,.

Society of Petroleum Engineers

WE 26906 Sour Natural Gas and Liquid Equation of State

Mohsen Mohsen-Nia, U. of !Ilinois; Hamid Moddaress, Amlr-Kabir U.; and G.A. MansoorL* U. of Illinois
q SPE Member

of PetroleumEngineers, Inc. %Yk@ 19S3, SOCW

Thh pe#arWOE prepamlfor preeanlatlon81the 1S93 Eastern RegionalC~~ference & Sxh!bltionheld in Pittsburgh,PA, U.S.A., 2-4

November 1SS3.

Th!dpepet waa aelectad for pr%enlalion by an SPE ProgramCommltfeefollowingreview of Informationcontainedin m abetracf eubmittedby the author(s).Contenteof the paper. as Weeentad.have not been reviewed by the Sdety of PetroleumEngmeereand are subjectto cofrecflonby the author(s).The matermt,as presented.d~s not neceaaarilyraflect any paaltkwr of the &clety of PetroleumEngineara,rfaofficer%or member%Papera preaenwdal SPE meetlngaare subjectto publicationreview by EditorialCommltfeeaof the Soclaty ofPefrofeum Er@were. Parmtaahntocopyla reafrkfadtoan abafractof M owe than3W wo+de. Illuefratlons m~ynotbe cqrled. The abstractshouldwntaln conaplcuoua acknowledgment ot wtrem and by whom the papnr la praaemed. Write Librarlen, SPE, P.O. Sox 6338SS, Richardson,TX 75023-3636. U.S.A., Telex 1S3245 SPEUT.

ABsTIwcr
Ilie major gaseous impurities in the subquality natural gas sources are acidic components, such as hydrogen sulfide and carbon dioxide. Considering that H2S easily dissociates into hydrogen and elemental sulfur, thermodynamic properties and specially phase equilibria of liquid and gaseous systems containing hydrogen, carbon dioxide, other acidic hydrogen sulfide, components, and light hydrocarbons are of much interest to the natural gas and gas condensate production industries. In this paper we report the development of a simple and accurate cubic equation of state for prediction of thermodynamic properties and phase behavior of sour natural gas and liquid mixtures. This cubic equation of state, which is based on statistical mechanical theoretical grounds, is applied to pure fluids as well as mixtures with quite accurate results. All the thermodynamic property relations of sour gaseous and liquid mixtures are derived and reported in this report. Parameters of this equation of state are derived for different components of sour natural gas systems. The resulting equation of state is tested for phase behavior and other thermodynamic properties of simulated and naturai sour gm mixtures. It is shown that the present equation of state, even though it is simple, predicts the properties of interest with ease and accuracy. ---------------_ _-,____ ______ ____ ._, References and Illustrations at enci of paper

INTRODUCTION In the past two decades, a number of subquality natural gas / gas condensate fields have been discovered around the worldl2. The major impurities of these subquality natural gas / gas condensate sources consist of N2, cm and H2S. since that H2S easily dissociates into hydrogen and elemental sulfur therefore, thermodynamic properties and specially phase equilibria of liquid and gaseous systems containing hydrogen, hydrogen sulfide, carbon dioxide, other acidic components, and light hydrocarbons are of much interest to the natural gas and gas condensate production industries24. Transportation, and processing of sour and hydrogen containing natural gas is of major concern to the industies involved. Carbon dioxide and hydrogen sulfide are considered as being impurities in natural gas and oil and are responsible for corrosion of the flow-line and pnxessing equipment. Separation of these gases from natural gas and oil is usually the most expensive part of natural gas and oil treatment processes. The economical importance of treatment of sour gas has made it important for the gas and oil industry to have accurate equation of state to represent properties of sour gases and liquid mixtures3~. Presence of sour gases in crude oiI could also cause deposition of heavy organics, such as asphaltene and wax, from oil which would plug the well, pipeline and refining equiprnen~. As of yet no satisfactory equation of state has been 173

SOUR NATUR4L GAS AND LIQUIDEQUATIONOF STATE

SPE26906

available to predict the behavior of sour gases and liquids in reservoir, well, pipeline and compression / Recently, experimental and expansion facilities. modeling studies on the phase behavior of high H2Scontent natural gas mixtures were reported by Gu, et al.*. These workers used the Peng-Robinson (PR) equation of state for phase equilibria calculations, but because the PR equation was not accurate for PVT calculation, they used, instead, a 33-constant super equation of state. By using this equation of state, Li and GU09 studied the supercompressibility and compressibility factors of However, it is not convenient for natural gas mixtures. engineering calculations to use such a lengthy equation. Morris and Byers 0 have performed some experimental work to obtain VLE data for binary and ternary systems containing CH4, C02, and H2S. Afterwards, they used the PR and Soave-Redlich-Kwong (SRK) equations of state for VLE calculations of the same systems and compared their experimental results with these calculations. Huron, et all. and Evelein and Moore* used the SRK equation of state to study the hydrocarbon systems containing hydrogen sulfide and carbon dioxide They reported phase equilibria calculations, bu other thermodynamic property calculations were not reported in their paper. On the same subject, some other experimental research -works have been reported, such as the works of Morris and Byers13, Hunage et. al, Hall et al , Robinson et alls, Mraw et al7, and Eakin and Devaney 18. By reviewing the above literature on equations of state of sour gases and liquids it is concluded that there is no simple and accu?ate equation of state available for predicting thermodynamic properties of sour and hydrogen containing gases and liquids. In this paper we report the development of an accurate equation of state for sour and hydrogen containing natural gas / gas condensate systems. This equation of state is tested with success for variety of cases of interest in the natural gas engineering for which experimental data are available for comparisons. The basic aim of the present paper is to produce a simple two-constant cubic equation of state which is capable of calculating thermodynamic properties and phase behavior of sour natural gases and liquids. This equation of state is designed specially to predict thermodynamic properties and phase equilibria of liquids and vapors which consist of hydrogen, methane, other light hydrocarbons and acidic components appearing in the natural gas and gas condensate streams. In the first part of this report we introduce a two-constant cubic equation of state. This cubic equation of state, which is based on statistical mechanical theoretical grounds, is extended to mixtures. Then parameters of this equation of state are derived for different components of sour natural
15

gas systems. The resulting equation of state is tested for phase behavior and other thermodynamic properties of simulated and natural sour gas mixtures. It is shown that the present equation of state, even though it is simple, predicts the properties of interest with ease mid accuracy.

THE EQUATION OF STATE A new simple two-constant cubic equations of state for hydrocarbons, hydrocarbon mixtures, and other nonassociating fluids was introduced earlier 9. This equation of state model is based on the statistical mechanical information available for the repulsive thermodynamic functions and the phenomenological knowledge of the attractive potential tail contributions to the thermodynamic properties. This new two-constantparameter cubic equation is in the following form: Z = (v + 1.3191b)/(v -b)- a /
[RT32(v +

b)]

(1)

Equation (1) is cubic in terms of volume and contains only two adjustable parameters. By applying the critical point constraints on the above equation, parameters a & b are determined to be*9 a = ().486989R2TC52 /PC and b =0. W2RTC/PC (2)

The critical compressibility factor based on this equation of state is calculated to be,

Zc = 1/3,

(3)

the same as the Redlich-Kwong (RIO equation of state. It is shown that this equation of state is more accurate than the Redlich-Kwong equation, which had been considered to be the best two-constant-parar.leter cubic equation of state19. For multicomponent mixtures this equation of state assumes the following form9 Zm =
v +

~.3191bRm- arn/R~2 V +b~ v-b~ and

(4)

where we use the following mixing rule for am, bk %. a~=~,~,xjl bh = (3/4)~ifi~x~ij bAm ~ bti
+ 1/4)~/%b.

(5) (6) (7)

174

.,

WE 269(M

M. MOHSEN-MA, H. MODDARESS AND G.A. MANSOORI of fluids21 we may expression for fl(Tr)
8(TJ1/3

3 polynomial (13) we use

Subscript (R) in bm stands for the repulsive mixing rule and subscript (A) in b~ ~ stands for the attractive mixing rule of b. For reasons mentioned elsewhere19 the mixing rule for parameter b when appears in the repulsive (positive) term of the equation of state (bR~) will be different from that of the attractive (negative) term @A~).For unlik~interaction parameters aij and bij we use the following combining rules, bij= (bti113 +b@/8 aij = (1 - ki)(au a#2. (8) (9)

use the following

.]/[l+ $+ $+]

=[1+ ~/Tr+

$/T:+

Then for simplicity, and as a first approximation, the following form for f?(Tr) t?(Tr)= (1+
fll/Tr)3/(1 +i$)3

(14)

Eq. (14) satisfies the basic where f$ is a constant. theoretical conditions for fi(Tr) at the critical point, i.e.: f.l(Tr)+l at Tr+l. This fuwtional form will remain finite and positive for all possible temperature ranges. For symmetry and simplicity we also use the same functional form for parameter a(Tr), i.e. a(Tr)= (1 + al /TJ3/(1 + al)3 Where
a, is

Parameter ~j is defined as the coupling parameter which The can be determined using some mixture data. theoretical foundations for the choice of the above mixing and combining rules are discussed elsewhere9. The above cubic equation of state was applied for calculation of thermodynamic properties of hydrocarbons and other nonassociating fluids and fluid mixtures. It was shown that this two-constant cubic equation of state and its mixture version are far superior to the RK equation of state which is also a two-constant cubic equation. However, the better accuracies achieved by this simple cubic equation of state is not still sufficient enough to be used for engineering design calculations. In order to improve the accuracy of the present equation of state to the level that it could be used for engineering design calculations it is necessary to make parameters a & b temperature-dependent similar to the many modifications of the van der Waals and RK equations o: state4$~1s~20. For this purpose we replace parameters a & b with the following temperature-dependent expressions a = aCa(Tr) Where aC= 0.486989R%C52/Pe bC= 0.064662RTC/PC . (11)
and

(15)

a constant. Eq. (15) also satisfies the basic

theoretical conditions for oc(Tr) at the critical point, i.e.: a(Tr) +1 at Tr +1. It can also beinferred from the form of the equation of state, that as the temperature tends to infinity, the attractive term of the equation of state, -a/ [Rp2(v-tb) 1, must tend. to zero. The form of a (Tr) considered in this work is conducive to this requirement. The constants
al

and i$ have been determined

for the

components of the sour natural gas and gas-condensate mixtures as reported in Table 1. These constants were found by minimization of vapor pressures and saturation liquid densities. For ease of calculations, we have correlated parameters al and g, of the major components of natural gas (see Table 1) to their acentric factor in the following form% al = -0.036139+ 0.14167 co; 0.22 s o s 0.18 ().~< u ~ (),l& (16) (17)

b= bCf3(Tr)

(10)

The dimensionless tem~rature-dependent parameters a(Tr) & il(Tr) while are different from each other reduce to unity at the critical Poinfi a(Tr=l) = NT,.1
There

$ = 0.0634-0.18769 co

) = 1

(12)

have beerI a variety of empirical functional forms for a & R reported in the literature. However, in line with the variational and perturbation molecular theories

These correlations are for a) in the range of -0.22<w<0.18 and they do not hold very well for parameters of the components of natural gas which are in minute quantities (C4 till ~,). However, because of the very small concentrations of these components in natural gas streams application of correlations (15) for these components will not cause any appreciable error in the computation of the 175

,,

SOUR NATURAL GAS AND LIQUIDEQUATIONOF STAI5

SPE269(% -23191 T bh/(v-b~ + [~bA;~iq

natural gas thermodynamic properties. Formulation of equation of state of hydrocarbon mixtures containing appreciable amounts of heavier hydrocarbons requires the application of the continuous thermodynamics and C,+ fraction characterization techniques which is out of the XOpe of the present repOr@J201~M.

k%!?k

= InZm + 2319ln((v-b~/v)

s [a~/(b.~Ti2)]

)n[v/(v+bA#

{(1/b~~2) InIv/(v+bAJl

+ l/(bA#+bA~2)} (18)

ln[v/(v+b~ J] + [aJ(2bA ~ 2)] 1 lnfi = -2.31915 In(l-bM/v) + 2.3191[d(nb#&,]/(v-b~

Table 1: Equafwn o~sfafe constants Substances

al %

+ [&*A#~][a/(b#+b~2) + (a~~2 ln(l+bb /v)] /(R@2) - lnz~ - [d(nza~)/d@ ln[(l+b~/v)l /RT%b%

Sm - %tg

(19)
are the

Major Components of Sour NaturaI Gas In the above equations Hm - Hmig ~d H2 N2 co co~ H2S CH4 C2H4 C2H6 C3H6 c3Hg -0.07099 4.02474 -0.02281 -0.00580 -0.02351 -0.03662 -0.02898 -0.02133 -0.00841 -0.01457 0.12307 0.06393 0.06066 0.01456 0.04207 0.05957 0.03865 0.04504 0.04624 0.03657 mixture enthalpy departur~~nction and r%xture entropy departure function, respectively, and fi is the fugacity of mmpcment i in a mukicomponent titure. am, b~and bb are defkd by eqs (5), (6) and (7) and parameters a and b refer to (da/dT) and (db/dT), respectively. Expressions for the other thermodynamic functions can be easily derived t%omthe above equations. RESULTS AND DXSCUSSION In order to test the accuracy and applicability of the present equation of state it is first used for density, enthalpy and entropy calculations of the major pure components of the sour natural gas at different temperatures and pressures. Table 2 shows results of these calculations using the present equation of state along with the SRK and PR equations. According to this table even though predictions by the SRK and PR equations are some times better than the present equation, over all the present equation of state is more accurate than the SRK and PR equations. We have used the present equation of state for calculation of compressibility factors of binary mixtures of methanehydrogen sulfide at T= 377.65 K and at two different pressures. Fig. 1 shows the results of this calculation by using the present equation of state along with the PR equation (all with kij=O). According to this figure the results of calculations by the present equation of state are generally closer to the experimental data than the PR equation. Another compressibility factor calculation was performed for a methane-carbon dioxide mixture (xcoz = 0.4761) at
(17)

Components of Natural Gas in Minute Quantities n-C4H10 i-C4Hlo ~-%w2 n-C6H14 n-C7H~6 -0.00663 -o.olw3 -(MNW78
-fMW761

0.00425

0.03613 0.02852 0.02251 0.01258 0.01342

One of the requirements of equations of state tor industrial applications is their analytic representation of thermodynamic functions. Such properties of fluids (like entropy, enthdpy, and fugacity) are of direct interest in energy balance and phase behavior calculations in industrial practice. The analytic expressions of these functions a;e as the following Hm-H * = (Z~ - 1) -2.3191Tbw/(v-b~ RT . amInlv/(v+bA #/~~ ~T12 + [bAm/ RFq {(am /bh~2)Jn[v/(v+bA J] +aJ1bJV+b~Jl +0.5aJbJ@~ ~[ V/(V+bJl

250 K and at different pressures. Fig. 2 shows results of this calculation based on the present equation of state along with those obtained form the PR and SRK equations (all with \j=O). According to this figure also the present 176

SPE269W

M. MOHSEN-NIA, H. MOI)DARESS AND G.A. MANSOORI

equation of state is more accurate than the other equations reported. A third set of compressibility factor calculations were performed for the nitrogen-carbon dioxide (xcoz = 0.447) mixture at constant volume (isochore) and at different temperatures and pressures. Table 3 shows the results of this calculation as compared with the results of the PR and SRK equations of state (all with kij=O).According to this table also the compressibility factors calculated by the present equation are closer to the experimental data than the other equations. A fourth set of compressibility factor calculations were performed for three different sour natural gas mixtures. Table 4 shows the compositions of these sour natural gas mixtures. The results of these calculations are reported in Table 5. According to this table the compressibilities calculated using the present equation of state are much closer to the experimental data than the PR equation, while the calculations by the SRK equation are equally accurate as the present equation of state. The present equation of state is used for the vapor-liquid equilibria (VLE) calculations of seven different binary sour and hydrogen containing fluid mixtures for which experimental data are available. Table 6 compares results of the VLE calculations using the present equation of state, PR equation and SRK equation assuming ki~s=O for all the equations. According to this table the present quation of state is overall superior to the other equations for the mixtures tested. On I@res 3 through 7 the results of the VLE calculations along with the experimental data for five different binary mixtures comprising the major components of sour natural gas systems are reported. According to these figures the present equation of state can predict thermodynamic properties of sour and hydrogen containing vapor and liquid mixtures with good accuracy. The calculations and comparisons reported hwe indicate that the present equation of state is quite suitable for property prediction of sour and hydrogen containing natural gas and liquid systems of interest in the oil and gas industries. One major advantage of this equation of state is its sound theoretical basis in the choice of its mixing and combhing rules and the functional forms of a(Tr) and f3(Tr) as reported by eqs (14) and 05). These theoretically correct choices make the present equation of state more suitable for extrapolation purposes than the empirical equations, beyond the ranges of the available expimental data on which equation of state parameters are basal upon. a b f H kij n P PR R RK ~RK T T, ; parameter in equation of state parameter in the equation of state fugacity enthalpy coupling parameter total number of moles pressure Peng-Robinson equation of state Universal gas constant Redlich-Kwong equation of state entropy Soave-Redlich-Kwong equation of state absolute temperature =T/TC molar volume =Pv/RT, compressibility factor

% fl @l P z 0)

parameter in equation of state constant in equation of state parameter in equation of state constant in equation of state density 3.1415927 acentric factor

=ttractive c itj ij ig m r R critical mmponent indims property of i-j interaction ideaI gas mixture reduced repuIsive

ACKNO} J?.EGMI?NTS This research is supported in part by the Gas Research Institute contract No. 5090-260-2085, and in part by Rotoflow Corporation, Inc. REFERENCES 1. International Petoleum Encyclopedia, Publishing Co., Tulsa, Oi(, 1993. PennWell

2. Campbell, J.M.: Gas Conditioning and Processing, Campbell Petrol. Series, Norman, OK 1976.

SOURNATURALGAS AND LIQUIDEQUATION OF STATE

SPE 26906

3. Katz, D.L. and Lee, L.L.: Natural Gas Engineering, McGraw-Hill Book Co., New York, NY 1990. 4. Mansoori, G.A. and Savidge, J.L.: Predicting Retrograde Phenomena and Miscibility using Equations of State; SPE Paper No. 19809, Proceedings of the 1989 Annual SPE Meeting, Society of Petroleum Engineers, Richardson, TX. 5. Edmister, W.C. and Lee, B.i: Applied Hydrocarbon Thermodynamics, Gulf Pub. Co., Houston, TX 1986. 6. Mansoon, G.A. and Jian& T.S.: Asphaltene Deposition and its Role in Enhanced Oil Recovery Miscible Gas Fioodin& Proceedings of the 3rd European Conference on Enhanced Oil Recovery, Rome, Italy, April 1985. 7. Wichert, E. and Aziz, K.: Calculation of Zs for Sour Gases, Hydrocarbon Processing, 1972, VOL 51, No.5, pp.119-12. 8. Gu, M.X., Li, Q., Zhou, S.Y., Chen, W.D. and Guo, T.M.: Experimental and Modeling Studies on the Phase Behavior of High H2S-Content Natural Gas Mixtures: Fluid Phase Equilibria, 1993, VOL82,173-182. 9. Li, Q. and Guo, T. M.: A Study on ~he %qxrcompressibility and Compressibility Factors of Natural Gas Mixtures: Journal of Petroleum Science and Engineering 1991,6,235-247. 10. Morris, J.S. and Byers, C. H.: Near-Critical-Region Equilibria of the Methane-Carbon Dioxide and Hydrogen Sulfide System: Fluid Phase Equilibria, 1991, 66, 291308. 11. Huron, M.J. and Dufour, G.N., and Vidal, J.: VaporLiquid Equilibria and Critical Locus Curve Calculations with the Soave Equation for Hydrocarbon Systems with Carbon Dioxide and Hydrogen Sulfide, Fluid Phase Equilibria, 1978,1,247-252. 12. Evelein, K.A. and Moore, G.R.: *Prediction of Phase Equilibria in Sour Natural Gas Systems Using the SoaveRe#lich-Kwong Equation of State, Ind. Eng. Chem. Process Des. Dev., 1979, vol. 18, No. 4,618-624. 13. Morns, ],S. and Byers, C.H.: Critical Region VaporLiquid Equilibria of the CH4-C02-H2S System, 1990, ORNL/TM-10806, Oak Ridge, TN. 14. Huang, F.H., Li, M.H., Lee, L.L., and Starling, K.E.: An Accurate Equation of State for Carbon Dioxide,, J. Chem. Eng. of Japan, 1985,18,490-498.

15. Hall, K.R. et al: PhaseEquilibria Calculated for the Systems N2+C02, CH4+C02, CH4+H2S~ J. Fluid Phase Equilibria, 1983, VOI15,11-32. 16. Robinson, D.B., Kalra, H. and Rempis, H.: The Equilibrium Phase Properties of a Synthetic Sour Gas Mixture and a Simulated Natural Gas Mixturet Research Report, 1978, RR-31, Gas Processor Association. 17. Mraw, S.C. and Hwang, S.C., Kobayashi, R.: The Vapor-Liquid Equilibria of the CH4-C02 System at Low Temperatures; J. of Chemical Engineering Data, 1978, Vol. 23, No. 2,135-139. 18. Eakin, B.E. and Devaney, W. E.: Enthalpies of Hydrogen Sulfied-Methane-Ethane Systems, 1975, Research Report, RR-9, Gas Processor Association. 19. Mohsen-Nia, M., Moddaress, H. and Mansoori, G.A: A Simple Cubic Equation of State for Hydrocarbons and Other Compound% SPE Paper #26667, Proceedings of the, 1993 Annual Technical Conference and Exhibition of the Socitey of Petroleum Engineers, Houston, TX. 20. Chore, L.G. and G.A. Mansoori (Editors): C7+ Fraction Characterization Advances in Thermodynamics, Taylor & Francis Pub. Co., New York, N.Y., 1988. Vol. 1,

21. Mansoori, G.A. and Canfield, F.B.: Perturbation and Variational Approaches to the Equilibrium Thermodynamic Properties of Liquids and Phase Transitions, Industrial and Engineering Chemistry (monthly), 1970, Vol. 62, No. 8,12-29. 22. Du, P.C. and Mansoori, G.A.: A Continuous Mixture Computational Algorithm for Reservoir Fluids Phase Behavioral SPE Paper # 15082, Proceedings of the 1986 California Regional Meeting of SPE, Society of Petroleum Engineers, Richardson, TX, 1986. 23. Du, P.C. and Mansoori, G.A.: Continuous Mixture Computational Algorithm of Reservoir Fluid Phase Behavior Applicable for Compositional Reservoir Simulation; SPE Paper # 15953, Proceedings of the 1986 Eastern Regional Meeting of SPE and Proceed~qgs of the 9th SPE Synqmsium on Reservoir Simulation, Society of Petroleum Engineers, Richardson, TX, 1986. 24. Sage, B. H. and Lacey, W. N.: Some Properties of the Lighter Hydrocarbons, Hydrogen Sulfide and Carbon Dioxide;, 1955, pp., 44..57, Am. Petroleum Inst., New York. 25. Bailey, D.M., Esper, G.J., Holste, J.C., Hall, K.R., Eubank, P.T., Marsh, K.M. and Rogers, W.J.: Properties of C02 Mixtures with N2 and with CH4; Research Report

178

SPE 26%

M. MOHSEN-NIA, H. MODDARESS AND G.A, MANSOORI

RR-122, Gas Processors Association and the Gas Research Institute, July 1989. 26. Buxton, T.S. and Campbell, J.M.: Comperessibility Factors for Lean Natural Gas-Carbon Dioxide Mixtures at High pressures; Trans. AIME, 1967, Vol. 240,80-86 27. Satter, A. and Campbell, J.M.: Non-Ideal Behavior of Gases and thier Mixtures: Trans. AIME, 1963, Vol. 228, 333-347. 28. Wichterle, L and Kobayashi, R.: Vapor-Liquid Equilibrium of Methane-Ethane System at Low Temperatures and High Presures, J. C.hem. Eng. Data, 1972, vol. 17,1,9-14. 29. Reamer, H.H., Sage, B.H. and Lacey, W.N.: Phase Systems,* Ind. Eng. Equilibria in Hydrocarbon Chem.,1951, 43,976-981. 30. Sobocinski, D.P. and Kurata, F.: Heterogeneous Phase Equilibria of the Hydrogen Sulfide-Carbon Dioxide System; AIChE J., 1959,5,4,545-551. 31. Sagara, H., Arai, Y. and Saito, S.: Vapor-Liquid Equilibria of Einary and Ternary Systems Containing Hydrogen and Light Hydrocarbons;, J. Chem. Eng. of Japan, 1972, vol. 5, No. 4.,339-348.

179

..

, Table2-

Comparfeonof the present, PRand SRKWpU@W of state fOrdensity (p), enthdpy (H) and entropy (S) predtcttonaof the major pure components ofsournatural gas .

Substarm Mtthane

T (K) 110.500 200.500 150.450 150.560

Ethnr
Ethylenr

Propane

Propylene 100.600

Hydrogen 20-500 Nitrogen 74-700

co cm H#i w% 80-600 250.1000 255.480

[
t5RK ---- ---- ,---- -----p%
H%

sPE26w16
.-
Present

PR --H%

---We

----p 70
1.8

,---- ---Hk w 1.0 1.1 3.1 1.9 0.6 0.8 0.5 0.4 1.7 7-IL.

P (bar)

10.500

of &ta .
No. 90 80 70 75

s%
0.5

p%

s%
0.6 0.5 1.2 0.5 2.1 1.2 0.4 0.8 0.5 0.1 - 0.6
-L

5.3

iT

63
1,3 1.1 0.4 2.3 1.7 0.5 0.3 0.5 0.4 r

1.5-350 10.400 10.400

3.1 3.7 4.5

1.0 2.6 0.8 0.5 0.8 0.5 0.5 2.4

0.5 0.8 2.5

5.1 4.7 4.6

0.6 0.8 2.5 1.6 2.1 0.6 0.6 0.4 3.1

2.2 1.7 2.5 1.6 2.3 2.2 1.4 2.1 1.5 1.9

0.5-500

80 70 60 90 00

0.5

4.0

2.6

5.0 6.0 4.7

0.1-400 0.75.500 5.0.500 2.0.500 1.0.210

1.3 2.9 1.4 8.0 2.6

2.4 0.7

85

0.7 1.7 0.2

5.3 1.8 4.4 4.7

xi

n--

n-

-1

Table 3- ComwsriaonLmtween the exwirnentd= and cakufeted comwessibilt~ factors for (Ni&ogen+ Carbon diordd;) sprn at Xm =0.SS3 using thi present, % and SRKequatfoneof state ~is = O)

T (K) 300.10 320.08 288.79 273.19 260.02 250.06 242.95 241.99 241.03 240.00 239.62

P(bar) 318.29 372.49 287.52 245.07 209.51 163.16 165.10 162.69 180.45 157,98 157.57

Zexp. 0.8870 0.9738 0.8326 0.7500 0.8736 0.6123 0.5680 0.5620 0.5564 0.5502 0.5492

SRK 0.9311 1.0169 0.8763 0.7923 0.7127 0.6467 0.5967 0.5897 0.5828 0.5753 0.5740 5.1

PR 0.8629 0.9439 0.8113 0.7322 0.6574 0.5955 0.5464 0.5418 0.5353 0.5282 0.5270 3.2

present 0.9148 0.9997 0.8803 0.7789 0.6976 0.6321 0.5621 0.5751 0.5682 0.5607 0.5594 2.7

Table4- Compositions (in mole fractions)of Uueedtfferent samples of sour naturet gas usedtn the cakulatione reported in Table5 -------------------------------.-------Components Sample Sample Sample A B c L
C2H6 H2S C3H8 0.0000 0.9130 0.0000 0.0900 r).1970 0.0000

0.0052
0.7458 0.2016 o.oA74 0.0000 0.0000

0.0081
0.8303 0.0744 0.0130 0.0735 0,0007

Oweretf % devfatiorrs

arrd calculated Table 5- Comparison buIweenthe experimenta13,M,v for the three sour natural gas samples ofTable4 using the mmpressibfljty fartors presen~ Pil end SRKequations of state SUwith ~;s. O.
Compreasibiiity Factor (Z)

Sample
A A A A B B B c

T (K) 311.93 327.87 311,93 327.87 310.93 310.93 310.93 310.93

P(bar) 70.72 70.72 139.65 139.65 70.72 139.65 208.58 112.0 0.630 0.856 0.714 0.762 0.665 0.778 0.778 0.821

present

J0.855 0.709 0.765 0.661 0.762 0.791 0.823

0.820

0.790 0.625 0.665 0.721 0.631 0.738 0.737 0.763

0.830 0.857 0.711 0.767 0.864 0.765 0.791 0.626 -

160

iPi26906
Table 6= Thepercentagedeviations of pressures and vapor compositionsfrom the axparfmcntsl data~7*1 for seven different bfnary mixtures by using the present, PRandSRK equations ofstate allAh ki;s=o.

I
Systems (1) + (2) I T Range () ;:;-::; 183-230 103.143 173.198 173.223 233-316 No.of data 26 20 25 12 16 :: (CH4+C2H8) (cFf4+H2s) (w&&c&) (H2+C2H4) (H2+C2H6) (C02+H2S)

P %Deviation

y, v. Deviation

1.07
J

1-377.65

I T3
SF?
3.3 20.0 19.2 24.4 22.1 1$.8 1?.0

Prasent

sw

Present

21.3 20.3 16.2 38 29.2 17.1

2.5 20.4 17.7 19.4 4.9 7.6 17.1

0.5 14.8 9.9 4.2 2.2 1.5 22.6 9.3

0.2 16.7 10.3 5 3 3.5 23.2 lri

0.1 15.3 9.6 2 0.2 1.4 22 8.4

Overall % deviations

---t=

24.1 14.9

1 Oy
g = = i! g Z o.70.6-

0.9

a
Thlawom

o.50.4-

m
q

0.6

P=126afrn P=os.latrn
1

0.6

o.30~ .

1=
THISWORK ----

ExP.

\\

% *, \

* %*

X(CI14]. Figure 1 - Comparison of the calculated compresaibiMy factor of the m.fxfureof (methane+ as hydrogen sulfide) with the experimentaldata24 calculatedby the presentand PR equationsof state
@js = O)at differentmole fractionaat 3T7.65K and
two different

praamres of1%and66.1 atrrt.

Figure 2 - Comparison of the calculated Ccsmpressibtity factorof the mixtureof (methane+ carbon dioxide) with the experimentaldata= as calculatedby the present,SRKand PRequationa of state ~jS = O)at differentpressuresand at 250K and ~z = 0.4761.

so
40

Tfv3wosk ma work

O
b

EXP.(T = 189.65 K) EXP,(T.

-.-.

156.15)

10 o
0.0

.....x...-- K..4.w*..*....""" m."-""".". "..."".".-".#

0.2 0.4 0.6 0:8

1;0

X{l),v(l)
Figure 3 - comparison of the calculated equilibrium pressure-composition diagram of (methase + eti,ane) VStem by the prsaent equation of state (%,= O)with the --e-, xperimental data~s at two different temperatur~ of 139.65 and 156.lSK. 181

SPE26?;

150-1

80--...---.

This work
ExP.
Q@.

~60 -

o
q

x
q

..6

..4YO

...09QQ

~40n *

/ *:*,*e ,a..-..~lf--

)
0.8

---1 479
--)-o- This Wodt 0 ExP.
q ..

.,..

.*,.,.. .. .. -------q o

%,
q .a&

..*&G*o

EXP.

. .P

4 9

&20

T-230K

-0:0

0:2

C.4

0.6

x(1) , Y(1)

oo~ .

1?
J
q

-a

\ .t

s! *-..,.,.e..e ~ ......- ..
x(1) , Y(t)

..*4 ..-a~

,.44 ,...
T m277.6 K

0.8

Figure 4 - Comparison of the calculated equilibrium pressure-composition diagram of (methane + carbon dioxide) system by the present equation of state (tqi = 0.07) with the experimentaldatal~ at 23oK.

Figure 5 - Comparison of the calculated equilibrium pressure-composition diagram of (methane + hydrogen sulfide)system by the presentequation of state (lqj = 0.055) with the experimentaldatazg at 277.6K.

120 This Wolk

q

EXP.(T=143.05 K)

0.0

0.2

* Hgure 6 - Comparison of the calculated equtlibrtumtemperature-compositiondiagram of (carbondioxide+ hydrogensulfide) system by the presentequationof state (kjj= 0.08) with the experimental dats?o at two differentpressures of 6.895 and34.473 bar.

0.4 0.6 x(1), Y(1)

0.8

oo~
x(1) , Y(i)
Figure 7 - Comparison of the calculated equilibrium pressure-composition diagram of (hydrogen + methane) system by the presmt equationof state*{= 0.144) with the experimental datasl at two differenttem~eraturesof 143.05 and 173.65K.