Journal of Natural Gas Chemistry 20(2011)364–371

Experimental determination and prediction of the compressibility factor

of high CO2 content natural gas with and without water vapor
Xiaoqiang Bian∗ , Zhimin Du, Yong Tang
The State Key Laboratory of Oil & Gas Reservoir Geology and Exploitation Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China
[ Manuscript received December 13, 2010; revised March 31, 2011 ]

Abstract
In order to study the effect of different CO2 contents on gas compressibility factor (Z-factor), the JEFRI-PVT apparatus has been used to
measure the Z-factor of dry natural gas with CO2 content range from 10.74 to 70.42 mol% at the temperature range from 301.2 to 407.3 K and
pressure range from 7 to 44 MPa. The results show that Z-factor decreases with increasing CO2 content in natural gas at constant temperature
and increases with increasing temperature for natural gas with the same CO2 content. In addition, the Z-factor of water-saturated natural
gas with high CO2 content has been measured. A comparison of the Z-factor between natural gas with and without saturated water vapor
indicates that the former shows a higher Z-factor than the latter. Furthermore, Peng-Robinson, Hall-Yarborough, and Soave-Benedict-Webb-
Rubin equations of state (EoS) are used for the calculation of Z-factor of high CO2 content natural gas with and without water vapor. The
optimal binary interaction parameters (BIP) for PR EoS are presented. The measured Z-factor is compared with the calculated Z-factor based
on three models, which shows that PR EoS combined with van der Waals mixing rule for gas without water and Huron-Vidal mixing rule for
water-saturated gas, are in good agreement with the experimental data.
Key words
compressibility factor; CO2 ; natural gas; water vapor; equation of state

1. Introduction
In recent years, more and more natural gas reservoirs with
high CO2 content around the world have been discovered [1].
Natural gas with different CO2 contents results in different
gas compressibility factor (Z-factor), which is one of the most
important parameters in upstream and downstream operations
and is used in calculating gas properties such as formation vol-
ume factor, density, compressibility [2,3]. All these properties
are necessary in the natural gas industry for evaluating newly
discovered gas reservoirs, estimating the original gas in place,
analyzing production performance, and predicting future gas
production.
There are four methods to measure or predict Z-factor,
i.e., experimental measurement [4−7], equation of state
[8−11], corresponding state correlations [12−14], and em-
pirical formula [15−19]. Experimental measurement of Z-
factor has the highest accuracy among all these methods. The
most commonly used cubic equation of state for calculating
the Z-factor was presented by Peng and Robinson (PR EoS)
[20]. However, as discussed by Elsharkawy [21], cubic equa-
tions of state have poor ability to predict the volumetric prop-
erties of hydrocarbon gas mixtures in comparison with empir-
ical correlations. Thus, different empirical correlations have
been proposed, such as Soave-Benedict-Webb-Rubin noncu-
bic equation of state (SBWR EoS) [22,23], Hall-Yarborough
equation of state (HY EoS) [24], and Dranchuk-Abou-Kassem
correlation [25]. Moreover, prediction of the Z-factor for high
CO2 content natural gas is much more difficult than that for
sweet gases. Wichert and Aziz (WA) [26] presented cor-
rections for the presence of H2 S and/or CO2 in natural gas
for determining Z-factor of sour gases. Fortunately, in the
present study, due to the absence of C7+ fraction, the crit-
ical properties of the C7+ fraction are not calculated from
correlations [27].

∗Corresponding author. Tel: +86-28-83032091; Fax: +86-28-83032901; E-mail: bxqiang3210 88@163.com

This work was supported by the National Science and Technology Major Project of P.R.China (No.2008ZX05016-001) and the National Natural Science
Foundation of China (No. 50774062).

Copyright©2011, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
doi:10.1016/S1003-9953(10)60210-1
 Journal of Natural Gas Chemistry Vol. 20 No. 4 2011 365

The present work is concentrated on two objectives.
One is to measure the Z-factors of dry natural gases with
different CO2 contents about 10%–70% and those of water-
saturated natural gases with different CO2 contents by apply-
ing JEFRI-PVT experimental equipments which were made
by the Schlumberger Company, Canada. The water consid-
ered in this work refers to pure water, and its salinity is zero.
The second objective is to calculate the Z-factor for high CO2
content dry natural gas using the three models, i.e., PR EoS
combined with van der Waals (vdW) mixing rule; SBWR
EoS and HY EoS coupled with Stewart-Burkhardt-Voo (SBV)
mixing rule [28]; WA correction to make a comparison be-
tween the experimental and predicted data. As far as high CO2
content natural gas with saturated water vapor is considered,
we will use the same three models but PR EoS combined with
Huron-Vidal (HV) mixing rule [29]. The binary interaction
parameters (BIP) for PR EoS were also presented.
2. Experimental
(2) Control and maintain the desired temperature using
the constant-temperature air bath.
(3) Introduce a tested gas (about 100 mL) into PVT vessel
to a desirable pressure, adjust the oven through the thermo-
stat to a desirable temperature, stir the gas for 1 h, and then
maintain for 30 min and measure the gas volumes of the PVT
vessel.
(4) Slightly open the valve between the cells and bleed
gas from the PVT vessel into the flash separators; at the same
time, keep the pressures of the PVT vessel constant using an
automatic pump.
(5) Record the bleed gas volumes and remain gas volumes
of PVT vessel.
(6) Use Equation 1 to determine Z-factors.
Repeat the Procedures 4−6 at least three times, and en-
sure the tested Z-factors in good repeatability. More detailed
descriptions of the experimental procedure can be found in
Refs. [30,31].

2.1. Measured principles

For natural gas, Z-factor can be calculated using the fol-

lowing equation:
P V Ts
Z= (1)
P sV sT
where, P is experimental pressure, Ps is ambient pressure, T
experimental temperature, Ts is ambient temperature, V is
volume of gas bled from the PVT vessel, and Vs is the volume
of gas released at ambient pressure and temperature. Figure 1. Schematic diagram of the experimental apparatus

2.2. Experimental apparatus and procedure

In the present work, mercury free DBR-PVT vessels
made in Canada were used to measure Z-factors. A schematic
diagram of the corresponding equipment is given in Figure 1.
The experimental apparatus used consisted of PVT vessel
of approximately 135 mL capacity, automatic pump, gas chro-
matograph, gasometer, constant temperature air bath, flash
separator and ground separator.
Typical experimental procedure is as follows:
(1) Clean PVT vessel and cells, then connect the PVT
vessel to the cells and evacuate the cells.
2.3. Experimental results
The gas samples were analyzed using the HP-6890 and
Shimadzu GC-14A gas chromatograph. The results are shown
in Table 1. The critical pressure and temperature [32−36] of
the pure components which are normally presented in natu-
ral gas are also listed in Table 1. Notably, the gas samples
CS-1 and P7 were directly taken from surface of the gas-
liquid separator, and other samples (Gas 1, Gas 2 and Gas 3)
were made from P7, dry natural gas, and pure carbon dioxide
(purity>99.95%).

Table 1. Composition of various gas mixtures and the critical properties of the related component
Components CS-1 (mol%) P7 (mol%) Gas 1 (mol%) Gas 2 (mol%) Gas 3 (mol%) Pc /MPa Tc /K ω
N2 3.79 3.47 1.47 2.45 1.17 3.394 126.2 0.040
CO2 20.74 26.66 10.74 50.33 70.42 7.376 304.2 0.225
CH4 74.33 68.84 84.21 46.49 28.33 4.600 190.6 0.008
C2 H6 1.03 0.94 2.97 0.64 0 4.884 305.4 0.098
C3 H8 0.05 0.04 0.43 0.03 0.02 4.246 369.8 0.152
i-C4 H10 0 0 0.06 0 0 3.640 408.1 0.176
n-C4 H10 0.02 0.01 0.05 0.01 0.01 3.800 425.2 0.193
i-C5 H12 0 0 0.02 0 0.03 3.384 460.4 0.227
n-C5 H12 0.01 0.01 0 0.01 0 3.374 469.6 0.251
C6 H14 0.03 0.03 0.05 0.04 0.02 2.969 507.4 0.296
H2 O 0 0 0 0 0 22.064 647.1 0.344
366 Xiaoqiang Bian et al./ Journal of Natural Gas Chemistry Vol. 20 No. 4 2011

Experimental Z-factors for different CO2 content natu- at initial reservoir pressure and temperature (CS-1 is under
ral gases are shown in Figure 2. It can be seen from Fig- 42.34 MPa and 407.3 K; P7 under 42.34 MPa and 400.7 K)
ure 2 that the Z-factor decreases with increasing CO2 content are indicated in Table 2. It should be noted that water content
in natural gas at 400.7 K isothermal conditions. Z-factor de- in vapor phase slightly increases due to a slight decrease in
creases with increasing pressure at lower pressure range, i.e., pressure during the measurement process. In this work, we
less than 19 MPa, while increases with increasing pressure at are not going to study the variation of water content in detail.
higher pressures, i.e., higher than 19 MPa. The effects of tem-
perature and pressure on the experimental Z-factors for the
gas samples CS-1 and P7 are shown in Figure 3. It can be
seen clearly from Figure 3 that the dependence of the Z-factor
on the pressure follows the same trends as mentioned in Fig-
ure 2. The Z-factor decreases with decreasing temperature
and a greater decrease can be observed in a pressure range
from about 15 MPa to 22 MPa.
Furthermore, the experimental Z-factors of natural gas
with and without saturated water vapor are shown in Fig-
ure 4. Based on these experimental data, it is obvious that the
Z-factors of both CS-1 and P7 gas samples without water are
higher than those of natural gas samples with saturated water
vapor, and that the variation trend of the Z-factor of water-
saturated natural gas with pressure is in accordance with that
of dry natural gas.
For CS-1 and P7 gas samples with water-saturated nat- Figure 2. Variation of Z-factor of natural gases with different CO2 contents
ural gas, measured equilibrium compositions of vapor phase with pressure at 400.7 K

Figure 3. Variation of the Z-factor of CS-1 (a) and P7 (b) gas samples with pressure under different temperatures

Figure 4. Comparison of Z-factors measured and calculated by different models with and without water. (a) CS-1 at 407.3 K, (b) P7 at 400.7 K
 Journal of Natural Gas Chemistry Vol. 20 No. 4 2011 367

Table 2. Measured equilibrium composition of CS-1 and P7 gas samples with water vapor
Components (mol%) H2 O N2 CO2 CH4 C2 H6 C3 H8 n-C4 H10 n-C5 H12 C6 H14
CS-1 2.32 3.76 19.12 73.67 1.02 0.05 0.02 0.01 0.03
P7 2.16 3.46 24.75 68.60 0.94 0.04 0.01 0.01 0.03

3. Z-factor calculation methods

ψ[1 + βψ + γψ 2 + δψ 4 + εψ 2 (1 + ϕψ 2) exp(−ϕψ 2 )]
In this work, three models, i.e., PR, HY and SBWR are
= Ppr /Tpr
used to calculate the Z-factors of high CO2 content natural gas
(14)
without water vapor. For mixtures, PR EoS can be described
The detailed equation parameters and solving equation of
as below:
the SBWR EoS are listed in Appendix B.
RT am Since water is a strongly polar compound, the common
P= − (2)
v − bm v(v + bm) + bm (v − bm) vdW mixing rule can not be applicable for such systems.
Further, PR EoS in term of Z-factor is: Herein, PR EoS coupled with HV mixing rules [29] is pro-
posed to predict the Z-factors for the high CO2 content natu-
3
Zm − (1 − B m)Zm2
+ (Am − 2B m − 3Bm
2
)Z m − ral gas with saturated water vapor. The HV mixing rules are
(3)
(Am B m − Bm − Bm ) = 0
2 3 given by:
n
am P bm = xi bi (15)
Am = (4)
R2 T 2  i=1

n
bm P ai αi GE
Bm = (5) am = b m (xi ·
)− (16)
RT bi c0
i=1
And vdW mixing rules can be written as follows:  √ 
1 2+ 2
n n c0 = √ ln √ (17)
am = xi xj (ai aj αi αj )0.5 (1 − kij ) 2 2 2− 2
(6)
i=1 j =1
The value of the excess Gibbs energy at infinite pressure
n is then calculated using the NRTL [37] equation as follows:
bm = xi bi (7) n
i=1
xj Gji Cji
R2Tc2i n
j =1
ai = 0.4572355 (8) G =
E
xi n (18)
Pci
i=1 xk Gki
RTci
bi = 0.0777961 (9) k=1 
Pci Cji
Gji = bj exp −αji · (19)
RT
αi = [1 + (0.37464 + 1.54226ωi − 0.26992ωi )(1 − Tri0.5)]2
2

(10) Cji = gji − gii (20)

The HY EoS [24] can be given as follows: ai
gii = −c0 (21)
  bi
1 + ρr + ρ2r − ρ3r 14.76 9.76 4.58
Z= − − 2 + 3 ρr (bi bj )0.5
(1 − ρr )3 Tpr T Tpr gij = −2 · (gii gjj )0.5 (1 − kij ) (22)
   pr  (11) bi + bj
. 2.82
90.7 242.2 42.4 1 18+ Tpr
+ − + 3 ρr where, kij and αij are empirical binary interaction parameters
Tpr Tpr2 Tpr (BIP) which can be determined by minimizing the following
objective function:
  
Ppr 1 2 1 nc exp
ρr = 0.06125 exp −1.2 × 1 − (12) OF = (x − xcal
i )
2
(23)
ZTpr Tpr nc i=1 i

In this work, HY EoS combined with SBV mixing rule

[28] and WA correction are used to predict the Z-factor of gas 4. Results and discussion
mixtures with and without water content. Details about SBV
mixing rule and WA correction are given in Appendix A. In this study, the following schemes of BIP are given to
The SBWR EoS [22,23] can be expressed as follows: predict the Z-factor of high CO2 content natural gas.
Ppr 1 (1) Neglecting the BIP for all the hydrocarbons compris-
Z= · (13) ing the natural gas.
Tpr ψ
368 Xiaoqiang Bian et al./ Journal of Natural Gas Chemistry Vol. 20 No. 4 2011

(2) Considering the BIP as a constant for both non-
hydrocarbons with hydrocarbons and water with all other
components.
Through the minimization of the objective function
(Equation 23), the results of the BIP are listed in Table 3. For
convenience’s sake, the corresponding mixing rules are also
presented in Table 3. From Table 3, it is important to notice
that HV mixing rules are used only for water with other com-
ponents, whereas vdW mixing rules are available for other
conditions; The αij is not zero only for water with other com-
ponents, while αij is set to zero in other cases.

Table 3. Binary interaction parameters (kij ) and mixing rules for PR EOS
Components H2 O N2 CO2 CH4 C2 H6 C3 H8 n-C4 H10 n-C5 H12 C6 H14
αij H2 O 0.1474 0.0285 0.1444 0.0855 0.0654 0.117 0.1464 0.1449
kij H2 O −0.48 0.0952 0.45 0.45 0.53 0.52 0.50 0.50
N2 HV 0.05 0.05 0.515 0.0852 0.08 0.10 0.08
CO2 HV vdW 0.20 0.20 0.12 0.12 0.12 0.12
CH4 HV vdW vdW 0 0 0 0 0
C2 H6 HV vdW vdW vdW 0 0 0 0
C3 H8 HV vdW vdW vdW vdW 0 0 0
n-C4 H10 HV vdW vdW vdW vdW vdW 0 0
n-C5 H12 HV vdW vdW vdW vdW vdW vdW 0
C6 H14 HV vdW vdW vdW vdW vdW vdW vdW

Figure 4 shows the experimental and calculated Z-factors
for the high CO2 content natural gas with saturated water va-
por or without water system.
For high CO2 content natural gas without water vapor as
for CS-1 and P7, it can be seen from Figure 4 that the predic-
tions of PR EoS are in better agreement with the experimental
data than those of the other models in wide ranges of pressure
conditions, and that the predictions of the SBWR EoS are the
worst one. It is also clear that the predictions of the HY EoS
give a higher accuracy at low pressure (less than 25 MPa) than
at high pressure. Moreover, the PR EoS provides the average
absolute relative deviations (AARD) in the Z-factor of 0.37%
and 0.39% for CS-1 and P7, respectively; while the AARD for
HY EoS are 1.34% and 0.87%, and for SBWR EoS are 3.66%
and 4.35%, respectively.
For the water-saturated natural gas with high CO2 content
for CS-1 and P7, Figure 4 demonstrates that the PR EoS com-
bined with HV mixing rule gives the best results among the
three models, while the SBWR EoS gives the worst one. The
HY EoS give almost the same results for natural gas with and
without water vapor, and only at higher pressure (more than
35 MPa) can the predictions of Z-factor of water-saturated nat-
ural gas be slightly higher than those for natural gas without
water. It is surprising that the calculation results of the SBWR
EoS for high CO2 content natural gas without water vapor are
the same as that for high CO2 content with water-saturated
natural gas. The AARD for PR EoS is 0.40% and 0.42% for
water-saturated CS-1 and P7, respectively; for HY EoS it is
2.60% and 2.12%, and for SBWR EoS it is 4.80% and 5.46%,
respectively.
We assumed that the tiny deviations for PR EoS are due
to the absence of C7+ fraction in the systems, a small amount
of C2 –C6 compositions, as well as appropriate BIP and mix-
ing rules. In addition, with more careful examination on Fig-
ure 4 we find out that the predictions of PR EoS are slightly
underestimated, but the predictions of HY EoS are slightly
overestimated as compared to the experimentally measured
Z-factor at higher pressure (more than 40 MPa). Again, the
predictions of SBWR EoS are the worst for both CS-1 and
P7 gas samples with and without water.
5. Conclusions
In this work, the Z-factor for different CO2 content natu-
ral gases without water vapor has been measured at pressures
range from 7 MPa to 44 MPa and temperatures range from
301.2 K to 407.3 K. Moreover, the Z-factor of high CO2 con-
tent and water-saturated natural gas has also been measured
at temperatures of 400.7 K and 407.3 K. The results show that
the Z-factor decreases with increasing CO2 content in natu-
ral gas at isothermal conditions and increases with increasing
temperature, and that the Z-factor of dry natural gas is higher
than that of water-saturated natural gas.
In addition, the binary interaction parameters for PR EoS
were presented by minimizing the errors between experimen-
tal and calculated data of component mole fraction in the gas
phase.
Furthermore, by the comparison between the experimen-
tal and predicted data, it is indicated that PR EoS combined
with vdW mixing rule can provide the best predictions of the
Z-factor of high CO2 content natural gas without water over
a wide range of pressure and temperature; and that PR EoS
coupled with HV mixing rule can satisfactorily be used for
the calculation of the Z-factor of high CO2 content natural gas
with saturated water, with the overall AARD of 0.38% and
0.41%, respectively. SBWR EoS gives the worst results for
high CO2 -natural gas, with the overall AARD of 4.01% and
5.13% for natural gas without water and with water, respec-
tively. The global AARDs of HY EoS are 1.10% and 2.36%
for natural gas without and with water, respectively.
 Journal of Natural Gas Chemistry Vol. 20 No. 4 2011 369

Nomenclature at infinite pressure

Z compressibility factor of natural gas
References
R gas constant, 8.3147 MPa·cm3 ·mol−1 ·K−1
a energy parameter, MPa·cm6 ·mol−2
[1] Jokhio S A, Tiab D, Escobar F H. SPE 70017, 2001: 1
b volume parameter, cm3 ·mol−1 [2] Shokir E M E M. J Can Petrol Technol, 2008, 47(10): 45
v molar volume, cm3 ·mol−1 [3] Heidaryan E, Moghadasi J, Rahimi M. J Petrol Sci Eng, 2010,
P pressure, MPa 73(1-2): 67
T absolute temperature, K [4] Adisoemarta P S, Frailey S M, Lawal A S. SPE 89466, 2004: 1
[5] Greenwood H J. Am J Sci, 1969, 267A: 191
Tpc pseudocritical temperature, K
[6] Tabasinejad F, Moore R G, Mehta S A, Van Fraassen K C,
T  pc corrected pseudocritical temperature with wichert- Barzin Y, Rushing J A, Newsham K E. SPE 133595, 2010:1
Aziz correlation, K [7] Rushing J A, Newsham K E, Van Fraassen K C. SPE 114518,
Tpc,cor corrected pseudo critical temperature with Casey 2008: 1
correlation, K [8] Elsharkawy A M. Petrol Sci Technol, 2003, 21(11-12): 1759
[9] Firoozabadi A, Stanford U, Nutakki R, Stanford U, Wong T W,
T  pc corrected pseudo critical temperature with Wichert-
Stanford U, Aziz K, Stanford U. SPE Res Eng, 1988, 3(2): 673
Aziz and Casey correlations, K [10] Evelein K A, Moore R G, Heidemann R A. Ind Eng Chem Proc
Tpr pseudoreduced temperature Des Dev, 1976, 15(3): 423
Ppc pseudocritical pressure, MPa [11] Duan Z H, Mφller N, Weare J H. Geochimica et Cosmochimica

P pc corrected pseudocritical pressure with wichert- Acta, 1992, 56(7): 2605
[12] Riazi M R. ASTM Stock Number: MNL 50, West Con-
Aziz correlation, MPa
shohocken, USA, 2005: 215
Ppc,cor corrected pseudo critical pressure with Casey [13] Buxton T S, Campbell J M. SPE J, 1967, 7(1): 80
correlation, MPa [14] Elsharkawy A M. J Can Petrol Technol, 2006, 45(6): 55

P pc corrected pseudocritical pressure with Wichert- [15] Azizi N, Behbahani R, Isazadch M A. J Nat Gas Chem, 2010,
Aziz and Casey correlations, MPa 19(6): 642
[16] Bahadori A, Mokhatab S, Towler B F. J Nat Gas Chem, 2007,
Ppr pseudoreduced pressure
16(4): 349
ρr pseudoreduced density [17] Heidaryan E, Salarabadi A, Moghadasi J. J Nat Gas Chem,
ψ reduced density 2010, 19(2): 189
β, γ, δ reduced parameters [18] Kamyab M, Sampaio J H B, Qanbari F, Eustes A W. J Petrol Sci
ε, φ reduced parameters Eng, 2010, 73(3-4): 248
[19] Al-Anazi B D, Pazuki G R, Nikookar M, Al-Anazi A F. Petrol
nc numbers of components in the gas mixtures
Sci Technol, 2011, 29(4): 325
kij binary interaction parameters for components i [20] Peng D, Robinson D B. Ind Eng Chem Fundam, 1976, 15(1): 59
and j [21] Elsharkawy A M. Fluid Phase Equilib, 2004, 218(1): 1
αij non randomness parameter for binary i-j [22] Soave G S. Ind Eng Chem Res, 1995, 34(11): 3981
interactions [23] Soave G S. Ind Eng Chem Res, 1996, 35(5): 1794
[24] Hall K R, Yaborough J. Oil Gas J, 1973, 71(25): 82
Gji coefficient as defined in Equation (19)
[25] Dranchuk P M, Abou-Kasem J H. J Can Petrol Technol, 1975,
gij energies of interaction between an i-j pair of 14(3): 34
molecules, J·mol−1 [26] Wichert E, Aziz K. Hydrocarb Process, 1972, 51(5): 119
x mole fraction of component [27] Pedersen K S, Fredensland A, Thomassen P. Properties of oils
ω acentric factor and natural gases, Texas: Gulf Pub., 1989. 137
[28] Lee J, Wattenbarger R A. Gas Reservoir Engineering, SPE Text
J SBV parameter, K·MPa−1
Book Series Vol.5, Texas, 1996: 3
K SBV parameter, K·MPa−0.5 [29] Huron M J, Vidal J. Fluid Phase Equilib, 1979, 3(4): 255
A the sum of the mole fractions of CO2 and H2 S [30] SY/T 6434-2000. China National Oil and Gas Industry Stan-
in the gas mixture dards, 2000: 1
B the mole fraction of H2 S in the gas mixture [31] Pedersen K S, Milter J, Rasmussen C P. Fluid Phase Equilib,
2001, 189(1-2): 86
[32] Reid R C, Prausnitz J M, Poling B E. The Properties of Gases
Superscripts or subscripts
and Liquids. 4th eds, New York: McGraw-Hill, 1987. 664
i, j component index [33] Setzmann U, Wagner W. J Phys Chem Ref Data, 1991, 20(6):
r reduced property 1061
c critical property [34] Span R, Wagner W. J Phys Chem Ref Data, 1996, 25(6): 1509
[35] Span R, Lemmon E W, Jacobsen R T, Wagner W, Yokozeki A.
cal calculated value
J Phys Chem Ref Data, 2000, 29(6): 1361
E excess property [36] Wagner W, Pruss A, Wagner W, Yokozeki A. J Phys Chem Ref
Exp experimental value Data, 2002, 31(2): 387
m mixture [37] Renon H, Prausnit J M. AICHE J, 1968, 14(1): 135
370 Xiaoqiang Bian et al./ Journal of Natural Gas Chemistry Vol. 20 No. 4 2011

Appendices
P
Ppr = 
(A13)
Appendix A: Stewart-Burkhardt-Voo mixing rule and Wicher- Ppc
Aziz correction
Appendix B: Soave-Benedict-Webb-Rubin equation of state
The Stewart-Burkhardt-Voo (SBV) mixing rule [28] can
be given as follows: Soave (1995) [22,23] modified the Benedict-Webb-Rubin
   2 noncubic equation of state which can be solved as following
1 nc xi Tci 2 nc 0.5
xi Tci procedure.
J= + (A1)
3 i=1 Pci 3 i=1 Pc0i.5
mi = 1.4ωi (B1)
nc
xi Tci
K= 0.5
(A2) nc nc
Tci Tcj
i=1 Pci S1m = xi xj (1 − kij )  (1 + mi)(1 + mj ) (B2)
i=1 j =1 Pci Pcj
K2
Tpc = (A3)
J
nc nc
Tci Tcj
Tpc S2m = xi xj (1 − kij ) mi mj (B3)
Ppc = (A4) i=1 j =1 Pci Pcj
J
Wichert and Aziz [26] developed a correction to account nc
Tci
for the effects of CO2 and H2 S on the pseudocritical pressure S3m = xi (B4)
i=1 Pci
and temperature. The WA correlation is given as follows:
Critical parameters for gas mixtures can be obtained as below:
5

S1m
ξ= 120(A0.9 − A1.6) + 15(B 0.5 − B 4 ) (A5) Tcm = √ √ (B5)
9 ( S2m + S3m )2
 , and pres-
The corrected pseudocritical temperature, Tpc Tcm

sure, Ppc are Pcm = (B6)
S3m


Tpc = Tpc − ξ (A6) 1 S2m
ωm = (B7)
1.4 S3m

Ppc Tpc

Ppc = (A7) Zcm = 0.2908 − 0.099ωm + 0.04ωm
2
(B8)
Tpc + B(1 − B)ξ
On the basis of WA correlation, Casey (1990) [28] pro- Correlation parameters can be given as follows:
posed a correction to account for the effects of N2 and H2 O T
on the pseudocritical pressure and temperature. The correla- Tpr = (B9)
Tcm
tions are
P
Ppr = (B10)
Tpc,cor = −136.72xN2 + 222.22yH2O (A8) Pcm

ϕ = 0.06 (B11)
Ppc,cor = −1.117xN2 + 8.756yH2O (A9)
ϕ
f= 2
(B12)
 − 126.22x − 647.22x Zcm

Tpc N2 H2 O
Tpc = + Tpc,cor (A10)
1 − xN2 − xH2 O e = 0.5 (B13)

 − 3.40x − 22.06x
Ppc 15Zcm − 8 + (2f 2 − 2f 3) exp(−f )

Ppc =
N2 H2 O
+ Ppc,cor (A11) b= (B14)
1 − xN2 − xH2 O 3

Reduced pressure (Ppr ) and reduced temperature (Tpr ) for

the interest system are calculated using the following correla- 5Zcm − 4 − 3b − (1 + f + f 2 ) exp(−f )
c= (B15)
tions: 2

T
Tpr = (A12)

Tpc d = Zcm − 1 − b − c − e(1 + f ) exp(−f ) (B16)
 Journal of Natural Gas Chemistry Vol. 20 No. 4 2011 371

βc = bZcm (B17)
c2 = 0.00605 + 0.07544ωm − 0.06134ωm
2
(B26)
γc = cZcm
2
(B18)
c3 = 0.00153 + 0.03828ωm + 0.01191ωm
2
(B27)
δc = 4
dZcm (B19)
e1 = 0.1087 + 0.2154ωm − 0.0591ωm
2
(B28)
εc = 2
eZcm (B20)

    e2 = 0.0705 + 0.3007ωm + 0.4948ωm

2
(B29)
1 1
β = βc + 0.422 1 − + 0.2971 1 − ωm
Tpr1.6 Tpr3.2
e3 = −0.0068 + 0.1858ωm − 0.1157ωm
2
(B30)
(B21)
The final equation is
   2  3
1 1 1
γ = γc + c1 − 1 + c2 − 1 + c3 −1 Ppr
Tpr Tpr Tpr ψ[1 + βψ + γψ 2 + δψ 4 + εψ 2 (1 + ϕψ 2) exp(−ϕψ 2 )] =
(B22) Tpr
(B31)
δc
δ= (B23) Ppr 1
Tpr Z= · (B32)
Tpr ψ
   2  3 The above equation can be solved with the Newton-
1 1 1
ε = εc + e 1 − 1 + e2 − 1 + e3 −1 Raphson iteration in which the choice of the starting point is
Tpr Tpr Tpr important. Herein, we choose the starting value using the ideal
(B24) gas reduced density:
where
Ppr
c1 = −0.02663 + 0.06170ωm + 0.00779ωm
2
(B25) ψ= (B33)
Tpr