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Thermodynamic Analysis of Co2 Reforming of Methane in View of Solid Carbon Formation
Thermodynamic Analysis of Co2 Reforming of Methane in View of Solid Carbon Formation
Thermodynamic Analysis of Co2 Reforming of Methane in View of Solid Carbon Formation
Chemical Reaction Engineering Group (CREG), Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia
Dept of Catalyst and Process, R&D of Bandar Imam Petrochemical Complex (BIPC), Mahshahr, Iran
a r t i c l e
i n f o
Article history:
Received 23 July 2010
Received in revised form 16 November 2010
Accepted 26 November 2010
Available online 30 December 2010
Keywords:
Thermodynamic equilibrium
Gibbs free energy
Reforming
Carbon formation
Methane
Carbon dioxide
a b s t r a c t
A thermodynamic equilibrium analysis on the multi-reaction system for carbon dioxide reforming of methane
in view of carbon formation was performed with Aspen plus based on direct minimization of Gibbs
free energy method. The effects of CO2/CH4 ratio (0.53), reaction temperature (5731473 K) and pressure
(125 atm) on equilibrium conversions, product compositions and solid carbon were studied. Numerical
analysis revealed that the optimal working conditions for syngas production in FischerTropsch synthesis were at
temperatures higher than 1173 K for CO2/CH4 ratio being 1 at which about 4 mol of syngas (H2/CO = 1) could be
produced from 2 mol of reactants with negligible amount of carbon formation. Although temperatures above
973 K had suppressed the carbon formation, the moles of water formed increased especially at higher CO2/CH4
ratios (being 2 and 3). The increment could be attributed to RWGS reaction attested by the enhanced number of
CO moles, declined H2 moles and gradual increment of CO2 conversion. The simulated reactant conversions and
product distribution were compared with experimental results in the literatures to study the differences between
the real behavior and thermodynamic equilibrium prole of CO2 reforming of methane. The potential of
producing decent yields of ethylene, ethane, methanol and dimethyl ether seemed to depend on active and
selective catalysts. Higher pressures suppressed the effect of temperature on reactant conversion, augmented
carbon deposition and decreased CO and H2 production due to methane decomposition and CO disproportionation reactions. Analysis of oxidative CO2 reforming of methane with equal amount of CH4 and CO2 revealed
reactant conversions and syngas yields above 90% corresponded to the optimal operating temperature and feed
ratio of 1073 K and CO2:CH4:O2 = 1:1:0.1, respectively. The H2/CO ratio was maintained at unity while water
formation was minimized and solid carbon eliminated.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Numerous efforts are being directed at limiting CO2 and CH4
emissions to halt global green-house warming. Utilization of landll
gas (LFG) and a CO2-rich fossil natural gas (NG) to produce highervalue added chemicals seems promising to reduce green house
effects, since CH4 and CO2 are the predominant constituents in both
LFG and fossil natural gas. The CO2/CH4 ratio in LFG varies widely
depending on the type of waste, age of landll and its extraction
systems. Landll gas commonly consists of 4070% CH4 and 3060%
CO2. Similarly the compositions of fossil NG vary from one eld to
another. For example, the CO2/CH4 ratio for NG in Natuna's eld
(located in the South China Sea) [1] and zone D of the Dalan Formation
(located in south of Iran) are 71/28 and 85/2.5 [2], respectively.
However, only several industrial processes involving CO2 as reactant
gas have been developed due to the inert and stable characteristics of
Corresponding author. Tel.: +60 7 553 5579; fax: +60 7 5581463.
E-mail addresses: m_k_nikoo@yahoo.com (M.K. Nikoo), noraishah@fkkksa.utm.my
(N.A.S. Amin).
0378-3820/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2010.11.027
Nomenclature
aik
Ak
g
fi
s
fi
fis
fig
tg
G(T,
P)
ts
G(T,
P)
g
Gl
Gsl
Gs
c
Gg
i
Gs
i
t
G(T,
P)
g
Gi, e
GgC
GSC
g
Gfi
GS
fC
Gr
ni
N
P
P
R
T
yi
Greek Symbol
k
Lagrange multiplier
Si
Chemical potential of species i in a solid phase
gi
Chemical potential of species i in a gas phase
CS
Chemical potential of carbon in a gas phase
usc
Chemical potential of carbon in a solid phase
yi
Stoichiometric coefcient of species i
i
Superscript
G
Gas phase
S
Solid phase
T
Total
Subscript
i
Component in the mixture
k
Element in each molecule
679
680
-g
GT; P = i = 1 ni Ggl = i = 1 ni i = i = 1 ni Gi
-g
N
g
+ RTi = 1 ni ln f i = fi
tg
ts
-s
GT;P = i = 1 ni Gsl = i = 1 ni i = i = 1 ni Gi
-s
N
s
+ RTi = 1 ni ln f i = fi :
-g
g
=
Gi +
ln fi = fi
-s
-s
N
N
s
+ i = 1 ni Gi + RTi = 1 ni ln fi = fi :
N
i = 1 ni
-g
N
RTi1 ni
Since the standard state is dened as the pure ideal gas state at
1 atm, fig = P = 1 atm and since Gi,ge equals to zero for each element
g
in its standard state; hence, Gg
i = G [33]. Meanwhile, the solid
phase is assumed as a pure solid carbon. As the reference state for the
solid phase is at atmospheric pressure and 25 C, the partial fugacity
can be written as shown in Eq. (4):
-s
f i = fi :
s
-s
-s
g
g
By substituting fi = yi
i P; fi = P = 1 and Gi = G in Eq. (1)
and using the Lagrange multiplier method, the Gibbs free energy
minimization of gaseous species can be expressed as Eq. (6):
g
fi
fig = P = 1,
= yi i P,
In the same manner, by substituting
-g
Gg
i = G and Eq. (5) into Eq. (3) the Gibbs free energy minimization with considering solid carbon can be expressed as Eq. (7):
N
i P
-g
y i
+ aik k + nC GfC S = 0: 7
ni Gfi + RT ln
i=1
P-
The above equations (Eqs. (6) and (7)) along with the constraint
shown in Eq. (8) are simultaneously solved to obtain the equilibrium
composition of the reaction system.
i ni aik = Ak
10
i P
-g
y i
Gfi + RT ln
+ aik k = 0:
P-
Gr = i Gfi :
Table 1
Reactions in CO2 reforming of methane.
Reaction number
Reaction
H298 (kJ/mol)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
247
41
106
284
136
90.6
49.1
74.9
172.4
90
131.3
258.4
136
204.8
37
165
206.2
681
682
Table 2
Reactant conversions (X) and product yield (Y) for CO2 reforming of methane with CO2/CH4 ratio of 1 at atmospheric pressure.
Temperature (K)
XExpCH4 (%)
XEqCH4 (%)
XExpCO2 (%)
XEqCO2 (%)
YExpH2 (%)
YEqH2 (%)
YExpCO (%)
773
52.5a
71a
20.4b
81.9a
40.6b
90.7a
58b
95.4a
72.4b
97.9a
82.6b
100a
85.1b
70.9
37.1b
59.1b
78.4b
91.7b
95.7b
96.5b
45.9
47a
64a
78.8a
87.7a
91.1a
91.5a
92.8a
28.5
31.1a
45.3a
61.6a
75.6a
80.6a
83.2a
84.4a
823
873
923
973
1023
1073
76.6
82.3
87.4
91.5
94.4
96.3
44.8
47.2
54.5
66.3
79.1
88.6
40.1
52.5
64.9
75.9
84.6
90.6
YEqCO (%)
3.5
8.3
17.4
31.9
50.8
69.3
82.9
H2/COExp
H2/COEq
1.5a
1.4a
0.41b
1.28a
0.49b
1.16a
0.55b
1.13a
0.6b
1.1a
0.63b
1.1a
0.65b
8.1
4.8
3
2
1.5
1.2
1.1
Exp and Eq are representatives of experimental data by the other researchers and equilibrium values calculated in our work, respectively.
a
The values are corresponding to Sr0.8La0.2Ni0.3Al0.7O2.6 taken from a research by Khalesi et al. [38].
b
The values are corresponding to Pt/Na(0.3 wt.%)Al2O3 taken from a research by E. L. Jablonski et al. [39].
683
684
Fig. 6. H2/CO ratio as a function of temperature (573823 K) and CO2/CH4 ratio at 1 atm
for n (CH4 + CO2) = 2 mol.
Fig. 7. Moles of carbon as a function of temperature and CO2/CH4 ratio at 1 atm for
n (CH4 + CO2) = 2 mol.
685
which is not plausible when CO2 is the limiting reactant, just as was
discussed for carbon formation. Increasing CO2/CH4 ratio ( N1) at
specied temperature (b973 K) causes a decrease of water formation
since fewer hydrogen atoms would be available to form water and
even H2 as CH4 is the limiting reactant. This can be corroborated by
Fig. 4 where H2 production decreases at CO2/CH4 ratios larger than 1
at the identical temperatures.
Raising the CO2/CH4 ratio from 0.5 to 3 increases the moles of
water at higher temperature (N1000 K). It is in good agreement with
the results of equilibrium composition of water that did not consider
solid carbon irrespective of the amount of water formed [14,43]. The
moles of water formed considering carbon deposition exceeded the
equilibrium ones when carbon formation was not taken into account
due to participation of CH4 decomposition, carbon monoxide and
carbon dioxide hydrogenation reactions associated with solid carbon
and water production while carbon deposition is considered. From
Fig. 8, the increasing number of moles of water at CO2/CH4 ratios being
2 and 3 within the temperature range of higher than 9731023 K
(depending on the reactant molar ratios) is reasonably owed to RWGS
reaction (reaction 2) which is conrmed by enhanced moles of CO,
declined moles of H2 and smooth increase of CO2 conversion. These
outcomes are compatible with preceding research regardless of a little
difference in the value of the temperature at which water formation
increased [14,44]. However, exploiting Ir/CGO catalyst in CO2
reforming of methane reduced water production at higher than
700800 C depending on the CO2/CH4 ratios due to improving
preferable reaction between water formed and methane (steam
reforming of methane) which lowered water concentration [41].
Fig. 8. Moles of water as a function of temperature and CO2/CH4 ratio at 1 atm for
n (CH4 + CO2) = 2 mol.
Fig. 9. Moles of C2H6 as a function of temperature and CO2/CH4 ratio at 1 atm for
n (CH4 + CO2) = 2 mol.
686
Fig. 10. Moles of C2H4 as a function of temperature and CO2/CH4 ratio at 1 atm for
n (CH4 + CO2) = 2 mol.
From Fig. 10, two different trends for C2H4 formation are observed
depending on the reactant molar ratio. When CO2/CH4 ratio b1, the
number of moles of C2H4 increases with increasing temperature. This
result resembles that of previous work [14] regardless of the values for
C2H4 formed. In this case, considering CO2 as the limiting reactant,
there are sufcient H atoms available from CH4 that can contribute in
the reactions leading to C2H4 production. Moreover, moles of C2H4
increases with a swift incline owing to reaction 5 which multiplies
C2H4 formation. From Fig. 10, a considerable increase of moles of C2H4
is exhibited relative to that of C2H6 (see Fig. 9) at temperatures higher
than 1073 K due to the higher equilibrium constant in reaction 4
compared to reaction 3 (see Fig. 1).
From Fig. 10 the trends for CO2/CH4 ratios being 2 and 3, are similar
to those for CO2/CH4 ratio b1, except at a temperature above
923973 K (depending on the reactant molar ratio) at which the
number of moles of C2H4 decreases. The decreasing trend of C2H4 for
CO2/CH4 ratios being 2 and 3 reveals that there is a relation between
reaction temperature and contribution of H atom from methane at
equilibrium system leading to a notable effect on C2H4 formation
[14]. As a result, temperatures lower than 1073 K and CO2/CH4 ratios
below 1 is more in favor of C2H6 production than C2H4 although
temperatures above 1073 K and similar CO2/CH4 ratio are more
favorable to C2H4 production as the predominant product relative to
C2H6. As CO2/CH4 ratio b1 produces a large amount of carbon (see
Fig. 7) which causes clogging in the reactor, CO2/CH4 ratio of 1 and
temperature of 1273 K are suggested for C2H4 production at which
carbon deposition is negligible. Meanwhile, due to production of the
large amount of solid carbon at CO2/CH4 ratio b1, it seems CO2/CH4
ratio of about 2 and temperature of about 1000 K is suitable for higher
C2H6 production while eliminating solid carbon. Since the number of
moles of C2H6 and C2H4 formed are very low, an active and selective
catalyst with decreasing operational temperature is strongly necessary. The catalysts performance using CaO/MnO/CeO2 to produce C2
(ethylene and ethane) has shown the optimal factors of CO2/CH4 ratio
and reactor temperature at 2 and 1127 K, respectively, corresponding
to maximum CH4 conversion of 5.1% and C2 hydrocarbons yield of 3.9%
[52]. However, the value of equilibrium CH4 conversion is 99.5%, while
an only negligible amount of C2 equilibrium yield is calculated. These
large differences from the thermodynamic equilibrium values arise
from the synergistic effect between the catalyst basicity and
reducibility, enhancing the activity towards CO2 OCM (reactions 3
and 4) [52,53]. Some preceding researches for C2 production from
CO2 reforming of methane over different metal oxide catalysts such
Fig. 11. Moles of methanol as a function of temperature and CO2/CH4 ratio at 1 atm for
n (CH4 + CO2) = 2 mol.
Fig. 12. Moles of DME as a function of temperature and CO2/CH4 ratio at 1 atm for
n (CH4 + CO2) = 2 mol.
687
Fig. 13. The effect of pressure on a) equilibrium conversion of reactants and products
distribution for CO2/CH4 = 1, 1173 K and n (CH4 + CO2) = 2 mol and on b) carbon
deposition as a function of temperature.
previous work [14], H2/CO ratio was less than 1. This contradict
mainly arises from methane decomposition (reaction 8) which assists
CO2 reforming of CH4 to produce the higher amount of H2. These
equilibrium data are compatible with the thermodynamic equilibrium
calculations by S-W. Hong et al. [40].
Fig. 13b shows the effect of pressure on carbon deposition at
variable temperatures during CO2 reforming of CH4. The moles of solid
carbon go up with increasing pressure to attain the maximum. Shamsi
and Johnson [45], performing thermodynamic calculations on the CO
disproportionation and methane decomposition (as the two major
reactions of carbon formation) showed that the carbon deposited by
methane decomposition decreased with increasing the pressure,
while increased by CO disproportionation. These results suggest that
disproportionation reaction is the most favorable contributor to
carbon formation at a higher pressure, particularly when the CO2/CH4
ratio is higher than 1. Meanwhile, due to disproportionation reaction,
CO decreases with a steeper incline than H2 when increasing the
pressure. On the contrary, as said before methane decomposition is a
favorable reaction when CO2 is a limiting reactant (CO2/CH4 b1).
688
Name of reaction
Reaction formulae
H 298 (kJ/mol)
1
2
3
36
802
110
689
Fig. 14. Equilibrium conversion of reactants and product distribution as a function of temperature and O2/CH4 ratio at 1 atm and CO2/CH4 = 1 for n (CH4 + CO2 + O2) = 2 mol: (a) CH4
conversions; (b) CO2 conversions; (c) moles of H2; (d) moles of CO; (e) moles of water; and (f) H2/CO ratios.
690
Fig. 15. Moles of solid carbon as a function of temperature for different O2/CH4 ratios at
1 atm and n (CH4 + CO2 + O2) = 2 mol.
691
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