc)-l..( 1935)~.: “Cubic Equations of State Which.D = EOS constants E= error function f= fugacity Kw = Watson characterization factor .o at Tr=0. 7 1.++fi”-nf-~~~~~ ra~ictions:lt Paper SPE 11200 presented at the 57th Annual Fall Technical Conference and Exhibition.” ..” Trans. J.AIME.)/meas.: “A New Two-Con~tant Equation of State.: “Improve Predictions of Enthalpy of Fractions. G. 7. ~e~hc& coefficients.-.” Ind. V: An Equation of State..D. Crump.Fund. C. —— 13. Redlich. and Daubert...2.E. ~f . PeC~Q~~IJm Fractions$” .J~ p. API.AIME(1945).: Uflh. C.” Chem..” Hydro.Tech.B.H. Sept. —— —.R. A.7 Q= numerical EOS constants .S. M.— 8.Eng.: “Equilibrium Constants from a Modified Redlich-Kwong Equation of State.: “Predicting Phase Behavior of Condensate/Crude-Oil Systems Using Methane Interaction Coefficients.” ~dro. If experimental saturation pressure is not predicted accurately with the proposed method.ar. and Kwong. 1982. a procedure is recommended whereby the boiling point of the heavieat C7+ fraction is adjusted to match measured saturation pressure of the mixture. R.1460-1464. A new method for calculating critical factor of petroleum properties and acentric fractions based on an EOS appear to give promising improvements in both volumetric and phase behavior predictions.raff~p. and Murphy.-meas. B. (March 1977)153-158. and Firoozabadi. 6.. O. J.i~i~v) the Watson characterization ~-.C. (1979)~. Z = pv/iiT Zc = critical compressibility factor correction factor for EOS constant A proportionality constant between EOS constants SICand fib. Edmister. It is felt that boiling point of the heaviest fraction is the greatest unknown of measurable C7+ properties and can therefore be adjusted within reasonable limits.59-64. .77-99.Science(1972)~.. ~.Chem.H. Whitson. W.--.Holland. Martin.a.. 10..(1976)~. (August.Proc. Katz. 1873. Kesler.++z+ “ . and Kesler.G.G.” Ind. and Hocott.” Trans.Trans. D.173. A.: “Volumetric and Viscosity Studies of Oil and Gas from a San Joaquin Valley Field. R. ~.: “Effect of Physical Properties m.B. Reviews(1948)~.. M. 27th Meeting. .4-. z= compressibility factor. 14.J. C. B.AIMK (1949).: Equilibrium Constants for a Gas-Condensate System. 4.: “Simplify property Predictions.csfo ~tch experimental VLE data. p v nsLLulaLL”L. volume .: AIChE(1975)21.~. 2..defining the proposed family of cubic equations A= deviation. WHITSON REFERENCES 1.l197-1203.Refiner(1958)~. W. 1978)1649-1655. B.” J..B. K.a&.R.I. The method for calculating critical properties has been tested using the Peng/Robinson EOS.A”. 9. Fund.” Chem. Tr = T/Tc v= molar volume v.H. The method requires molar volume (ratio of molecular weight to specific gravity) The acentric factor relation and boiling point.” Trans.~.Ae.287-302.= FifiPiP -. J.e. van der Waals. Whitson.E. .SPE 12634 CONCLUSIONS CURTIS H. and Robinson.(Nov. New Orleans. 3. 11. B. 3. Fugacities of Gaseous Solut ons.N.C. and Lee. J. R.N.

1.65 66 PR-2 8.6753 0..7209 PR-1 —— 0.----=. given in parentheses..EFFECT OF CRITICAi.6315 0.. Jr.. Riazi/Daubert + E~mister: 3.7.. — .4 1 4 h-i..7164 1*5O — PR-4 0. ..6536 0. EOS-Based (proposed) .: “Application of a Generalized Equation of State to Petroleum Reservoir Fluids.3) With Katz/ Firoozabadi Methane Binaries 3632 (-5.30 16.23 16.75 12. RESERVOIR GAS DEW POINT PRESSURE.93 .6520 0.6475 0.C...5) 3668 (-4. A..21 12.4Au-.6675 2.7390 2.56 16.53 16.45 2. PR-3 0.— 9.93 15.6637 0. .. Lee/Kesler . -. and Frealctlon or vapur LLI+UAU the Redlich-Kwong Equation of State. . and Joffe.48 Liquid Yieid (bbil’iilisci) Press. = ..” Li-m TABLE 1 .Yu .. L. Deviation.00 15.6392 0.08 PR-1 ...6619 0. .6709 0..6538 0.5921 0.31 11.48 17.01 15... (1970)16. @!@l&E!&_ 2915 2515 2015 1515 515 IAI(%) 9*O7 12. . K.... J. Robinson..6834 0.7) 4049 (+5. m .. ...7029 2.6486 0.112-119. RESERVOIR GAS Liquid Density. .6565 0....97 14.6957 0. ..4) 3870 (+0.4) ~ Same as reported by Katz and Firoozabadi.u.... Dew Point Pressure (psia) Correlation Experimental .6779 0.. (eds. .32 PR-2 0.-.54 — PR-4 10.97 3.6300 0. Zudkevitch.7160 0.17 4....6364 0..8 CRITICAL PROPERTIES ESTIMATION FROM AN EQUATION OF STATE SPE 12634 18.7148 0. “..-. 2.6665 0.) 19. Cavett + Edmister . %.” AIChE J.37 12...61 15.80 ..09 14.44 15. @@% 2915 2515 2015 1515 1015 515 IAI:%) 0. Predicted without Methane Binaries 3841 4044 (+5. .r+*h .5) 3523 (-8.6020 0.6822 0. ET AL.73 3.46 — PR-3 9..3)2 3322(-13.PROPERTIES USED WLM PENG/ROBINSON EOS TO PREDICT THE HOFFMAN ET AL. D.: “Correlation . Yarborough.6159 0.33 17.” Equations of State in Engineering and Research.. .74 15.COMPARISON OF MEASURED AND EXPERIMENTAL LIQUID DENSITIES FOR THE HOFFMAN.. 4.L.6967 0. TABLE 2 .98 15.. glee Press. Chao and R.

29 44.8 +6.12 46.96 43.68 37.2 +18.0 +3*9 +1.52 38.15 ——— +5.13 33.0 49.85 25.75 +1.54 48.2 +3. SPE12534 .4 27.6 +5.96 15.2 +1.9 +4.5 -13..5 +3..1 +2.— 274 274 274 460 460 460 620 620 620 811 811 811 1.1 +5.9 42.65 36.v--< pressure assuming a single phase mixture.37 24.1 +4.21 +1.8 +4.44 31.62 43. Bubble-Point Density (lb/ft3) Exp.3 +8.2 +6.8 +3.24 14..3 +3.-. 1 A(%) 552 552 552 940 940 940 2205 2205 2205 100 190 250 100 190 250 100 190 250 1112 1410 1675 1870 2210 2380 3430 3542 3595 1065 1383 1549 1723 2174 2375 3102 3691 3880 -4.90 20.4 +1.2 +5.55 41.35 19. Calc.l=A-Aat the experimental saturation ~=ab.34 46.7 +2. Calc.2 z .68 41.49 -— ———28.52 39.8 +9.04 43.4 +4.7 +6.TABLE 3 .2 +7.61 27.08 16.78 35.3 Saturateciciensit%esZrs .2 -9.78 47.COMPARISON OF SATURATED PROPERTIES FOR OLDS-SAGE-LACEY RESERVOIR MIXTURES (1945) USING THE EOS-BASED CRITICAL PROPERTY METHOD WITH THE PR EOS.6 +3.I.0 -3.65 20.6 +5.13 29.5 -14.7 -3.1 +4*4 +4. 1 A(%) A(%) 100 190 250 100 190 250 100 190 250 100 190 250 817 1020 1170 1540 1830 2020 2085 2439 2670 2656 3067 3384 796 1067 1236 1361 1805 2051 1799 2360 2656 2273 2944 3284 -3.98 39.9 -7.6 -11.34 40.96 46.01 22.96 44...5 +4.66 47.5 -7.70 49.— ——— —— -——— 100 190 250 100 190 250 100 190 250 —— ——-— 4348 4836 4869 4615 4981 4933 4556 4709 4504 ———— ———— -——— -3. Calc.05 16.36 44.08 46.73 42.3 +3.5 +6.52 28. as is correctly predicted by the PR EOS.40 21.2 -1.66 34.46 18.6 +4.87 47..COMPARISON OF SATURATED PROPERTIES FOR OLDS-SAGE-LACEY RESERVOIR MIXTURES (1949) USING THE EOS-BASED CRITICAL PROPERTY METHOD WITH THE PR EOS. TempGOR erature (F) (scf/bbl) Saturation Pressure (psia) Meas.4 +5.2 -0. A(%) Saturated Density (lb/ft3) Exp .54 24.6 +7. TempGOR erature (scf/bbl) (F) Bubble-Point Pressure (psia) Meas. 2 TABLE 4 .8 +2.88 37. 1 +7.19 45.50 40. .02 19.2 +0.6 5361 5361 5361 7393 7393 7393 14440 14440 14440 1 4490 4590 4630 4560 4730 4780 3835 4305 4440 Saturated densities are calculated at the experimental saturation pressure assuming a single phase mixture.07 43.6 +7.9 -1.4 -9.92 43.6 -104 +1.2 +5.50 45.05 20.44 35.55 39.53 44. Calc.99 22. Lower GOR’s are bubble-point mixtures and higher GOR’s are dew-point mixtures.6 -0.

. -...9... NEW t4ZTHO0 ITERATIVE PROCESS FOR CRITICAL PRLWERTV CALCULATION EST WATEO w 1 ASS4Ko Pc Tc J t I I CTWI rrmAmhHdT -.....e -. s-. ---------MIxTIK?E Yes I I ---i ---- ---- ---- -- d F*... Fig.= method for cafculatmg petroleum Iracfii cdcicd prc9atis. .. ..=. itli. ma iterative procaaa used by the WJ_ ...--.-. .. . c ~-. Pattieum + rw. . I Yes AL. i..* TRADITIONAL tETHOo t@fAIREO P Distillation Tby M Pc Fk \\~:~\T>Tc Increasing Temperature Enpirical correlations ESTIMATEO TC pc ~ % I SIhGLE CCWOfWT --------MIX~U~ ------------‘--- ! I Ps(c- t ‘-=..:. . =... . SP E12S34 . zkF1OW diagram OuWiningthe propoaad method for cdculaWI fraction critical propartii..C L w-i ~c MOLAR VOLUME Fig.. 2A-FlOw diagram outlining the traditional method for calculating patrolaum fraction critical pmparfias. l-PreaaurelV@Jme schematic showing aaveral ikotherms predic$ed by a cubic EOS..

6 I 12. 1 I . K Fig. generalized correlation. 1 +0. o I I .127 .0 I I t J 750 ‘ I I I I . 5—Empifical relation between dewpoint pressure of a North Sea gas condensate and titling point and Watson characterization factor of the heaviest petroleum fracfion (Cm+).2 12. 12.4959%Tb(K)-o.042 .-- 650 40 Dew-Point I 50 Pressure.h . MPa 60 Fig.(M/Y) o. 700 c: c .75584 / \ . SP E12634 .4 x’ . NoRMAL PARAFFINS + AROMATICS cORRELATION: ~ =.Kw=lo. 12.#” ]enzene 1 I I 400 600 800 aromatics. and the moo NORMAL BOILING POINT..Kw+0.7 ... 1 1 KW=l Z.3—Relation between acentric factor and normal boiling point for normal parafflna.002180Tb(K) = 91.

cak. ~ < “y *.--&-&----& -200 BOILING POINT.ns fw petroleum Imctions. E ~.w the PrOPOS4 mathd withm. K mo moo BOILING POINT.latd P6n@Rtinmn and SOave/RedtchKwong OS.~~~i! -zoo q ?_ I_ -200 1 I 1 1 400 600 BOILING POINT. 4_crItical property correkti.PENG/ROBINSON PENG/ROBINSCIN U) EQUATION 1 OF STATE c EQUATION 1 OF STATP I q LQA 1“’<’’’””’ WI r “’’’’”” P ““7 t- .?E .- ? c J___.%. -. . I .L-1 d!oo 1 t 1 J 400 6W BOILING POINT. K Wo 10 ma us. K FIm. K SOAVE/REOLICH~tKU~G EQUATION OF STATE : r“~~ B: SOAVE/REDLICH/KUONG EQUATION OF STA.

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