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Article history: Natural gas engineering entails production, processing, storage and transportation of natural gas. A good
Received 26 November 2013 handling of the gas requires a sophisticated understanding of how its density, compressibility, pseudo-
Received in revised form pressure and specic heat capacity vary with the gas condition. A variety of methods have been pre-
15 April 2014
sented in petroleum and gas journals and a host of scholastic materials to evaluate other properties over
Accepted 17 April 2014
Available online
a wide range of temperatures, however, the available correlation for isobaric specic heat capacity is for
only 150 F. We generated 200 samples of natural gas mixture with methane component ranging from
0.74 to 0.9985 using normally distributed experimental design. The variations of the respective specic
Keywords:
Specic heat capacity
heat capacity of the components and the effect of composition on the specic gravity and overall specic
Isentropic expansion heat capacity of the gas were taken into consideration. The developed correlation reads in the specic
Processing gravity and temperature to generate the ideal gas specic heat capacity of the sample. The result yielded
Storage and transportation system design 99.75% accuracy at 150 F when compared to experimental data, as against the result from isentropic
coefcient method which overestimated the ideal gas specic heat capacity by 25% at the same tem-
perature. The ideal gas specic heat capacity developed compared to 6000 data points generated from
mixing rule at different temperatures resulted in correlation regression coefcient of 0.9999. To account
for the deviation from ideal gas behaviour, this work presents 99.7% R squared value for dimensionless
residual specic heat capacity as a function of reduced temperature and pressure compared to that
calculated from Starling Carnahan equation of state. This model is the rst explicit correlation for the
residual specic heat capacity of natural gas to be derived.
2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jngse.2014.04.011
1875-5100/ 2014 Elsevier B.V. All rights reserved.
L.A. Kareem et al. / Journal of Natural Gas Science and Engineering 19 (2014) 74e83 75
DH nG C v DT (3) Table 1
Constants of the degree three t of Cp as a function of temperature (Cengel and
Boles, 2002).
or
Compounds a b c d
ZT2 Methane (C1) 19.89 5.024 102 1.269 105 11.01 109
DH nG Cv dT (4) Ethane (C2) 6.900 17.27 102 6.406 105 7.285 109
Propane (C3) 4.04 30.48 102 15.72 105 31.74 109
T1 n-Butane (C4) 3.96 37.15 102 18.34 105 35.00 109
i-Butane (C4) 7.913 41.60 102 23.01 105 49.91 109
The expression remains the same except for the isochoric spe- n-Pentane (C5) 6.774 45.43 102 22.46 105 42.29 109
cic heat capacity which replaces its isobaric counterpart. The i-Pentane (C5) 6.774 45.43 102 22.46 105 42.29 109
majority of petroleum and gas journals and textbooks seem to have n-Hexane (C6) 6.938 55.22 102 28.65 105 57.69 109
neglected the necessity of a correlation for specic heat capacity of Heptane (C7) 9.118 73.20 102 37.98 105 76.47 109
Carbon 22.26 5.981 102 3.501 105 7.469 109
natural gas. The only available correlation is for isentropic exponent dioxide (CO2)
k as a function of specic gravity gg at 150 F from which the Nitrogen (N2) 28.90 0.1571 102 0.8081 105 2.873 109
isobaric specic heat can be calculated as follows:
2:738 log gg heat capacities of the two mixtures over a temperature range of
k150 F
; 0:55 < gg < 1 (5)
2:328 50e1550 C as shown in Fig. 1.
But,
3. Methodology
Cp
k (6)
Cv Certain properties, including pseudo-critical temperature and
pseudo-critical pressure, are calculated as the sum of partial
also, pseudo-critical pressures and temperatures of the components of
natural gas sample (Abou-kassem & Dranchuk, 1975; Farzaneh-
Cp Cv R (7)
Gord et al., 2010; George and Brown, 1944). These are elucidated
in the following mathematical expressions:
Where R is the universal gas constant 8134 J/kmol K
X
n
Cp Ppc yi Ppci (9)
k
Cp R i1
1 R X
n
1 Tpc yi Tpci (10)
k Cp
i1
R k1 Moreover, the specic gravity can be expressed in the same way.
For instance, consider:
Cp k
X n Xn
MWgas 1 MWi
so that, gg yi MWi yi
MWair MWair i 1 i1
MWair
kR
Cp (8) Therefore,
k 1
For the fact that Eq. (8) only gives the value of the isobaric X
n
Table 2
Constants of linear regression of ideal gas isobaric specic
heat capacity degree three coefcients against specic
gravity.
Constants Estimate
a1 10.9602
a2 25.9033
b1 2.1517 101
b2 6.8687 102
c1 1.3337 104
c2 8.6387 105
d1 3.1474 108
d2 2.8396 108
Cp 10:9602gg 25:9033 2:1517 101 gg 6:8687
102 T e1:3337 104 gg 8:6387 105 T 2
kJ
3:1474 108 gg 2:8396 108 T 3 ;
kmol K
0:55 < gg < 1 and 100 K < T < 1500 K
(19)
Fig. 1. Comparison of the specic heat capacities of (80% CH4, 20% C2H6) and (90% CH4,
In eld units,
10%C3H8).
specic gravity, because it will carry the information on the mole Cp 8:0211gg 3:3359 2:0744 102 gg 4:2441
fraction of the constituent gases.
The following procedures were applied in carrying out this: 103 T 8:1528 106 gg 4:8536 106 T 2
1:2887 109 gg 1:1626 109 T 3 BTU=lbmol R;
1. Qualitative and quantitative analyses of the natural gas samples
to identify individual constituents and their respective mole 0:55 < gg < 1 and 280 F < T < 2240 F
fractions. (20)
2. Evaluation of specic gravity of the natural gas samples.
3. Evaluation of the coefcients (a, b, c and d) of the degree three t It is important to note that Eq. (19) has been presented in
for the samples using the degree three t coefcients of the graphical form in Fig. 6 and this has made it easier than calculation
constituents and their mole fractions. for a quick estimate.
4. Generation of linear t for the coefcients as a function of
specic gravity of the samples.
5. Combining the results to form the required expression.
3.1. Results
a a1 gg a2 (14)
b b1 gg b2 (15)
c c1 gg c2 (16)
d d1 gg d2 (17)
X
n X
n
a yi ai 18:126; b yi bi 8:3407 102
i0 i0
X
n X
n
c yi ci 7:9480106 ; d yi di 6:1263109
i0 i0
T 150 F 324:33 K
Cp a bT cT 2 dT 3
Cp 18:126 8:3407102 324:33
7:9480106 324:332 6:1263109 324:333
kJ
44:133
kmolK
Therefore,
To test the validity of the result, the Cp obtained at 150 F using
the correlation in Eq. (19) was compared with the result obtained kR 1:17612 8:314 kJ
from Eq. (13) for the test sample shown in Table 3. Cp 55:499
k1 1:17612 1 kmol K
The specic gravity of the sample is evaluated thus:
Substituting 0.708451 for gg and 324.333 K for T in Eq. (19),
therefore:
MWgas 1 X n kJ
gg y MWi 0:708451 Cp 44:242
MWair MWair i 1 i kmol K
This result implies an error of 0.25%.
The constants (a, b, c and d) of the ideal gas isobaric specic heat
capacity are calculated as follows:
Fig. 4. Least square t for specic heat capacity constant c. Fig. 5. Least square t for specic heat capacity constant d.
78 L.A. Kareem et al. / Journal of Natural Gas Science and Engineering 19 (2014) 74e83
Table 3 130
Test sample data.
1400
Compounds Mole fraction 120
Methane (C1) 0.8833
Ethane (C2) 0.0270 110
Propane (C3) 0.0203 1200
n-Butane (C4) 0.0174
i-Butane (C4) 0.0106 100
n-Pentane (C5) 0.0096
1000
Temperature (K)
i-Pentane (C5) 0.0087
90
n-Hexane (C6) 0.0082
Heptane (C7) 0.0068
Carbon dioxide (CO2) 0.0052 80
Nitrogen (N2) 0.0029 800
70
By using the chart in Fig. 6, the specic heat capacity of the ideal 600 60
gas is also estimated as 44 (kJ/kmol K).
50
400
4. Validation of the ideal gas specic heat capacity correlation
40
To validate this correlation, the plot of the ideal isobaric specic 200
heat capacity obtained from the mixing rule shown in Fig. 7 was 30
compared with that obtained from Eq. (19) shown in Fig. 8. In Fig. 9, 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95
a cross plot of isobaric specic heat capacity by mixing and corre- Specific gravity (Air = 1)
lation shows the nearly unit correlation of the regression coef-
Fig. 7. Contour plot of the specic heat capacity by mixture law.
cient. The statistical analyses in Table 4 denote that the standard
deviations of the constants are of 102 order less than the value of
the constant. The narrow 95% condence intervals and the P-values
indicate that the probabilities that these constants could have been
Fig. 6. Specic heat capacity chart as a function of temperature and specic gravity.
L.A. Kareem et al. / Journal of Natural Gas Science and Engineering 19 (2014) 74e83 79
vHreal
Cp; real
vT
vHideal Hresidual
Cp; real
vT
vHideal vHresidual
vT vT
vHresidual
Cp; ideal
vT
vHresidual
Cp; residual
vT
From thermodynamics of residual properties, we know that:
The ratio of the residual specic heat capacity to the molar gas
5. Correction for the effect of pressure constant is the dimensionless residual specic heat capacity.
Using change of variable by putting:
An ideal gas maintains a constant specic heat capacity
regardless of its pressure as long as temperature is constant. But
P Ppc Ppr
natural gas is far from ideal (Abou-kassem & Dranchuk, 1975; Abou-
Kassem and Dranchuk, 1982; Dranchuk and Quon, 1964; Farzaneh- Therefore,
Gord et al., 2010; George and Brown, 1944; Goodwin, 1961; Dran-
chuk et al., 1976; Seifarthi and Joffe, 1952; Weissl and Joffe, 1957;
0 1
ZPpr
Yorizane et al., 1983). Therefore, the deviation is accounted for by Cp; residual v B 2 vZ dPpr C
@T A
the residual specic heat capacity which is the temperature de- R vT vT Ppr
rivative of the residual enthalpy. To obtain the residual specic heat 0
capacity, the widely accepted Hall and Yarborough z factor Performing the derivative, we have:
ZPpr ZPpr 2 !
Cp; residual vZ dPpr 2 v Z dPpr
2T T
R vT Ppr vT 2 Ppr
0 0
T Tpc Tpr
Therefore,
ZPpr ZPpr !
Cp; residual vZ dPpr 2 v2 Z dPpr
2Tpr Tpr (21)
R vTpr Ppr vTpr
2 Ppr
0 0
APpr
z
y
2
Fig. 9. Cross plot of the mixture Cp against the correlation Cp for an ideal gas. where A 0:06125te1:21t and y is the root of:
80 L.A. Kareem et al. / Journal of Natural Gas Science and Engineering 19 (2014) 74e83
Table 4
Statistical parameters of the constants of correlation of the ideal gas isobaric specic heat capacity.
Ppc 10.960 1.516 101 {11.259, 10.661} 72.289 8.849 10144 0.9637
a2 25.903 1.123 101 {25.681, 26.125} 230.617 1.294 10241
b1 2.151 101 7.779 104 {2.136 101, 2.167 101} 276.144 5.567 10257 0.9974
b2 6.869 102 5.772 104 {6.983 102, 6.755 102} 118.991 1.970 10185
c1 1.333 104 5.033 107 {1.344 104, 1.324 104} 264.539 2.564 10253 0.9972
c2 8.639 105 3.727 107 {8.565 105, 8.712 105} 231.286 7.329 10242
d1 3.147 108 1.343 1010 {3.121 108, 3.174 108} 234.249 6.028 10243 0.9964
d2 2.839 108 9.953 1011 {2.859 108, 2.820 108} 285.275 9.315 10260
dA 2 2
y y2 y3 y4 0:06125e1:21t 0:147t1 te1:21t
APpr By2 CyD 0 (22) dt
1 y3
dB
14:76 19:52t 13:74t 2 ;
where dt
dC dD
B 14:76t 9:76t 2 4:58t 3 ; C 90:7t 242:2t 2 42:4t 3 ; 90:7 484:4t 127:2t 2 ; 2:82
dt dt
D 2:18 2:82t
Tpc 3. Using the values of y and vy/vt from Eqs. (24) and (25), v2y/vt2 is
t
T computed from:
ZPpr !
Cp; residual v2 Z dPpr
t 2 d2 A d2 B 2 d2 C D d2 D D dC dD D
R vt 2 Ppr P y 2 y 2 Cy ln y 2 y ln y
0 pr
dt 2 dt 2 dt dt dt dt
2
We have: dD dB dC D1
ln y CyD 2 2 y Dy
! dt dt dt
"
vZ dA y
dt
A vy
vt dD D1 vy 8 20y 4y2
Ppr Cy D ln y 1
vt y2 vt
dt 1 y5
0 #
2 2 1 vy 2
vy
y A vvt2y 2 dA vy
2
d Ay2 2A 2B CDD 1yD2
2
v Z B dt 2 vt dt vt C vt
B
@
CPpr
A " #
vt 2 y3 2
1 4y 4y2 4y3 y4 D1 v y
2By CDy 0
1 y4 vt 2
Hence,
0 (26)
2 2 1
d Ay2 2A vy y A vvt y2 2 dA vy
2
ZPpr
Cp; residual B dt 2 vt dt vt C
t 2 B CdPpr d2 A
R @ y3 A 2
0:2941 te1:21t 0:147t1 te1:21t
2
0 dt 2
2
2 3
2 6
a1 ea2 1t Ppr t a3 Ppr t 7
7
2 3 3 5;
dA dB dC dD D a7 a6 Ppr t a5 Ppr t a4 Ppr t
Ppr y2 yD Cy ln y
dt " dt dt dt # 1:2 Tpr 3 and 0:01 Ppr 15
1 4y 4y2 4y3 y4 D1 vy
2By CDy 0 (27)
1 y4 vt
(25) where
L.A. Kareem et al. / Journal of Natural Gas Science and Engineering 19 (2014) 74e83 81
The values for the constants in Eq. (27) are contained in Table 6. 6.2. Example 2
The excellent performance of Eq. (27) is reected in the comparison
of its result to that of Sterling Carnahan as indicated by 99.9% cor- To calculate the amount of heat to be extracted from a 0.6
relation of regression coefcient (Table 7). gravity natural gas at 5000 psi in order to bring its temperature
The specic heat capacity of natural gas can thus be written as: down from 600 F to 200 F.
In order to demonstrate how the model can be applied, the ZT2 "
following examples are provided. Please note that the solutions to 50 X
4
DH Cp; real dT 10:6121 4 Cp; real 2i
Example 1 are provided after each problem, while the solution to 3
i2
T1
Example 2 is provided in subsection 6.2.1. #
X
3
2 Cp; real 2i 1 18:0886
6.1. Example 1
i1
Table 6
Statistical parameters of the constants of correlation of the residual isobaric specic heat capacity.
7. Conclusions with those obtained from natural gas enthalpy chat (George and
Brown, 1944) and can be used in the design of gas transportation
A robust correlation for isobaric specic heat capacity has been system or any other application where the isobaric specic heat
developed. This correlation is in two parts. The rst is the ideal gas capacity of natural gas is a requirement.
isobaric specic heat capacity given by Eqs. (19) and (20). The
second part is the residual of the isobaric specic heat capacity
given by Eq. (27). Eq. (19) has a correlation of regression of 0.9999
and a maximum relative error of 0.04. It is applicable to samples
with specic gravity in the range of [0.55, 1.0] and temperature in
the range of [100, 1500] K. Eq. (27) has a regression coefcient of
0.997 and maximum relative error of 0.05 compared to the Starling
Carnahan equation of state. It is applicable when the pseudo
reduced pressure and temperature fall within [0.01, 15] and [1.1, 3],
respectively. An exhaustive regression analysis of the constants of
the correlations developed was also conducted. The P-values
(max 0.022628) and 95% condence interval show that the
probability that these constants could have been derived by chance
is negligible. This correlation gives results in excellent agreement
Table 7
Result of statistical analysis of least square t for the residual specic heat
capacity.
References
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Nomenclature
Weissl, A., Joffe, J., 1957. Generalized correlation for effect of pressure on isobaric
heat capacity of gases. J. Ind. Eng. Chem. 49 (1), 120e124 http://dx.doi.org/
a Constant of degree 3 t for Cp (kJ/kmol K) 10.1021/ie50565a039.
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Most Information from Experiments, second ed. Springer.
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d constant of degree 3 t for Cp (kJ/Kmol4 K) Pure Gases at High Pressures by Use of a Coaxial Cylindrical Cell, pp. 454e458.