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1, June 2010
ISSN: 2010-0221
as follow: N N 1 N 2
C T un i =1
*
n (bn cn K n D k n ) D bn exp( c n D k n )
n =13 Where {Uij } is the binary interaction parameter for mixture
Where D is reduced density, B is second virial energy
coefficient, K is mixture size coefficient and {Cn*} are the The above equations have been discussed more in
AGA8/1992 and ISO-12213-2/1997 and can be utilized to
temperature dependent coefficients, While {bn}, {cn} and calculate the natural gas compressibility factor [1],[2]. In this
{kn} are the equation of state parameters given in study, the aim was to calculate the thermodynamics
properties of natural gas mixture such as internal energy and
ISO-12213-2/1997. The gas molar density d and reduced
enthalpy. To calculate the internal energy of the gas mixture,
density D are defined as
the fundamental thermodynamics relation has been the
D = K 3d (3) starting point as follow:
P u u
d= (4) du = dT + dv (15)
ZRT T v v T
The second virial coefficient and the mixture size
According to Maxwell relations the equation (15) can also be
coefficient are calculated using the following equations:
2
expressed as below:
N N 1 N
u
K = X i K i5 / 2 + 2 X i X j ( K ij5 1)( K i K j )5 / 2
5
du = cv dT + dv (16)
i =1 i =1 j = i +1 v T
(5) The equation (16) can be integrated to evaluate the internal
18 N N
energy of natural gas at any position if a reference value is
B = anT un
X X i j
un
E ( Ki K j )
ij
3/ 2
B*
nij (6)
given as follow:
n =1 i =1 j =1
T2 v2 p
*
Where the coefficients {Bnij }, {Eij } and {Gij } are defined by u u ref = c v dT + T p dv (17)
the following formulas:
Tref vref
T v
To be able to evaluate the above integral, the value of
*
Bnij = (Gij +1 gn)gn.(QiQj +1qn )qn (Fi1/ 2Fj1/ 2 +1 fn) fn . P has to be known. Here, the value was derived using
(7)
T v
(Si Sj +1 sn)sn .(WiWj +1 wn)wn
general state equation (1) as below:
E ij = E ij* .( E i E j )1 / 2 (8) p Z .R Z R .T
= + (18)
GiJ* (Gi + G j ) T v v T v v
Gij = (9) Finally, by replacing equation (1) and (18) into equation
2 (17), the following equation could be obtained:
Where T is temperature, N is the total number of gas
T2 v2 R .T 2
Z (19)
mixture components, X i is the molar fraction of the u u ref = Tref
c v dT +
vref
v
dv
T v
component i , {an }, {f n } , {gn} , {qn }, {sn }, {un } and {w n} In which, the first derivative of the compressibility factor
are the equation of state parameters, {Ei }, {Fi }, {Gi }, {Ki }, with respect to temperature ( Z ) is:
T v
{Qi }, {Si } and {Wi } are the corresponding characterization 3
Z D 18 N N
* * = 3 . u n a n T ( u n 1 ) X i X j E iju n ( k i k j ) 2 B n*ij +
parameters while {E } and {G } are the corresponding
ij ij T v k n =1 i =1 j =1
binary interaction parameters. The temperature dependent 18
58
D u n C n*T ( u n 1 ) u n C n*T ( u n 1 ) ( b n c n k n D k n ) D b n
n =13 n =13
coefficients {Cn*, n =1,",58} are defined by the following
exp( c n D k n )
relation: (20)
C n* = a n (G + 1 g n ) g n (Q 2 + 1 q n ) q n ( F + 1 f n ) f n U u n (10) The ideal molar heat capacity C v is also needed in
and the mixture parameters U, G, Q and F are calculated
equation (19) for evaluating internal energy. By knowing the
using the following equations:
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International Journal of Chemical Engineering and Applications, Vol. 1, No. 1, June 2010
ISSN: 2010-0221
calculated as below:
0.9
21 T=333(K)
0.85 T=313(K)
i =1 T=303(K)
Z
T=283(K)
0.7
0 2 4 6 8 10 12
Z
P=9(Mpa)
0.7
P=11MPa
PseudoC6 PseudoC6 0.12 0.5
Internal Energy (J/Kg)
-1
PseudoC10 PseudoC10 0.01
-1.5
PseudoC11 PseudoC11 0.01 260 270 280 290 300 310 320 330 340
Temperature (K)
Figure 3- Effects of temperature and pressure on specific internal energy
5
x 10 Shanol Gas Field
3
1.5
0
gas filed natural gas. As expected, the compressibility factor
decreases as pressure increases and increases as temperature -0.5
1 2 3 4 5 6 7 8 9 10 11
6
Temperature (K)
thermodynamic model has been shown in figure 5. The same
340
system has been simulated and modeled in Farzaneh [12]
when working fluid assumed to be pure methane . For the 320
Methane
thermodynamic system as shown in figure 5, the governing 300
Natural gas
equations are conservation of mass and first law of 280
0 1 2 3 4 5 6 7 8
thermodynamic as:
Time (seconds)
dm e
= m i (23) Figure 6- Variation of NGV cylinder temperature during filling process
dt
du e 25
u e m i + me = m i h0 (24)
Pressure (Mpa)
dt 20
10
is specific enthalpy of reservoir thank and m i is inlet mass 5 Methane
Natural gas
flow rate. In the filling simulation, equations (23) and (24) 0
have been solved numerically to find specific volume and 0 1 2 3 4 5 6 7 8
Time (seconds)
internal energy. Then the developed program was used to
find temperature and pressure of the gas. Farzaneh [12] Figure 7- Variation of NGV cylinder pressure during filling process
utilized methane thermodynamics table to find temperature
and pressure. For more information about the fast filling Figure 7 shows dynamic pressure profiles in NGV cylinder
process and the thermodynamics model which utilized here during filling process for pure methane and natural gas. It can
see Farzaneh [12]. be seen that both profile have similar trends and are in good
agreement. It is worth mentioning that the differences
between the two profiles are expected as the thermodynamic
properties of two working fluids are not the same.
V. CONCLUSION
Given the current surge in the petrochemical and natural
gas businesses, trustworthy estimates of thermodynamic
properties are necessary to design engineering processes.
Accurate prediction of thermodynamics properties for
hydrocarbon fluids is an essential requirement in optimum
design and operation of most process equipment involved in
Figure 5- A schematic diagram of the thermodynamic model petrochemical production, transportation, and processing.
In current study, a computer program has been developed
Here to validate the numerical method of calculating to calculate the thermal properties of natural gas mixture such
thermodynamics properties of the natural gas, a comparison as enthalpy and internal energy in addition of the
has been made between pure methane and natural gas compressibility factor. The method has been applied to a
dynamic properties for filling process of a NGV cylinder. typical Iranian natural gas mixture to calculate the properties
Figure 6 shows dynamic temperature profiles in NGV of the natural gas. To validate the method, the developed
cylinder during filling process for pure methane and natural program has been utilized to model fast filling process of
gas. As shown in Figure 6, in early filling time, the cylinder natural gas vehicle natural gas cylinder. The computed
gas temperature dips significantly, before rising to a final results have been compared with simulation results of same
value. The reason for the dip in temperature profile, in the process in which the pure methane was acted as working
early part of the filling of a nearly empty cylinder is result of fluid. The results show the similar trends and good
the Joule-Thompson cooling effect, which the gas undergoes agreements.
in the isenthalpic expansion through the orifice, from the 205
bar supply pressure to the initially low 1 bar cylinder pressure. VI. ACKNOWLEDGMENTS
This cold gas mixes with and compresses the gas originally in
The authors would like to thank officials in Semnan Gas
the tank, with the result that the combined mixed gas
Company for providing financial support for this research.
temperature initially reduces. It can be seen that the dip for
natural gas profile is higher than for pure methane case. This
shows that the Joule-Thompson effects are higher in natural VII. NOMENCLATURE
gas than pure methane. This behavior is expected for a
Symbol Description units
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International Journal of Chemical Engineering and Applications, Vol. 1, No. 1, June 2010
ISSN: 2010-0221
VIII. REFERENCES
[1] AGA 8, 1992, Compressibility and super compressibility for natural
gas and other hydrocarbon gases, Transmission Measurement
Committee Report No. 8, AGA Catalog No. XQ 1285, Arlington, VA.
[2] ISO-12213-2, 1997, Natural gasCalculation of compression
factorPart 2: Calculation using molar-composition analysis, ISO, Ref.
No. ISO- 12213-2:1997(E).
[3] Estela-Uribe, J.F., Trusler, J.P.E., 2001. Extended corresponding states
equation of state for natural gas systems. Fluid Phase Equilib. 183184,
2129.
[4] Estela-Uribe, J.F., De Mondoza, A., Trusler, J.P.E., 2004. Extended
corresponding states model for fluids and fluid mixtures II. Application
to mixtures and natural gas systems. Fluid Phase Equilib. 216, 5984.
[5] Farzaneh Gord M.,, Moradi K., Mohebbi R., Maghrebi M.J., Hashemi
S., 2008, Simulation of Natural Gas EOS (Equation of State)
Investigation Using PENG-ROBINSON EOS, The first International
conference on Emerging technologies and applications in Engineering,
Technology and Sciences, 13-14 January 2008, Rajkot Gujarat
(India).
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