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State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, 100029 Beijing, China
Beijing Engineering Research Center of Low Metamorphic Coal and Organic Wasters Pyrolysis Upgrading, Beijing Shenwu Environment & Energy
Technology Co., Ltd., 102200 Beijing, China
b
a r t i c l e
i n f o
Article history:
Received 18 October 2015
Received in revised form 20 April 2016
Accepted 23 April 2016
Available online 30 April 2016
Keywords:
Numerical simulation
Computational uid dynamics
Oxidative coupling of methane
Two-stage reactor
Beds-interspace distributed dioxygen
feeding
a b s t r a c t
A three-dimensional geometry model of the particle/monolithic two-stage reactor with beds-interspace
distributed dioxygen feeding for oxidative coupling of methane (OCM) was set up. The improved Stansch
kinetic model adapting different operating temperatures was established to calculate the OCM reactor
performance using computational uid dynamics (CFD) and FLUENT software. The results showed that
the calculated values matched well with the experimental values of the conversion of CH4 and the selectivity of products (C2 H6 , C2 H4 , CO2 , CO) in the OCM reactor. The distributed dioxygen feeding with the
percentage of 520% based oxygen ow rate of top inlet promoted the OCM reaction in monolithic catalyst bed and led to the conversion of CH4 and the selectivity and yield of C2 (C2 H6 and C2 H4 ) increase
obviously. The distributed dioxygen feeding was 15%, the conversion of CH4 , the selectivity and the yield
of C2 reached 34.1%, 68.2% and 23.3%, respectively.
2016 Elsevier Ltd. All rights reserved.
1. Introduction
Methane is the predominant compound of natural gas. During
the past decades, there has been a worldwide interest in the conversion of methane to high value chemical products by two way:
the direct methods and the indirect methods (Lunsford, 2000). The
direct methods are more concise because they avoid the syngas
step. Oxidative coupling of methane (OCM) is regarded as a promising direct way for methane conversion (Gesser and Hunter, 1998).
Many efcient metal catalysts were developed and can be found
from review paper (Khammona et al., 2012). Among these catalysts,
Na2 WO4 -Mn/SiO2 particle was synthesized by Li and his coworkers (Fang et al., 1992; Jiang et al., 1992), and it is believed to be one
of the most promising catalysts for commercialization because of
its excellent catalytic performance. Unfortunately, there are some
other obstacles of OCM commercialization except catalyst. One of
the main obstacles is that OCM reaction is highly exothermic and
hot spots are easily formed in reactor (Pak and Lunsford, 1998;
Schweer et al., 1994; Taniewski et al., 1997). The hot spot may lead
to temperature runaway, catalyst deactivation and even thermal
Corresponding author.
E-mail address: jisf@mail.buct.edu.cn (S. Ji).
http://dx.doi.org/10.1016/j.compchemeng.2016.04.036
0098-1354/ 2016 Elsevier Ltd. All rights reserved.
cracking of the main products (Talebizadeh et al., 2009). The alteration of contact mode between reactant and catalyst is a way to
inhibit the formation of hot spots and improve the selectivity of
main products (H. Liu, Wang et al., 2008; Talebizadeh et al., 2009;
Taniewski et al., 1997).
Monolithic catalyst can change the contact mode and has lower
pressure drop and more excellent ability of mass and heat transfer than the traditional particle catalyst (Groppi et al., 2001). The
monolithic catalyst for OCM reaction can effectively depress hot
spot and improve the selectivity of target products reported by
Liu et al. (2008a, 2008b) and Tang et al. (2009). However, channels of monolithic catalyst are relatively short. It leads to a low
methane conversion and low yields of individual target products.
It is favorable to construct a two-stage reactor for OCM reaction
by combination of particle and monolithic catalysts together based
on their advantages and disadvantages. Pan et al. (2010) and Wang
et al. (2011) studied OCM reaction in a two-stage reactor loaded
with both particle and monolithic catalysts. When raw gas rstly
goes through the particle catalyst bed of the reactor with suitable
particle and monolithic bed heights, C2 yield reaches its maximum
value of 23.6%. Wang et al. (2011) also found that the OCM reaction
is restrained by the low partial pressure of O2 in monolithic catalyst bed since the raw gases rst react in the particle catalyst bed.
Therefore, a supplementary O2 is necessary between two catalyst
248
Nomenclature
Ea,j
Had,CO2
HO2
k0,j
Kj,CO2
KO2
mj , nj
T
r
R
beds to improve the reactor performance (Ji and Wang, 2012). After
a series of researches, they improved the C2 yield to 24.3% when the
ow rate of supplementary O2 was 15% of the inlet O2 ow rate.
Experimental research involves many disadvantages for reactor scaling up and commercialization, such as high cost and long
research period. The traditional models of OCM xed bed include
1D models (Hoebink et al., 1994; Tye et al., 2002) and 2D models
(Holst et al., 2012), which omit the inuence of three-dimensional
ow eld on heat transfer and chemical reaction. Great errors may
occur during the scaling up of the reactor. Computational uid
dynamics (CFD) is a simulation method based on ow eld analysis. It can accurately predict the impact of three-dimensional ow
eld on reactor performance. In recent years, with the improvement of the CFD software and computer hardware, CFD is greatly
used in chemical industry domain (Galletti et al., 2013; Hassan et al.,
2013; Khoshhal et al., 2011; Zhang et al., 2008), particularly in complex chemical reactors (Mishra and Verma, 2012; Rudniak et al.,
2004; Yu et al., 2015; Yu et al., 2014) and heat exchange equipment
(Aslam Bhutta et al., 2012; Hung et al., 2015; Khoshvaght-Aliabadi
et al., 2015; Yaci et al., 2014). It guides laboratory reactor scaling
up, plant reactor design and operating optimization (Khan et al.,
2014; Philippsen et al., 2014) with low cost and short research
period. Experiment and the traditional simulation do not have such
advantages.
CFD can also be applied to the simulation of catalytic reactor,
such as Gtz (Gtz et al., 2015) simulate TEMKIN xed bed reactor for hydrogenation of acetylene. The results show that reaction
can be promoted through optimization of ow eld. Then, the reactor performance can be improved effectively. Besides, CFD method
is used to simulate catalytic packed bed reactors for methane
(Hong et al., 2013; Palma et al., 2014; Rowshanzamir et al., 2012;
Wehinger et al., 2015) and dimethyl ether (Yan et al., 2014) reforming and catalytic uidized bed reactor (Liu and Xiao, 2015; Pepiot
and Desjardins, 2012; Solsvik et al., 2014; Yan et al., 2011). The
CFD method has been successfully applied to predict the reaction performance of a packed bed reactor loaded with SnBaTiO3
catalyst (Nakisa and Reza, 2008, 2009) and a two-stage reactor
loaded with different amount of Na2 WO4 -Mn/SiO2 particle catalyst
and Na3 PO4 -Mn/SiO2 /cordierite monolithic catalyst at constant
temperature for OCM. It is also applied to optimizing the operation parameters of OCM reactor loaded with La2 O3 /CaO catalyst
(Eppinger et al., 2014).
In previous work, we had simulated the reactor lled with
Na2 WO4 -Mn/SiO2 particle catalyst (Zhang et al., 2015b) and
Na3 PO4 -Mn/SiO2 /cordierite monolithic catalyst (Zhang et al.,
2015a), respectively, and also the two-stage reactor lled
with both Na2 WO4 -Mn/SiO2 particle catalyst and Na3 PO4 Mn/SiO2 /cordierite monolithic catalyst. The effect of catalyst
heights in two-stage reactor at temperature of 800 C was investi-
Fig. 1. Sketch (a), meshes and geometric model (b, c) of packed bed reactor of
monolithic catalyst.
249
Table 1
Reaction equations and reaction rate equations of Stansch kinetic model.
No.
Reaction equation
r1 =
k0,1 e
Ea,1 /RT m1 n1
P
P
CH4 O2
1+K1,CO e
2
2CH4 + 0.5O2 = C2 H6 + H2 O
r2 =
1+
CH4 + O2 = CO + H2 O + H2
r3 =
k0,2 e
KO e
2
k0,3 e
CO + 0.5O2 = CO2
r4 =
C2 H6 + 0.5O2 = C2 H4 + H2 O
r5 =
1+K3,CO e
r6 =
1+K4,CO e
C2 H6 = C2 H4 + H2
CO + H2 O = CO2 + H2
10
CO2 + O2 = CO + H2 O
KO e
2
PO
Had,O /RT
2
n2
Had,CO /RT
2
PCO
Had,CO /RT
2
PCO
1+K5,CO e
Had,CO /RT
2
PCO
Had,CO /RT
2
PCO
n2
PO
m
P 2
2
CH4
Had,CO /RT
2
PCO
n3
2
n4
2
n5
2
E
/RT m6 n6
k0,6 e a,6
P
P
CO O2
1+K6,CO e
+K2,CO e
2
n
E
/RT m5
k0,5 e a,5
P
P 5
C2 H6 O2
n1
2
E
/RT m4 n4
k0,4 e a,4
P
P
CO O2
PCO
Ea,3 /RT m3 n3
P
P
CH4 O2
Ea,2 /RT
Had,O /RT
2
Had,CO /RT
2
n6
2
2 6
m9 n9
r9 = k0,9 eEa,9 /RT PCO
PH O
r10 = k0,10 e
Ea,10 /RT
m10 n10
PCO
P
2 H2
250
Table 2
Kinetic parameters for Na2 WO4 -Mn/SiO2 particle catalyst at 775825 C.
1
2
3
4
5
6
7
8
9
10
Kj,CO2 (Pa1 )
4.91E-29
6.20E-06
1.60E-08
3.43E + 09
1.73E-09
8.57E-08
6.00E + 05
1.86E + 05
9.50E-05
2.60E-02
392
62
68
404
17
106
226
300
173
220
2.50E-13
3.36E-10
1.66E-02
2.00E-11
1.62E-08
1.60E-13
175
126
53
168
126
211
KO2 (Pa1 )
1.15E-11
124
KO2 (Pa1 )
mj
nj
0.24
1.00
0.57
1.00
0.95
1.00
0.00
0.97
1.00
1.00
0.76
1.00
0.85
0.20
0.74
0.96
0.00
0.00
1.00
1.00
mj
nj
0.24
1.00
0.57
1.00
0.95
1.00
0.00
0.97
1.00
1.00
0.76
1.00
0.85
0.20
0.74
0.96
0.00
0.00
1.00
1.00
Table 3
Kinetic parameters for Na3 PO4 -Mn/SiO2 /cordierite monolithic catalyst at 775825 C.
1
2
3
4
5
6
7
8
9
10
Kj,CO2 (Pa1 )
2.62E-30
1.74E-04
2.41E-10
2.75E + 08
2.51E-10
8.57E-09
6.00E + 04
1.86E + 04
1.90E-06
1.30E-03
392
62
68
404
17
106
226
300
173
220
2.50E-13
3.36E-10
1.66E-02
2.00E-11
1.62E-08
1.60E-13
175
126
53
168
126
211
and 20 percent of oxygen ow rate at reactor top inlet, respectively. Then, the inuence of temperature on two-stage reactor
performance was investigated when the ow rate of supplementary oxygen was 3 ml/min.
In view of the symmetry of catalyst beds, we intercepted a plane
passing through the symmetry axis of the catalyst beds which
was intercepted and the parameters (such as the mass fraction
of reactants and products) contours on this plane was shown. We
also investigated the reaction performance of the two-stage reactor according to the simulation results. The plane was marked as
P1 in this article. The CFD model was validated by experimental
data in operating condition of supplementary oxygen ow rate
from 1 ml/min to 4 ml/min and temperature at 775 C 825 C.
The difference between simulation data and experimental data (Ji
and Wang, 2012) was shown in Tables S2 and S3 of Supplementary material. From Tables S2 and S3, All parameters, such as CH4
conversion and the selectivity of main products and byproducts,
relative error of simulated values to experimental values was in an
acceptable range of 5%. This indicated that the simulated parameters values were agreeing well with those obtained by experiment,
indicating that the OCM reactor model we established in this paper
was reliable.
As shown from Tables S2 and S3, when Supplementary oxygen
was 15% and temperature was at 800 C, the conversion of CH4 ,
the selectivity and the yield of C2 reached 34.1%, 68.2% and 23.3%,
respectively. These values were elevated to 4.6%, 1.6% and 6.4%,
respectively, compared with the case of the one without supplementary oxygen in the two-stage reactor.
3.1. Inuence of supplementary oxygen on species mass fraction
The upstream particle catalyst bed in two-stage reactor was
under the same operating conditions as packed bed reactor loaded
particles catalyst reported in previous work (Zhang et al., 2015b).
The parameters of particle bed were not inuenced by the bedsinterspace distributed oxygen feeding, so the parameter courters
of this bed were the same as those of the packed bed reactor
loaded particles catalyst and these will not be discussed again in
this paper. The parameter courters of monolithic bed in two-stage
2.30E-13
124
251
Fig. 2. Average value of reaction rates in Monolithic catalyst bed of two-stage reactor with supplementary oxygen.
Fig. 3. The contours of CH4 (a) and O2 (b) mass fractions on plane P1 of two-stage reactor with supplementary oxygen ow rate of 0 (1), 1 (2), 2 (3), 3 (4) and 4 (5) ml/min.
From Fig. 4(b), we can also see that the mass fraction of C2 H4 at
the outlet of monolithic catalyst bed reached the best value when
the ow rate of supplementary oxygen was 3 ml/min because the
rate of reaction 5 reached maximum value simultaneously (see
Fig. 2).
3.2. Inuence of supplementary oxygen on temperature and wall
heat ux
In order to simulate the reactor at constant temperature,
thermal boundary condition of side wall was set at constant temperature of 800 C, and the heat of reaction was removed through
252
Fig. 4. The contours of C2 H6 (a) and C2 H4 (b) mass fractions on plane P1 of two-stage reactor with supplementary oxygen ow rate of 0 (1), 1 (2), 2 (3), 3 (4) and 4 (5) ml/min.
Fig. 5. The contours of temperature on plane P1 (a) and heat ux on side wall (b) of two-stage reactor with supplementary oxygen ow rate of 0 (1), 1 (2), 2 (3), 3 (4) and 4
(5) ml/min.
Fig. 5(a) shows that the high temperature zones were distributed in the upper portion of monolithic catalyst bed, and they
were symmetric along the axis of reactor. The monolithic catalyst
bed can be considered as constant temperature since they ranged
within 1073.150 K and 1073.165 K when the ow rate of supplementary oxygen increased from 0 to 4 ml/min. The temperature
increase of monolithic catalyst bed was 0.009 K when the reactor with no supplementary oxygen and was 0.011 K and 0.013 K
when the ow rate of supplementary oxygen was 1 and 2 ml/min,
respectively. The upper value of the temperature range in monolithic catalyst bed and the area of high temperature zone increased
with the increase of the ow rate of supplementary oxygen.
Fig. 5(b) showed that the heat ux of the wall surrounding
monolithic catalyst bed varied from 600 W/m2 to 10 W/m2 . The
area having low value of heat ux increased with the increase of
supplementary oxygen. This illustrates that the OCM reaction rate
was deepening gradually when the ow rate of supplementary oxygen changed from 0 to 4 ml/min, and it agreed well with the results
above (see Figs. 3 and 4).
3.3. Inuence of supplementary oxygen on pressure, density and
velocity
The pressure in two-stage reactor gradually decreased along the
ow direction due to the friction drag produced by the catalyst beds
and the wall surface (see Fig. 6). The pressure drop in the particle
253
catalyst bed was the same as that in the reactor lled with particle
shown in previous work (Zhang et al., 2015b).
In this work, the gauge pressure at the reactor outlet was also
set to zero, and then the gauge pressure of the monolithic catalyst
bed changed from 7.2 Pa, 7.3 Pa, 7.4 Pa 7.6 Pa and 7.7 Pa at the bed
inlet to 6.7 Pa, 6.9 Pa, 7.1 Pa, 7.2 Pa and 7.3 Pa when the ow rate
of supplementary oxygen was 0, 1, 2, 3, and 4 ml/min, so the pressure drop of the catalyst bed had range of 0.3-0.5 Pa. Although the
gauge pressures of the bed inlet and outlet were increased with the
ow rate of supplementary oxygen, the pressure drop in monolithic
catalyst bed was barely affected by supplementary oxygen.
Since the molecular weight of oxygen is higher than the average
molecular mass of the reaction gas (about 20 g/mol), the gas density
of monolithic catalyst bed increased with supplementary oxygen
(see in Fig. 7(a)). Particularly, the high density zone was in the upper
portion of catalyst bed and nearby the boundary layer of side wall
where the O2 mass fraction had high value. According to the integral
results of Fluent post, the average values of gas density were 0.2220,
0.2242, 0.2257, 0.2273 and 0.2289 kg/m3 at the inlet of monolithic
catalyst bed and 0.2206, 0.2228, 0.2242, 0.2257 and 0.2273 kg/m3
at the bed outlet when the ow rate of supplementary oxygen was
0, 1, 2, 3, and 4 ml/min, respectively.
If the temperature and pressure are kept constant, gas density
in the reactor is only associated with the species mass fraction
according to the previous work (Zhang et al., 2015a). As shown in
Supplementary materials, Fig. S1, H2 mass fraction increased with
the ow rate of supplementary oxygen. This would lead to gas density fall. Therefore, the reduction of gas density between the bed
inlet and outlet was increased slightly with supplementary oxygen.
As it can be seen from Fig. 7(b), the gas velocity in monolithic
catalyst bed increased with the supplementary oxygen because of
the additional gas ow. According to the previous work (Zhang
et al., 2015a), rstly the velocity increased and then decreased along
the normal direction of the inner surface of the catalyst bed wall
due to the effect of the boundary layer, chemical reactions and the
monolithic catalyst channel. This phenomenon was also shown in
Fig. 7(b). The maximum value of velocity and the area of high velocity increased with the supplementary oxygen because of the depth
of OCM reaction.
3.4. Inuence of temperature on species mass fraction
Firstly, the average values of reaction rates in particle and monolithic catalyst beds were calculated by FLUENT software and shown
in Fig. 8 and 9. From Fig. 8, we can see that the rate of CO2 formation reaction (reaction 1) decreased as the temperature increased
in particle catalyst bed of two-stage reactor. In addition to this,
all rates of other reactions increased with temperature. The rates
of reaction 2 (C2 H6 formation from CH4 ) and 5 (C2 H4 formation
from C2 H6 ) increased rapidly when the temperature was increased
from 775 C to 800 C, but their rates grew slowly as temperature
increased from 800 C to 825 C. Meanwhile, the rates of reaction
4 (CO oxidized reaction to form CO2 ) and 10 (water-gas shift reaction to generate CO) increased rapidly when the temperature was
raised from 800 C to 825 C.
From Fig. 9, we can also see that the rate of CO2 formation reaction decreased in monolithic catalyst bed the temperature was
increased. When the temperature was increased from 775 C to
825 C, the rates of reaction 2, 5 and 9 increased signicantly with
temperature. When the temperature was increased from 800 C to
825 C, the rate of reaction 10 increased more rapidly than when
the temperature was increased from 775 C to 800 C.
From Fig. 10(a), when the temperature was 775 C, 800 C and
825 C, the mass fraction of CH4 changed from 0.600 at inlet of
particle catalyst bed to 0.478, 0.437 and 0.428 at the bed outlet,
respectively. From Table 1, there was 2 and 1 mol CH4 consumed
254
Fig. 7. The contours of density (a) and velocity magnitude (b) on plane P1 in monolithic catalyst bed of two-stage reactor with supplementary oxygen ow rate of 0 (1), 1
(2), 2 (3), 3 (4) and 4 (5) ml/min.
Fig. 8. Average value of reaction rates in particle catalyst bed of two-stage reactor with supplementary oxygen at temperature of 775 C, 800 C and 825 C.
distribution of CH4 mass fraction in monolithic catalyst bed according to Fig. 10. So, CH4 conversion increased with the temperature in
monolithic catalyst bed in the same way as in particle catalyst bed.
There were 2 mol O2 consumed as 1 mol reaction 1 occurred (see
in Table 1). When the temperature was increased from 775 C to
800 C, the rate of reaction 1 decreased signicantly in particle catalyst bed (see in Fig. 8). Although the rates of reaction 26 increased,
the mass fraction of O2 was determined by reaction 1 and increased
rstly with temperature at the outlet of particle catalyst bed (see
in Fig. 10(b)). The rates of reaction 26 increased signicantly as
255
Fig. 9. Average value of reaction rates in monolithic catalyst bed of two-stage reactor with supplementary oxygen at temperature of 775 C, 800 C and 825 C.
Fig. 10. The contours of CH4 (a) and O2 (b) mass fractions on plane P1 in catalyst bed of two-stage reactor with supplementary oxygen at 775 C (1), 800 C (2) and 825 C (3).
of temperature on C2 H6 and C2 H4 was signicant when the temperature was increased from 775 C to 800 C due to the fact that
the rates of reaction 2 and 5 increased fast in particle catalyst bed
(see in Fig. 8). In monolithic catalyst bed, the rate of reaction 2
increased signicantly when the temperature was increased from
775 C to 800 C and then increased slightly, but the rate of reaction 5 increased gradually when the temperature was increased
from 775 C to 825 C (see in Fig. 9). So, the mass fraction of C2 H6
increased from 0.0262 to 0.0370 at the bed outlet rst and then
decreased slightly to 0.0363 because of the generation of C2 H4
from C2 H6 as the temperature was increased from 775 C to 825 C.
Meanwhile, the mass fraction of C2 H4 increased with temperature
in monolithic catalyst bed. In brief, the selectivity of C2 reached
their maximum value at the temperature of 800 C and the yield of
C2 H4 achieved high value at the temperature of 825 C. So, the high
temperature was favorable for C2 H4 yield.
256
Fig. 11. The contours of C2 H6 (a) and C2 H4 (b) mass fractions on plane P1 in catalyst bed of two-stage reactor with supplementary oxygen at 775 C (1), 800 C (2) and 825 C
(3).
Fig. 12. The contours of CO (a) and CO2 (b) mass fractions on plane P1 in catalyst bed of two-stage reactor with supplementary oxygen at 775 C (1), 800 C (2) and 825 C (3).
From Fig. 12(a), we can see that CO mass fraction increased from
0.0000 at the inlet of particle catalyst bed to 0.0275, 0.0317 and
0.0298 at the bed outlet when the temperature was 775 C, 800 C
and 825 C, respectively. From Fig. 9, the rate of water gas shift
reaction (reaction 9) was close to its inverse reaction rate (reaction 10) in particle catalyst bed with temperature increase. So, the
distribution of CO mass fraction in this catalyst bed was mainly
controlled by reaction 3 and 4. The rate of reaction 3 increased
gradually with the temperature but the rate of reaction 4 increased
faster. Eventually, the rate of reaction 4 exceeded the rate of reaction 3 as temperature was raised at 825 C. Consequently, the mass
fraction of CO at the bed outlet increased rst and then decreased
with the increase of temperature. In monolithic catalyst bed, the
distribution of CO mass fraction was controlled by the reaction 10
from Fig. 10. With the increase of temperature, the rate of reaction 10 gradually increased and the CO mass fraction in this bed
increased too.
257
From Fig. 12(b), it can be seen that the mass fraction of CO2
increased from 0.000 at the inlet of particle catalyst bed to 0.142,
0.106 and 0.116 at the bed outlet when the temperature was 775 C,
800 C and 825 C, respectively. The rates of reaction 1 and 4 governed the distribution of CO2 mass fraction in this bed according to
Fig. 9. The rate of reaction 1 (CO2 generation reaction) decreased
and the rate of reaction 4 (CO2 consumption reaction) increased
with the temperature. The net generation rate of CO2 reached its
minimum value at the temperature of 800 C. So CO2 mass fraction at the outlet of particle catalyst bed decreased rst and then
increased. In monolithic catalyst bed, the distribution of CO2 mass
fraction was governed by the rates of reaction 1 and 10 according
to Fig. 9. The generation rate of CO2 decreased and its consumption
rate increased with temperature in monolithic catalyst bed. The
difference of CO2 mass fraction from the inlet to outlet of monolithic catalyst bed was 0.017, 0.006 and 0.004 at the temperature
of 775 C, 800 C and 825 C and decreased with the temperature.
Fig. 13. The contours of gauge pressure on plane P1 in catalyst bed of two-stage
reactor with supplementary oxygen at 775 C (1), 800 C (2) and 825 C (3).
tary oxygen elevated the gas density near the inlet of monolithic
bed from Fig. 14(a).
The velocity magnitude in catalyst beds increased with temperature both in particle and monolithic beds due to the decrease of
gas density (see in Fig. 14(b)). The maximum value of velocity mag-
Fig. 14. The contours of density (a) and velocity magnitude (b) on plane P1 in catalyst bed of two-stage reactor with supplementary oxygen at 775 C (1), 800 C (2) and
825 C (3).
258
4. Conclusions
CFD can accurately predict the impact of ow eld and heat
transfer on reactor performance. In this work, a three-dimensional
numerical model was established to simulate the OCM two-stage
reactors with supplementary oxygen using FLUENT software when
the volume rate of mixture raw gas was 80 ml/min under standard
state with pressure of 1 atm. The effect of supplementary oxygen
ow rate and temperature on reactor performance was investigated using this model. The results showed that the simulated
values of the CH4 conversion, products selectivity and other parameters in the outlet of reactor are consistent with the experimental
values in acceptable errors. It was also observed that supplementary oxygen promoted the OCM reaction in monolithic catalyst bed
and the CH4 conversion increased as the ow rate of supplementary oxygen changed from 0 ml/min to 4 ml/min. Meanwhile, the
heat ux of side wall, gas density and velocity also increased with
the supplementary oxygen. When the ow rate of supplementary
oxygen was 3 ml/min, CH4 conversion of 34.1% was obtained at the
temperature of 800 C and C2 selectivity and yield reached their
best values of 68.2% and 23.3%, respectively. This trend was similar
with experimental results. Under the same operating conditions,
CH4 conversion was improved by 4.6%, C2 selectivity and yield were
increased by 1.6% and 6.4% respectively compared with the reactor
without supplementary oxygen according to the simulation results.
The counters of C2 H6 and C2 H4 mass fraction in catalyst beds at
different temperature showed that the high temperature of monolithic catalyst bed was benecial for the improvement of the yield
of C2 H4 in a two-stage reactor.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.compchemeng.
2016.04.036.
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