,.

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
●SPE Member

%Yk@ 19S3,SOCWof PetroleumEngineers, Inc.

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 paaltkwrof the &clety of PetroleumEngineara,rfaofficer%or member%Papera preaenwdal SPE meetlngaare subjectto publicationreview by EditorialCommltfeeaof the Soclaty
ofPefrofeumEr@were. Parmtaahntocopyla reafrkfadtoan abafractof M owe than3W wo+de.Illuefratlonsm~ynotbe cqrled. The abstractshouldwntaln conaplcuouaacknowledgment
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.

ABsT’Iwcr INTRODUCTION

‘Ilie major gaseous impurities in the subquality natural gas In the past two decades, a number of subquality natural
sources are acidic components, such as hydrogen sulfide gas / gas condensate fields have been discovered around
and carbon dioxide. Considering that H2S easily the worldl’2. The major impurities of these subquality
dissociates into hydrogen and elemental sulfur, natural gas / gas condensate sources consist of N2, cm and
thermodynamic properties and specially phase equilibria H2S. since that H2S easily dissociates into hydrogen and
of liquid and gaseous systems containing hydrogen, elemental sulfur therefore, thermodynamic properties
hydrogen sulfide, carbon dioxide, other acidic and specially phase equilibria of liquid and gaseous
components, and light hydrocarbons are of much interest systems containing hydrogen, hydrogen sulfide, carbon
to the natural gas and gas condensate production dioxide, other acidic components, and light hydrocarbons
industries. are of much interest to the natural gas and gas condensate
production industries24.
In this paper we report the development of a simple and
accurate cubic equation of state for prediction of
Transportation, and processing of sour and hydrogen
thermodynamic properties and phase behavior of sour
natural gas and liquid mixtures. This cubic equation of containing natural gas is of major concern to the industies
involved. Carbon dioxide and hydrogen sulfide are
state, which is based on statistical mechanical
considered as being impurities in natural gas and oil and
theoretical grounds, is applied to pure fluids as well as
are responsible for corrosion of the flow-line and
mixtures with quite accurate results. All the
pnxessing equipment. Separation of these gases from
thermodynamic property relations of sour gaseous and
natural gas and oil is usually the most expensive part of
liquid mixtures are derived and reported in this report.
natural gas and oil treatment processes. The economical
Parameters of this equation of state are derived for
importance of treatment of sour gas has made it important
different components of sour natural gas systems. The
for the gas and oil industry to have accurate equation of
resulting equation of state is tested for phase behavior
and other thermodynamic properties of simulated and state to represent properties of sour gases and liquid
mixtures3~. Presence of sour gases in crude oiI could also
naturai sour gm mixtures. It is shown that the present
equation of state, even though it is simple, predicts the cause deposition of heavy organics, such as asphaltene
properties of interest with ease and accuracy. and wax, from oil which would plug the well, pipeline
----------- -----_ _-,____ ______ ____ ._, and refining equiprnen~.
References and Illustrations at enci of paper As of yet no satisfactory equation of state has been

173
 . .
*

2 SOUR NATUR4L GAS AND LIQUIDEQUATIONOF STATE SPE26906

available to predict the behavior of sour gases and gas systems. The resulting equation of state is tested for
liquids in reservoir, well, pipeline and compression / phase behavior and other thermodynamic properties of
expansion facilities’. Recently, experimental and simulated and natural sour gas mixtures. It is shown that
modeling studies on the phase behavior of high H2S- the present equation of state, even though it is simple,
content natural gas mixtures were reported by Gu, et al.*. predicts the properties of interest with ease mid accuracy.
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, THE EQUATION OF STATE
instead, a 33-constant super equation of state. By using
this equation of state, Li and GU09 studied the A new simple two-constant cubic equations of state for
supercompressibility and compressibility factors of hydrocarbons, hydrocarbon mixtures, and other non-
natural gas mixtures. However, it is not convenient for associating fluids was introduced earlier ‘9. This equation
engineering calculations to use such a lengthy equation. of state model is based on the statistical mechanical
Morris and Byers ‘0 have performed some experimental information available for the repulsive thermodynamic
work to obtain VLE data for binary and ternary systems functions and the phenomenological knowledge of the
containing CH4, C02, and H2S. Afterwards, they used the attractive potential tail contributions to the
PR and Soave-Redlich-Kwong (SRK) equations of state thermodynamic properties. This new two-constant-
for VLE calculations of the same systems and compared parameter cubic equation is in the following form:
their experimental results with these calculations.
Huron, et all’. and Evelein and Moore’* used the SRK Z = (v + 1.3191b)/(v -b)- a / [RT3’2(v + b)] (1)
equation of state to study the hydrocarbon systems
containing hydrogen sulfide and carbon dioxide They
reported phase equilibria calculations, bu” other Equation (1) is cubic in terms of volume and contains only
thermodynamic property calculations were not reported in two adjustable parameters. By applying the critical point
their paper. On the same subject, some other constraints on the above equation, parameters a & b are
experimental research -works have been reported, such as determined to be*9
the works of Morris and Byers13, Hunage et. al”, Hall et
15 a = ().486989R2TC5’2
/PC and b =0. W2RTC/PC (2)
al , Robinson et alls, Mraw et al’7, and Eakin and
Devaney 18. By reviewing the above literature on The critical compressibility factor based on this equation
equations of state of sour gases and liquids it is concluded of state is calculated to be,
that there is no simple and accu?ate equation of state
available for predicting thermodynamic properties of Zc= 1/3, (3)
sour and hydrogen containing gases and liquids.
the same as the Redlich-Kwong (RIO equation of state. It
In this paper we report the development of an accurate is shown that this equation of state is more accurate than
equation of state for sour and hydrogen containing natural the Redlich-Kwong equation, which had been considered
gas / gas condensate systems. This equation of state is to be the best two-constant-parar.leter cubic equation of
tested with success for variety of cases of interest in the
state19. For multicomponent mixtures this equation of
natural gas engineering for which experimental data are
state assumes the following form’9
available for comparisons. The basic aim of the present
paper is to produce a simple two-constant cubic equation of
v + ~.3191bRm- arn/R~’2
state which is capable of calculating thermodynamic Zm = (4)
v-b~ V +b~
properties and phase behavior of sour natural gases and
liquids. This equation of state is designed specially to
where we use the following mixing rule for am, bk and
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. a~=~,~,xjl (5)

In the first part of this report we introduce a two-constant bh = (3/4)~ifi~x~ij + ‘1/4)~/%b. (6)
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 bAm =
~ “~
bti (7)
state are derived for different components of sour natural

174
., .

WE 269(M M. MOHSEN-MA, H. MODDARESS AND G.A. MANSOORI 3

Subscript (R) in bm stands for the repulsive mixing rule of fluids21 we may use the following polynomial
and subscript (A) in b~ ~ stands for the attractive mixing expression for fl(Tr)
rule of b. For reasons mentioned elsewhere19 the mixing 8(TJ1/3 =[1+ ~/Tr+ $/T:+ .]/[l+ $+ $+- ] (13)
rule for parameter b when appears in the repulsive
(positive) term of the equation of state (bR~) will be
Then for simplicity, and as a first approximation, we use
different from that of the attractive (negative) term the following form for f?(Tr)
@A~).For unlik~interaction parameters aij and bij we use
the following combining rules, (14)
t?(Tr)= (1+ fll/Tr)3/(1 +i$)3

bij= (bti113+b@/8 (8)

where f$ is a constant. Eq. (14) satisfies the basic
theoretical conditions for fi(Tr) at the critical point, i.e.:
aij = (1 - ki)(au a#2. (9)
f.l(Tr)+l at Tr+l. This fuwtional form will remain finite
Parameter ~j is defined as the coupling parameter which and positive for all possible temperature ranges. For
can be determined using some mixture data. The symmetry and simplicity we also use the same functional
theoretical foundations for the choice of the above mixing form for parameter a(Tr), i.e.
and combining rules are discussed elsewhere’9. The above
cubic equation of state was applied for calculation of (15)
thermodynamic properties of hydrocarbons and other non- a(Tr)= (1 + al /TJ3/(1 + al)3
associating fluids and fluid mixtures. It was shown that
this two-constant cubic equation of state and its mixture Where a, is a constant. Eq. (15) also satisfies the basic
version are far superior to the RK equation of state which
is also a two-constant cubic equation. However, the better theoretical conditions for oc(Tr) at the critical point, i.e.:
accuracies achieved by this simple cubic equation of state a(Tr) +1 at Tr +1. It can also “beinferred from the form of
is not still sufficient enough to be used for engineering
the equation of state, that as the temperature tends to
design calculations. infinity, the attractive term of the equation of state,
In order to improve the accuracy of the present equation of -a/ [Rp’2(v-tb) 1, must tend. to zero. The form of a (Tr)
state to the level that it could be used for engineering considered in this work is conducive to this requirement.
design calculations it is necessary to make parameters a &
b temperature-dependent similar to the many The constants al and i$ have been determined for the
modifications of the van der Waals and RK equations o: components of the sour natural gas and gas-condensate
state4$~1s~20.For this purpose we replace parameters a & b mixtures as reported in Table 1. These constants were
with the following temperature-dependent expressions found by minimization of vapor pressures and saturation
liquid densities.
a = aCa(Tr) and b= bCf3(Tr) (10)
For ease of calculations, we have correlated parameters
Where al and g, of the major components of natural gas (see Table
1) to their acentric factor in the following form%
aC= 0.486989R%’C5’2/Pe bC= 0.064662RTC/PC. (11)
al = -0.036139+ 0.14167 co; 0.22 s o s 0.18 (16)
The dimensionless tem~rature-dependent parameters
a(Tr) & il(Tr) while are different from each other reduce $ = 0.0634-0.18769 co ().~< u ~ (),l& (17)
to unity at the critical Poinfi
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
a(Tr=l) = NT,.1 ) = 1 (12)
components of natural gas which are in minute quantities
(C4 till ~,). However, because of the very small
There have beerI a variety of empirical functional forms concentrations of these components in natural gas streams
for a & R reported in the literature. However, in line application of correlations (15) for these components will
with the variational and perturbation molecular theories not cause any appreciable error in the computation of the

175
 . ,,

4 SOUR NATURAL GAS AND LIQUIDEQUATIONOF STA’I’5 SPE269(%

natural gas thermodynamic properties. Formulation of ‘k%!?k = InZm + 2319ln((v-b~/v) -23191 T bh’/(v-b~
equation of state of hydrocarbon mixtures containing
appreciable amounts of heavier hydrocarbons requires the s [a~/(b.~T’i2)] )n[v/(v+bA# + [~bA;~iq
application of the continuous thermodynamics and C,+
{(1/b~~2) InIv/(v+bAJl + l/(bA#+bA~2)}
fraction characterization techniques which is out of the
+ [aJ(2bA ~ “2)]
1 ln[v/(v+b~ J] (18)
XOpe of the present repOr@J201~M.

lnfi = -2.31915 In(l-bM/v) + 2.3191[d(nb#&,]/(v-b~

Table 1: Equafwn o~sfafeconstants + [&*A#~][a/(b#+b~2)
+ (a~~2 ln(l+bb /v)] /(R’@2) - lnz~
Substances al
%
- [d(nza~)/d@ ln[(l+b~/v)l /RT%b% (19)
Major Components of Sour NaturaI Gas
In the above equations Hm - Hmig ~d Sm - %tg
are the
H2 -0.07099 0.12307
mixture enthalpy departur~~nction and r%xture entropy
N2 4.02474 0.06393
departure function, respectively, and fi is the fugacity of
co -0.02281 0.06066
mmpcment i in a mukicomponent titure. am, b~and bb
co~ -0.00580 0.01456
H2S -0.02351 0.04207 are defkd by eq’s (5), (6) and (7) and parameters a’ and
CH4 -0.03662 0.05957 b’ refer to (da/dT) and (db/dT), respectively. Expressions
for the other thermodynamic functions can be easily
C2H4 -0.02898 0.03865
derived t%omthe above equations.
C2H6 -0.02133 0.04504
C3H6 -0.00841 0.04624 RESULTS AND DXSCUSSION
c3Hg -0.01457 0.03657
In order to test the accuracy and applicability of the
Components of Natural Gas in Minute Quantities present equation of state it is first used for density,
enthalpy and entropy calculations of the major pure
n-C4H10 -0.00663 0.03613 components of the sour natural gas at different
i-C4Hlo -o.olw3 0.02852 temperatures and pressures. Table 2 shows results of these
~-%w2 -(MNW78 0.02251 calculations using the present equation of state along with
n-C6H14 -fMW761 0.01258 the SRK and PR equations. According to this table even
n-C7H~6 0.00425 0.01342 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.
One of the requirements of equations of state tor industrial
applications is their analytic representation of
We have used the present equation of state for calculation
thermodynamic functions. Such properties of fluids (like
of compressibility factors of binary mixtures of methane-
entropy, enthdpy, and fugacity) are of direct interest in
hydrogen sulfide at T= 377.65 K and at two different
energy balance and phase behavior calculations in
pressures. Fig. 1 shows the results of this calculation by
industrial practice. The analytic expressions of these
using the present equation of state along with the PR
functions a;e as the following - -
equation (all with kij=O). According to this figure the
results of calculations by the present equation of state are
Hm-H generally closer to the experimental data than the PR
* = (Z~ - 1) -2.3191Tbw’/(v-b~ equation.
RT
. am’Inlv/(v+bA #/~~ ~T1’2
Another compressibility factor calculation was performed
for a methane-carbon dioxide mixture (xcoz = 0.4761) at
+ [bAm’/ R’Fq {(am/bh~2)Jn[v/(v+bA J]
250 K and at different pressures. Fig. 2 shows results of
+aJ1’bJV+b~Jl +0.5aJbJ@~ ~[ V/(V+bJl (17) 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 5

equation of state is more accurate than the other equations

reported.
a parameter in equation of state
A third set of compressibility factor calculations were b parameter in the equation of state
performed for the nitrogen-carbon dioxide (xcoz = 0.447) f fugacity
mixture at constant volume (isochore) and at different H enthalpy
temperatures and pressures. Table 3 shows the results of kij coupling parameter
this calculation as compared with the results of the PR n total number of moles
and SRK equations of state (all with kij=O).According to P pressure
this table also the compressibility factors calculated by PR Peng-Robinson equation of state
the present equation are closer to the experimental data R Universal gas constant
than the other equations. RK Redlich-Kwong equation of state
entropy
A fourth set of compressibility factor calculations were ~RK Soave-Redlich-Kwong equation of state
performed for three different sour natural gas mixtures. T absolute temperature
Table 4 shows the compositions of these sour natural gas T, =T/TC -
mixtures. The results of these calculations are reported in molar volume
Table 5. According to this table the compressibilities ; =Pv/RT, compressibility factor
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 a parameter in equation of state
accurate as the present equation of state. constant in equation of state
%
fl parameter in equation of state
The present equation of state is used for the vapor-liquid
equilibria (VLE) “calculations of seven different binary @l constant in equation of state
sour and hydrogen containing fluid mixtures for which P density
experimental data are available. Table 6 compares z 3.1415927
results of the VLE calculations using the present equation 0) acentric factor
of state, PR equation and SRK equation assuming ki~s=O
for all the equations. According to this table the present =ttractive
quation of state is overall superior to the other equations
for the mixtures tested. c critical
itj mmponent indims
On I@res 3 through 7 the results of the VLE calculations ij property of i-j interaction
along with the experimental data for five different ig ideaI gas
binary mixtures comprising the major components of sour m mixture
natural gas systems are reported. According to these r reduced
figures the present equation of state can predict R repuIsive
thermodynamic properties of sour and hydrogen
containing vapor and liquid mixtures with good accuracy.
ACKNO} J?.EGMI?NTS
The calculations and comparisons reported hwe indicate
that the present equation of state is quite suitable for This research is supported in part by the Gas Research
property prediction of sour and hydrogen containing Institute contract No. 5090-260-2085, and in part by
natural gas and liquid systems of interest in the oil and Rotoflow Corporation, Inc.
gas industries. One major advantage of this equation of
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6 SOURNATURALGAS AND LIQUIDEQUATION OF STATE
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SPE 26906
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179
 ..

sPE26w16
, Table2-

.—— ——

Substarm

Mtthane
T (K)

110.500
——

—-
Comparfeonof the present, PRand SRKWpU@W of state fOrdensity (p), enthdpy (H) and entropy (S)

I
predtcttonaof the major pure components ofsournatural

P (bar)

10.500
No.
&ta
—.
90
of
—

m
p%
t5RK

H%

T
—
---- ---- ,---- ------

s%
0.5
gas .

.—
p%

5.3
PR
---

H%

iT
----

We

63—
.—- ——

-----

p 70

1.8
Present
,---- ----

Hk

w
s%
0.6

[
Ethnr 200.500 1.5-350 80 3.1 1.0 0.5 5.1 0.6 1,3 2.2 1.0 0.5
Ethylenr 150.450 10.400 70 3.7 2.6 0.8 4.7 0.8 1.1 1.7 1.1 1.2
Propane 150.560 0.5-500 80 4.5 0.8 0.5 4.6 2.5 0.4 2.5 3.1 0.5
Propylene 100.600 10.400 75 4.0 2.6 2.5 5.0 1.6 2.3 1.6 1.9 2.1
Hydrogen 20-500 0.1-400 70 1.3 0.5 2.4 6.0 2.1 1.7 2.3 0.6 1.2
Nitrogen 74-700 0.75.500 60 2.9 0.8 0.7 4.7 0.6 0.5 2.2 0.8 0.4
co 80-600 5.0.500 85 1.4 0.5 0.7 5.3 0.6 0.3 1.4 0.5 0.8
cm 250.1000 2.0.500 90 8.0 0.5 1.7 1.8 0.4 0.5 2.1 0.4 0.5
H#i 255.480 1.0.210 00 2.6 2.4 0.2 4.4 3.1 0.4 1.5 1.7 0.1
—— -—
w% xi n-- n- 4.7 G r 1.9 7-I- 0.6
——— — -1 —— L. -L—

Table 3- ComwsriaonLmtweenthe exwirnentd= and cakufeted comwessibilt~

factors for (Ni&ogen+ Carbon diordd;) sprn at Xm =0.SS3using thi present, % Table4- Compositions (in mole fractions)of Uueedtfferent
and SRKequatfoneof state ~is = O) samples of sour naturet gas usedtn the cakulatione
reported in Table5
-------------------------------- .------- --
Components Sample Sample Sample
T (K) P(bar) Zexp. SRK PR present A B c

300.10 318.29 0.8870 0.9311 0.8629 0.9148 0.0000 0.0052 0.0081

320.08 372.49 0.9738 1.0169 0.9439 0.9997 L 0.9130 0.7458 0.8303
288.79 287.52 0.8326 0.8763 0.8113 0.8803 0.0000 0.2016 0.0744
273.19 245.07 0.7500 0.7923 0.7322 0.7789 C2H6 0.0900 o.oA74 0.0130
260.02 209.51 0.8736 0.7127 0.6574 0.6976 H2S r).1970 0.0000 0.0735
250.06 163.16 0.6123 0.6467 0.5955 0.6321 C3H8 0.0000 0.0000 0,0007
242.95 165.10 0.5680 0.5967 0.5464 0.5621
241.99 162.69 0.5620 0.5897 0.5418 0.5751
241.03 180.45 0.5564 0.5828 0.5353 0.5682
240.00 157,98 0.5502 0.5753 0.5282 0.5607
239.62 157.57 0.5492 0.5740 0.5270 0.5594

Oweretf % devfatiorrs 5.1 3.2 2.7

Table 5- Comparison buIweenthe experimenta13,M,varrd calculated

mmpressibfljty fartorsfor the three sour natural gas samples ofTable4 using the
presen~ Pil end SRKequations of state SUwith ~;s. O.

Compreasibiiity Factor (Z)

Sample T (K) P(bar) present

A 311.93 70.72 0.630 0.820 0.790 0.830

J-
A 327.87 70.72 0.856 0.855 0.625 0.857
A 311,93 139.65 0.714 0.709 0.665 0.711
A 327.87 139.65 0.762 0.765 0.721 0.767
B 310.93 70.72 0.665 0.661 0.631 0.864
B 310.93 139.65 0.778 0.762 0.738 0.765
B 310.93 208.58 0.778 0.791 0.737 0.791
c 310.93 112.0 0.821 0.823 0.763 0.626
-——

160
iPi26906
Table6=Thepercentagedeviations of pressures and vapor compositionsfrom the
axparfmcntsl data~7*1 for seven different bfnary mixtures by using the present, PRandSRK
equations
ofstateallAh ki;s=o.

I P %Deviation
I
y, v. Deviation —

I T3
Systems T Range No.of SF?’ m Prasent sw m Present
(1) + (2) I (’) data

(CH4+C2H8) ;:;-::; 26 3.3 2.5 0.5 0.2 0.1

(cFf4+H2s) - 20 20.0 21.3 20.4 14.8 16.7 15.3
(w&&c&) 183-230 25 19.2 20.3 17.7 9.9 10.3 9.6
103.143 12 24.4 16.2 19.4 4.2 5 2
(H2+C2H4) 173.198 16 22.1 38 4.9 2.2 3 0.2
(H2+C2H6) 173.223 1$.8 29.2 7.6 1.5 3.5 1.4
(C02+H2S) 233-316 :: 1?.0 17.1 17.1 22.6 23.2 22

Overall % deviations 24.1 14.9 9.3 lri 8.4

---t=

1.07
J
1’-377.65 K
0.9“
a
1 O“y
g o.7-
=
= 0.6- a ● ExP. ●

1=
—Thlawom ‘%
i! ~ 0.6 — THISWORK \\ *, *
g o.5- —m
---- %*
● P=126afrn E \
Z 0.4- 0 0.6
v o P=os.latrn Q —m
o.30~
. 1
“X(CI14]. “
Figure 1 - Comparison of the calculated Figure 2 - Comparison of the calculated
compresaibiMyfactor of the m.fxfureof (methane+ Ccsmpressibtityfactorof the mixtureof (methane+
hydrogen sulfide) with the experimentaldata24as carbon dioxide) with the experimentaldata= as
calculatedby the presentand PR equationsof state calculatedby the present,SRKand PRequationaof
@j’s = O)at differentmole fractionaat 3T7.65K and state ~jS = O)at differentpressuresand at 250K
two different praamresof1%and66.1atrrt. and ~z = 0.4761.
I
so
— Tfv3wosk O EXP.(T = 189.65 K) I

40 J ““-.-.” ma work b EXP,(T. 156.15’) A

10“

o .....x...-- K..4.w*..*-...."""
m."-""".".
"..."".".-".#
0.0 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?; i “

150-1 1
.*,.,.. .. .. --------

-“--1
‘--)-o- This Wodt .,.. %,
●.. o ●
0 ExP. ● .“a&
..*&G*o
● EXP. . .P ‘4 9
80-
‘--...-”-”-”.’ This work
...09QQ
479’”” -a

)
1?
o ExP. ..4Y””’O
~60 - ..6”””
a
● Q@. J“ \

x ●
.t

~40-
n
*
/“”
*:*,*’e
s! *-..,.,.e..e ,.4”4
,...
●
&20 ,a..-..~lf””--’”

T-230K
~......- .. ..-’a””~
..*”4
T m277.6 K
oo~
-0:0 0:2 C.4 0.6 0.8 . 0.8
x(1) , Y(1) x(1) , Y(t)
Figure 4 - Comparison of the calculated Figure 5 - Comparison of the calculated equilibrium
equilibrium pressure-composition diagram of pressure-composition diagram of (methane + hydrogen
(methane + carbon dioxide) system by the sulfide)system by the presentequation of state (lqj = 0.055)
present equation of state (tqi = 0.07) with the
with the experimentaldatazg at 277.6K.
experimentaldatal~ at 23oK. “

120
— This Wolk ● EXP.(T=143.05 K)

0.0 0.2 0.4 0.6 0.8 1

x(1), Y(1)
*
Hgure 6 - Comparison of the calculated
equtlibrtumtemperature-compositiondiagram oo~
of (carbondioxide+ hydrogensulfide)system by
x(1) , Y(i) “
the presentequationof state (kjj= 0.08) with the
Figure 7 - Comparison of the calculated equilibrium
experimental dats?o at two differentpressures pressure-composition diagram of (hydrogen + methane)
of 6.895 and34.473 bar. system by the presmt equationof state*{= 0.144) with the
experimental datasl at two differenttem~eraturesof 143.05
and 173.65K.