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Computers and Chemical Engineering 90 (2016) 247259

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Computers and Chemical Engineering


journal homepage: www.elsevier.com/locate/compchemeng

Numerical simulation of particle/monolithic two-stage catalyst bed


reactor with beds-interspace distributed dioxygen feeding for
oxidative coupling of methane
Zhao Zhang a,b , Shengfu Ji a,
a

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

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Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

Nomenclature
Ea,j
Had,CO2
HO2
k0,j
Kj,CO2
KO2
mj , nj
T
r
R

Activation energy of reaction j: kJ mol1


Adsorption heat of CO2 in specic reaction: kJ mol1
Adsorption heat of O2 in specic reaction: kJ mol1
Pre-exponential
factor
of
reaction
j:
mol g1 s1 Pa(m + n)
Adsorption constant of CO2 in reaction j: Pa1
Adsorption constant of O2 in reaction 2: Pa1
Partial reaction orders of species in reaction j
Temperature: K
Reaction rate: mol g1 s1.
Gas constant: kJ mol1 K1

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.

gated in previous work (Zhang et al., 2015c). The improved Stansch


model that was introduced as kinetics model in previous work
(Zhang et al., 2015c) is only validated at constant temperature of
800 C. In this work, the kinetics model is extended and adapted to
different operating temperatures by changing the values of active
energy and pre-exponential factor and keeping the reaction rates
consistent with previous work at temperature of 800 C. The simulation was executed once the kinetics model parameters changed
until the simulation data was close to the experimental data. The
three-dimensional models were established for the OCM tubular
packed two-stage reactors with beds-interspace supplementary
O2 . FLUENT commercial code was used to solve Navier-Stokes equations and species transport equations. The reaction kinetics models
were added by the user-dened function (UDF) of FLUENT software.
The effect of temperature and ow rate of supplementary O2 on
reactor performance was investigated using CFD model.
2. Model and numerical method
2.1. Geometric model and meshes
To minimize errors from this model, we established geometric model for two-stage reactor with distributed oxygen feeding in
accordance with the experimental apparatus (Ji and Wang, 2012).
According to the experimental apparatus, the particle catalyst and
the cordierite monolithic catalyst were placed in a quartz tube
(inner diameter 8 mm, length 600 mm) and separated with quartz
wool between the two catalyst beds to construct a two-stage reactor as shown in Fig. 1(a). The bed heights of particle and monolithic
catalyst were 10 mm and 50 mm, respectively. Two sections, above
the particle catalyst and under the cordierite monolithic catalyst,
were lled with quartz chips at a length of 75 mm (see Fig. 1(a)).
Besides, there were 8 holes, having a diameter of 1 mm, on the
side wall of quartz wool layer as the inlet of supplementary O2 .
For tubular reactor, its geometry model can be simplied to 2D
axisymmetric model. In CFD model, the existence of supplementary O2 inlet make the velocity, density and species mass fraction
et.cl distributed in circumferential direction (see Fig. S3 in Supple-

Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

249

Table 1
Reaction equations and reaction rate equations of Stansch kinetic model.
No.

Reaction equation

Reaction rate equation

CH4 + 2O2 = CO2 + 2H2 O

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

C2 H4 + 2O2 = 2CO + 2H2 O

r6 =

1+K4,CO e

C2 H6 = C2 H4 + H2

C2 H4 + 2H2 O = 2CO + 4H2

CO + H2 O = CO2 + H2

10

CO2 + O2 = CO + H2 O

mentary material). If 2D axisymmetric model was used, it would


lead to big error. The geometry models were portioned by meshes
in similar way with the model mentioned in previous work (Zhang
et al., 2015c) excepted that the part with inlet of distributed oxygen feeding was portioned by tetrahedron meshes. Three types of
mesh were generated to investigate mesh dependency. The mesh
number was 500,000, 700,000 and 900,000, respectively. The performance parameters of reactor dependent on mesh number were
listed in Table S1 of Supplementary material. According to Table S1,
the mesh number of 700,000 was enough to simulate the two-stage
reactor with supplementary oxygen. The meshes of cross section
and on reactor wall were shown in Fig. 1(b) and (c).
2.2. Governing equations
According to the operating conditions of experiment (Ji and
Wang, 2012), the ow in OCM packed bed reactor is laminar
(Re = 5.7) and can be described by the Navier-Stocks equations
(Batchelor, 2000). In order to reduce the computational time, a
quasi-homogenous model was used to simulate the reactor performance. In this model, porous medium model was employed to
describe drag of catalyst bed on reaction gas ow (Ergun, 1952).
The temperature gradient from gas to catalyst was estimated
by non-equilibrium thermal model in FLUENT software. Besides,
species transport equation should be used to describe molecular
and convection diffusions between species. The details of governing
equations was shown in previous work (Zhang et al., 2015b).
2.3. Kinetic model
Reaction kinetics model can mainly affect the accuracy of reactor model for CFD simulation. For OCM reactor simulation, the
blocking effect of CO2 and computational time must be considered
if we plan to select a suitable reaction kinetics model. A kinetic
model is built by Stansch et al. (Stansch et al., 1997), includes 10
step reactions and 8 species (see Table 1), is applied to the OCM
reaction catalyzed by La2 O3 /CaO particles rst and meet with our
selected subjects. But, the reaction rate on Na2 WO4 -Mn/SiO2 particle catalyst and Na3 PO4 -Mn/SiO2 /cordierite monolithic catalyst
is different from rate on La2 O3 /CaO particle catalyst. In previous
work (Zhang et al., 2015a, 2015b), we kept the reaction equations
and rate formulas same with original Stansch model and change

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

r7 = k0,7 eEa,7 /RT PCm7H

2 6

r8 = k0,8 eEa,8 /RT PCm8H PHn8 O


2 4

m9 n9
r9 = k0,9 eEa,9 /RT PCO
PH O

r10 = k0,10 e

Ea,10 /RT

m10 n10
PCO
P
2 H2

the model parameters. Firstly, a one-dimension model was build


using Matlab program to optimize the model parameters and make
the model be suitable to Na2 WO4 -Mn/SiO2 particle catalyst and
Na3 PO4 -Mn/SiO2 /cordierite monolithic catalyst, respectively. Secondly, the optimized parameters was used for 3D CFD model and
was changed further until the simulation data was close to experimental data.
To investigate the effect of temperature on the reactor performance, the values of activation energy and pre-exponential factor
in reaction rate equations were changed to adapt experimental
data at temperature range of 775825 C, while the reaction rates
at temperature of 800 C were consistent with those in previous
works (Zhang et al., 2015a, 2015b). The modied values of kinetic
parameters were suitable for Na2 WO4 -Mn/SiO2 particle catalyst
and Na3 PO4 -Mn/SiO2 /cordierite monolithic catalyst and these are
shown in Tables 2 and 3, respectively.
The modied kinetics model was added to FLUENT software in
the form of User Dened Function (UDF). The thermal chemical
parameters of each species were provided by the FLUENT database
or obtained from NIST database.
2.4. Operating conditions, boundary conditions and numerical
methods
The operating conditions for simulated condition were the same
as those for experimental condition (Ji and Wang, 2012). The volume ow rate of reactant at top inlet was 80 ml/min under standard
state with a CH4 /O2 ratio of 3 and the pressure was 1 atm. The temperature was 775 C, 800 C and 825 C, respectively. The reactor
outlet type was dened as pressure outlet, and the type of top inlet
and side inlet was designated as the mass ow inlet dependent on
the outlet type. The details of boundary conditions and numerical
methods can be found in previous work (Zhang et al., 2015b).
3. Results and discussion
In order to investigate inuence of supplementary oxygen on the
performance of two-stage packed bed reactor with beds-interspace
distributed oxygen feeding, we simulated the OCM reaction phenomenon of the reactor using the models and operation conditions
introduced above. The ow rate of supplementary oxygen from side
wall was 0, 1, 2, 3 and 4 ml/min and corresponding to 0, 5, 10, 15

250

Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

Table 2
Kinetic parameters for Na2 WO4 -Mn/SiO2 particle catalyst at 775825 C.

1
2
3
4
5
6
7
8
9
10

K0,j (mol g1 s1 Pa(m+n) )

Ea,j (kJ mol1 )

Kj,CO2 (Pa1 )

Had,CO2 (kJ mol1 )

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 )

Had,O2 (kJ mol1 )

1.15E-11

124

KO2 (Pa1 )

Had,O2 (kJ mol1 )

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

K0,j (mol g1 s1 Pa(m+n) )

Ea,j (kJ mol1 )

Kj,CO2 (Pa1 )

Had,CO2 (kJ mol1 )

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

reactor were focused on. In order to explain the distribution of


species on plane P1, the average values of reaction rates of monolithic catalyst bed were calculated by FLUENT software and shown
in Fig. 2 because that species mass fraction was directly related to
the reaction rate.
From Fig. 2, we can see that the rates of reaction 2 and 5
increased rst and then decreased with supplementary oxygen.
Their rates reached maximum values when the ow rate of supplementary oxygen was 3 ml/min. The rate of reaction 9 decreased
slightly with supplementary oxygen. Besides, the rates of other
reactions increased gradually with supplementary oxygen ow rate
increasing from 0 ml/min to 4 ml/min.
From Fig. 3 and 4, we can see that the mass fraction of each
species in particle catalyst bed of two-stage reactor with supplementary oxygen was completely the same as that in the packed bed
reactor with 10 mm height particle catalyst (Zhang et al., 2015b)
and was not affected by supplementary oxygen. From Fig. 3(a),
when ow rates of supplementary oxygen were 0, 1, 2, 3 and
4 ml/min, average values of CH4 mass fraction changed from 0.437,
0.431, 0.424, 0.416 and 0.408 at monolithic catalyst bed inlet to
0.404, 0.395, 0.385, 0.375 and 0.365 at this bed outlet, respectively.
The reductions of CH4 mass fraction from the bed inlet to outlet were 0.033, 0.036, 0.039, 0.041 and 0.043 and increased when
the ow rate of supplementary oxygen changed from 0 ml/min to
4 ml/min. CH4 was a reactant in reaction 13 (see Table 1). Although
the rate of reaction 2 decreased as ow rate of supplementary oxygen changed from 3 ml/min to 4 ml/min, the rates of reaction 1 and
3 increased. So, the sum consumption of CH4 in monolithic catalyst
bed increased gradually.
From Fig. 3(b), average values of O2 mass fraction decreased
from 0.144, 0.168, 0.183, 0.198 and 0.213 at monolithic catalyst bed
inlet to 0.100, 0.119, 0.130, 0.142 and 0.154 at this bed outlet, when
ow rates of supplementary oxygen were 0, 1, 2, 3 and 4 ml/min,
respectively. The reductions of O2 mass fraction from the bed inlet
to outlet increased with supplementary oxygen. Although the rates
of reaction 2 and 5 decreased when the ow rate of supplementary
oxygen changed from 3 ml/min to 4 ml/min (see Fig. 2), the sum
consumption of O2 in monolithic catalyst bed increased gradually
with supplementary oxygen.

Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

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(a), the average values of C2 H6 mass fraction changed


from 0.0350, 0.0343, 0.0337, 0.0331 and 0.0324 at monolithic catalyst bed inlet to 0.0399, 0.0367, 0.0366, 0.0383, 0.0365 at this bed
outlet, when the ow rates of supplementary oxygen were 0, 1, 2,
3 and 4 ml/min, respectively. The increases of C2 H6 mass fraction
from the bed inlet to outlet were 0.051, 0.024, 0.029, 0.052 and
0.041, increased rst because of the effect of supplementary oxygen dilution and then increased with supplementary oxygen. When
the ow rate of supplementary oxygen changed from 3 ml/min to
4 ml/min, the increases of C2 H6 mass fraction from the bed inlet to
outlet decreased again due to the fact that the rate of reaction 2
decreased (see Fig. 2).

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

Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

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.

the side wall. The contours of temperature on plane P1 and heat


ux on side wall are shown in Fig. 6. From this gure, it can be seen
that the temperature and the heat ux of particle catalyst bed were

the same as those of packed bed reactor loaded particles catalyst in


previous work (Zhang et al., 2015b).

Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

Fig. 6. The contours of gauge pressure 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. 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

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Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

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.

in reaction 2 and 1 when 1 mol reaction occurred. According to


Fig. 8, the rate of reaction 1 decreased, but the rate of reaction 2
increased signicantly with temperature. So, the rate of reaction
2 determined the distribution of CH4 mass fraction and the conversion of CH4 increased in particle catalyst bed with temperature.
CH4 was diluted by supplementary oxygen rst and then ow into
monolithic catalyst bed. In monolithic catalyst bed, CH4 mass fraction decreased sequentially from 0.450, 0.416 and 0.403 at bed inlet
to 0.427, 0.375 and 0.362, when the temperature was 775 C, 800 C
and 825 C, respectively. The rate of reaction 2 also determined the

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

Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

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).

the temperature changed from 800 C to 825 C and determined


the distribution of O2 mass fraction. Meanwhile, O2 mass fraction
decreased with temperature at the outlet of particle catalyst bed
(see in Fig. 10(b)).
From Fig. 10(b), it can also be seen that the mass fraction at inlet
and outlet also increased rst and then decreased with temperature in monolithic catalyst bed because of the effect of upstream.
The rates of reaction 26, particularly reaction 2 and 5 increased
obviously with temperature in this bed (see Fig. 9). The reduction
of mass fraction of O2 between this bed inlet and outlet was 0.046,
0.056 and 0.059 at the temperature of 775 C, 800 C and 825 C,
respectively. So, the consumption of O2 increased with temperature
in monolithic catalyst bed.
From Fig. 11, when the temperature was increased from 775 C
to 825 C, the mass fractions of C2 H6 and C2 H4 increased at the
outlet of particle catalyst bed. The values were 0.0236, 0.0350 and
0.0353 for C2 H6 and 0.0440, 0.0609 and 0.0689 for C2 H4 . The effect

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.

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Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

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.

Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

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.

3.5. Inuence of temperature on pressure, density and velocity


From Fig. 13, we can see that the gauge pressure increased with
temperature from 775 C to 825 C in both catalyst beds. However,
the pressure drop was about 2.0 Pa in particle catalyst bed and was
about 0.4 Pa in monolithic catalyst bed and kept consistent with
temperature increase. This meant the pressure drop of catalyst beds
is independent of their temperature.
Common sense says that gas density decreases when temperature increases. According to the previous work (Zhang et al., 2015a),
gas density was also inuenced by H2 mass fraction in the OCM
reactor at constant temperature. From the contours of H2 mass fractions at different temperature shown in Supplementary materials,
Fig. S2, we can see that H2 mass fractions increased with temperature. So, the gas density of catalyst bed decreased as temperature
increased (see in Fig. 14(a)). It can also be seen that the supplemen-

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).

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Z. Zhang, S. Ji / Computers and Chemical Engineering 90 (2016) 247259

nitude was in monolithic bed. The high velocity area in monolithic


bed became larger with temperature.

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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