28-3-62-Modeling of Microreactor For Methane Dry Reforming - Comparison of Langmuir-Hinshelwood Kinetic and Microkinetic Models

Journal of Natural Gas Science and Engineering 20 (2014) 99e108
Contents lists available at ScienceDirect
Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse
Modeling of microreactor for methane dry reforming: Comparison of

LangmuireHinshelwood kinetic and microkinetic models
Alireza Behroozsarand a, Ali Nakhaei Pour b, *
a
Department of Chemical Engineering, Urmia University of Technology, P.O.Box: 93187-57166, Urmia, Iran
b
Department of Chemistry, Ferdowsi University of Mashhad, P.O.Box: 9177948974, Mashhad, Iran
a r t i c l e i n f o a b s t r a c t
Article history: Synthesis gas production via CO2 (dry reforming) of natural gas (mostly CH4) has attracted increasing
Received 17 April 2014 since both are greenhouse gases. The aim of this work is the comparison of LangmuireHinshelwood
Received in revised form kinetic (LHK) and microkinetic (MK) models for dry reforming (DR) process in a micro-reactor. In this
13 June 2014
paper, synthesis gas (hydrogen and carbon monoxide) production was investigated by a two-dimensional
Accepted 14 June 2014
Available online
numerical model of single microchannel. Computational fluid dynamic (CFD) modeling with detailed
chemistry (MK model) and LHK model was conducted to understand the DR on rhodium (Rh) catalyst.
Microchannel wall temperature, pressure, CH4/CO2, hydrogen, carbon monoxide, and steam concentra-
Keywords:
Dry reforming
tions in feed stream are selected as the effective parameters on microchannel performance. Study results
Microchannel show that increasing wall temperature in LHK model, CO concentration and pressure in MK model have
LangmuireHinshelwood kinetic positive effect on methane conversion of microreactor. Also, decreasing CH4/CO, steam concentration in
Microkinetic LHK model and wall temperature, CH4/CO, hydrogen composition in MK model have same behavior.
Finally, results present LHK model is more suitable than current MK model for predicting DR process
behavior.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction current criticism on DR, pointing to the lack of competitiveness of

DR with conventional steam reforming. Only for the production of
It is well known that with appropriate catalysts, CO2 can reform H2 this statement is valid, since 96 and 124 kJ is needed to produce
hydrocarbons to synthesis gas (H2 and CO). For methane, dry 1 mol H2 by steam and DR, respectively (Corthals et al., 2011).
reforming (DR) can be represented globally as (McGuire et al., On the other hand, the commercial application of DR reaction is
2011): limited due to the lack of effective catalysts resistant to carbon
formation (Sadykov et al., 2011). Most group VIII metals, especially
CH4 þCO2 42H2 þ 2CO (1) Ni based and noble metals have been studied as catalysts for steam
reforming, DR, partial oxidation and mixed reforming of methane
Synthesis gas production via CO2 (dry reforming) of natural gas (Osaki and Mori, 2001; Rostrup-Nielsen and Christiansen, 1995;
(mostly CH4) has attracted increasing attention within the past Ruckenstein and Hu, 1995; Wang and Lu, 1998; Wei et al., 2000).
decade since both are greenhouse gases and the possibility of The two most prominent causes for the deactivation in DR are coke
conversion to more useful base chemicals via the FischereTropsch deposition and sintering of the active metal phase (Sadykov et al.,
reaction is appealing (Foo et al., 2012). Dry reforming (DR) process 2011). In recent years, extensive efforts have been devoted to the
becomes advantageous compared to steam reforming or partial carbon dioxide reforming of methane. Most of the studies are
oxidation for syngas production, since H2/CO product ratio (theo- focused on the investigation of novel and practical catalysts for the
retically equals to one) is suitable for its further use in the pro- process (Chen et al., 2010; Gao et al., 2009; Guo et al., 2009; He
duction of oxygenated compounds and liquid hydrocarbons by the et al., 2009; Lee et al., 2003; Meshkani and Rezaei, 2010; Pompeo
FischereTropsch synthesis using iron catalysts (Serrano-Lotina et al., 2007). At present, two kinds of supported catalysts are
et al., 2012). Dry reforming's high endothermicity is the subject of mainly employed for this reaction: nickel- and noble metal-based
catalysts. Compared to Ni-based catalysts, noble metal catalysts
such as supported Pt (Bitter et al., 1997), Rh (Erdohelyi et al., 1993),
* Corresponding author.
and Ru are less sensitive to carbon deposition and deactivation by
E-mail addresses: nakhaeipoura@yahoo.com, a.nakhaei@um.ac.ir (A.N. Pour).
http://dx.doi.org/10.1016/j.jngse.2014.06.011
1875-5100/© 2014 Elsevier B.V. All rights reserved.
100 A. Behroozsarand, A.N. Pour / Journal of Natural Gas Science and Engineering 20 (2014) 99e108
coking, but these metals are more expensive. Considering the high 2. Mathematical model
cost and limited availability of noble metals, the development of
transition metal catalysts with improved properties is an important Main assumptions of this model are:
topic. Therefore, improved nickel catalysts are more practicable
(Shang et al., 2011). ▪ Two dimensional models were assumed [Axial direction (x-di-
Monolith reactors are being studied as a replacement for con- rection) and Radial direction (r-direction)].
ventional multiphase reactors such as trickle-bed reactors, slurry ▪ Fluid flow was modeled as a laminar flow.
reactors, and slurry bubble column reactors for gaseliquidesolid ▪ Steady state condition was considered.
reactions (Roy et al., 2004).
Monolith structures are essentially a single structure with many DR was usually modeled by a 2D axisymmetric channel model
thin, vertical, parallel channels, separated from each other by walls. (McGuire et al., 2011). Transport phenomena in the channel can be
The channels are usually rectangular, but triangles, hexagons, or described by the conservation equations of mass, momentum,
more complex geometries also exist. To increase the surface area, chemical species and enthalpy.
internal fins can also be provided. Furthermore, the fins have a As mentioned above, six effective parameters in DR process
stabilizing effect on the gaseliquid flow and allow operation in were selected. For covering behavior of all parameters, 48 modeling
countercurrent mode without flooding (Lebens et al., 1999a,b,c). sets were predicted. Six levels of (TWall) and (CH4/CO2) ratio and five
Primary advantages of the monolith packing are low pressure levels of (CH4/CO2/H2) ratio, (CH4/CO2/H2) ratio, (CH4/CO2/H2O)
drop in the channels and high mass transfer rates attributed to ratio, and (P) are used for modeling of all cases. Table 1 and Table 2
small diffusion paths. Therefore, carrying out equilibrium-limited show classification levels of parameters and 49 modeling sets that
reactions, such as hydrogenation, steam reforming, DR, and par- have been done in this study, respectively.
tial oxidation in monoliths, is a promising proposition (Roy et al.,
2004). Because one of main advantage of monolith reactors is
2.1. Geometry of microreactor
high mass transfer rates, so the rate of coke formation in DR process
will be decreased drastically.
Fig. 1 shows a typical monolith structure and the particular
The aim of this work is the study of synthesis gas production by
single channel geometry used in this study. Since every channel
dry methane reforming using microreactors. These advanced re-
within the monolith structure behaves essentially alike, only one
action systems can be used for synthesis gas decentralized pro-
channel needs to be analyzed. Also, a 2D channel is used to
duction from natural gas. Thus, these system include microreactors
approximate the actual shape of the channels. In current case the
and active, selective, stable and/or cheap catalytic formulations.
channel boundary is divided into 3 sections:
Indeed, process intensification would allow better heat transfer
that plays a key role in reforming process (steam and dry reform-
1) Upper & lower wall: DR catalytic reactions occur on these walls.
ing) (Conant et al., 2007; Delsman et al., 2005; Kolb and Hessel,
Also, temperature constant type has been selected as thermal
2004).
boundary condition.
In this study, typical monolith structure and the particular
2) Input: Gas Feed enter to micro-channel from this section. Mass
single channel geometry is considered and the micro-reformer is
flow inlet has been selected as boundary condition.
represented by a two dimensional axisymmetric model. The
3) Output: Gas product exit from micro-channel from this section.
catalytic surface of microreactor is modeled as wall surface
Pressure outlet has been selected as boundary condition.
where DR reactions occur. For comparison of various models of
catalytic reactions, the DR reactions express in two states: A)
In section one, for Navier Stokes and boundary layer models,
Microkinetic model; B) LangmuireHinshelwood Kinetic model.
total length of micro-channel (100 mm) has been predicted where
In microkinetic surface reaction mechanism, 10 volumetric and
there is catalytic activity. The wall temperature is constant but in
13 site species exist (McGuire et al., 2011). Also, Lang-
different sets of modeling is different from 500 to 2000 K. The flow
muireHinshelwood Kinetic model has been reported in several
conditions were chosen to study the effective parameters that
references. In this study the reported kinetic model by Yin et al.
include pressure from 1 to 20 atm, (CH4/CO2) ratio from 0.75 to 3.0,
(Yin et al., 2007) has been applied. This model has two catalytic
(CH4/CO2/H2) ratio from 0.0 to 0.3, (CH4/CO2/CO) ratio from 0.0 to
reactions. Six main effective parameters, catalytic surface tem-
0.3, and (CH4/CO2/H2O) ratio from 0.0 to 0.3.
perature (T Wall), methane to carbon dioxide ratio (CH4/CO2),
hydrogen composition at feed stream (CH4/CO2/H2), carbon
monoxide composition at feed stream (CH4/CO2/CO), water 2.2. Conservation equations
composition at feed stream (CH4/CO2/H2O), and microreactor
pressure are studied and the effects of parameters on methane The mass conservation for the ideal gas mixture is:
conversion, hydrogen, carbon monoxide, and carbon dioxide
selectivity, H2/CO ratio, temperature profile, and concentration vr v 1 v
þ ðruÞ þ ðrryÞ ¼ 0 (2)
profiles of species are showed. vt vx r vr
Table 1
Levels of effective parameters.
Variables Twall (K) CH4/CO2 CH4/CO2/H2 CH4/CO2/CO CH4/CO2/H2O P(atm)
Level-1 500 0.75 0.5/0.5/0.0 0.5/0.5/0.0 0.5/0.5/0.0 1.0

Level-2 700 1.00 0.475/0.475/0.05 0.475/0.475/0.05 0.475/0.475/0.05 3.0
Level-3 900 1.50 0.45/0.45/0.1 0.45/0.45/0.1 0.45/0.45/0.1 5.0
Level-4 1200 2.00 0.4/0.4/0.2 0.4/0.4/0.2 0.4/0.4/0.2 10.0
Level-5 1500 2.50 0.35/0.35/0.3 0.35/0.35/0.3 0.35/0.35/0.3 20.0
Level-6 2000 3.00
A. Behroozsarand, A.N. Pour / Journal of Natural Gas Science and Engineering 20 (2014) 99e108 101
Table 2
List of Numerical models used in this study with their different parameters value.
Exp. No. Twall (K) CH4/CO2 CH4/CO2/H2 CH4/CO2/CO CH4/CO2/H2O P(atm)
Exp.1 500 1.0 No exist H2 No exist CO No exist H2O 5.0

Exp.17 700 1.0 0.5/0.5/0.0 No exist CO No exist H2O 10.0
Exp.27 1200 1.0 No exist H2 0.5/0.5/0.0 No exist H2O 10.0
Exp.32 700 1.0 No exist H2 No exist CO 0.5/0.5/0.0 10.0

Because in this paper the steady state has been considered, so v v 2 v vP v 4 vu 2 1 v
the term vr
vt will be zero.
ðruÞþ ru þ ðruyÞ ¼ þ m m ðryÞ
vt vx vr vx vx 3 vx 3 r vr
The axial and radial momentum conservation equations,
neglecting body forces, are given as (Ding et al., 2010): 1v vy vu
þ mr þ (3)
r vr vx vr

v v v 2 vP v vy vu
ðruÞ þ ðruyÞ þ ry ¼ þ m þ
vt vx vr vr vx vx vr

v 4 vu 2 vu y
þ m m þ
vr 3 vr 3 vr r

2m vy y
þ (4)
r vr r
At steady state condition, vtv ðruÞ will be zero.
The local dynamic viscosity is obtained based on the Chapman-

Enskog theory for multicomponent ideal gas and the dynamic
Fig. 1. Schematic of the computational domains for three configurations in geometry viscosity of each species is assumed as monoatomic gas (Bird et al.,
using 2D channel model (L ¼ 100 mm; d ¼ 2 mm). 2006). The species conservation is
2 3 sffiffiffiffiffiffiffiffiffiffiffiffi
v v v vJi;x 1 v rJi;r g RT
ðrYi Þ þ ðruYi Þ þ ðryYi Þ ¼ 4 þ 5 i ¼ 1; :::; Ng kf ;n ¼ t (11)
vt vx vr vx r vr G 2pMi
(5) Chemical reactions on the wall of the catalytic reactor lead to a

v species flux balance at the reacting surface for the gas phase
At steady state condition, will be zero. vt ðrYi Þ species:
Where the mass flux is composed of a concentration driven term
and a thermal diffusion term

vY vT Si Mi ¼ Ji;r þ ryYi i ¼ 1; :::; Ng (12)
Ji;x ¼ C
Ji;x þ T
Ji;x ¼ rDij i Di:T (6)
vx vx Since the steady state solution is considered in this work, the
time variation of the surface coverage is zero, that is
C T vYi vT
Ji;r ¼ Ji;r þ Ji;r ¼ rDij Di:T (7)
vr vr
The concentration driven and thermal driven diffusion co- vQ Si
¼ ¼0 ði ¼ 1; :::; Ns Þ (13)
efficients of each species are expressed by rigorous Maxwelle- vt G
Stefan formulation. The site density (G) is assumed to be 2.72 109 mol cm2
The energy conservation, assuming no body forces and no (McGuire et al., 2011). The above algebraic equation system is
viscous dissipation, is solved to obtain the surface coverage and flux of each gas species,
using the semi-implicit extrapolation method.
v rCp T v ruCp T v ryCp T v vT 1 v vT
þ þ ¼ k þ rk
vt vx vr vx vx r vr vr
! Table 3
v X
N g
Detailed reaction mechanism and kinetic coefficients that are used in this study[1].
Cp TJi;x
vx i Reaction A/[cm,mol,s] Ea/[kJ/mol]
!
v X
Ng
vP 1. Adsorption
Cp TJi;r þ H2 þ Rh(s) þ Rh(s) /H(s) þH(s) 0.01 s.c.a
vr i
vt O2 þ Rh(s) þ Rh(s) /O(s) þO(s) 0.01 s.c.a
vP vP CH4 þ Rh(s) /CH4(s) 0.008 s.c.a
þu þy H2O þ Rh(s) /H2O(s) 0.1 s.c.a
vx vr CO2 þ Rh(s) /CO2(s) 0.048 s.c.a
(8) CO þ Rh(s) /CO(s) 0.5 s.c.a
vðrCp TÞ 2. Desorption
At steady state condition, will be zero. vt H(s) þ H(s) /Rh(s) þRh(s)þH2 3 10þ21 77.8
Thermal conductivity of the ideal gas mixture is computed using O(s) þ O(s) /Rh(s) þRh(s)þO2 1.3 10þ22 355.2e280QO(s)
the mixture thermal conductivity based on kinetic theory (Bird H2O(s) /H2O þRh(s) 3 10þ13 45
CO(s) /CO þRh(s) 3.5 10þ13 133.4e15QO(s)
et al., 2006).
CO2(s) /CO2 þRh(s) 4.1 10þ11 18.0
CH4(s) /CH4 þRh(s) 1.9 10þ14 25.1
2.3. Reaction model 3. Surface reactions
H(s) þ O(s) /OH(s) þRh(s) 5 10þ22 83.7
OH(s) þ Rh(s) /H(s) þO(s) 3 10þ20 37.7
According to introduction section, for comparison of various H(s) þ OH(s) /H2O(s) þRh(s) 3 10þ20 33.5
models of catalytic reactions, the DR reactions express in two H2O(s) þ Rh(s) /H(s) þOH(s) 5 10þ22 106.4
states: A) Microkinetic model; B) LangmuireHinshelwood Kinetic OH(s) þ OH(s) /H2O(s) þO(s) 3 10þ21 100.8
model. H2O(s) þ O(s) /OH(s) þOH(s) 3 10þ21 171.8
C(s) þ O(s) /CO(s) þRh(s) 5.2 10þ23 97.9
CO(s) þ Rh(s) /C(s) þO(s) 2.5 10þ21 169
2.3.1. Surface chemistry model (microkinetic model) CO(s) þ O(s) /CO2(s) þRh(s) 5.5 10þ18 121.6
A detailed reaction mechanism (Table 3) with 10 gas phase CO2(s) þ Rh(s) /CO(s) þO(s) 3 10þ21 171.8
CO(s) þ H(s) /HCO(s) þRh(s) 5 10þ19 108.9
species and 12 surface absorbed site species, and 42 elementary
HCO(s) þ Rh(s) /CO(s) þH(s) 3.7 10þ21 0.0 þ 50QCO(s)
surface reactions is used to describe the surface reactions (McGuire HCO(s) þ Rh(s) /CH(s) þO(s) 3.7 10þ24 59.5
et al., 2011). The state of the catalytic surface is described by its CH (s) þ O(s) /HCO(s) þRh(s) 3.7 10þ21 167.5
temperature and coverage of the adsorbed species. The formation/ CH4(s) þ Rh(s) /CH3(s) þH(s) 3.7E þ 21 61
consumption rate of gas species and the absorbed species i by re- CH3(s) þ H(s) /CH4(s) þRh(s) 3.7E þ 21 51
CH3(s) þ Rh(s) /CH2(s) þH(s) 3.7E þ 24 103
actions is written as CH2(s) þ H(s) /CH3(s) þRh(s) 3.7E þ 23 44.1
CH2(s) þ Rh(s) /CH(s) þH(s) 3.7E þ 24 100
X
Ks g þNs
NY
yj;n CH(s) þ H(s) /CH2(s) þRh(s) 3.7E þ 21 68
Si ¼ yi;n kf ;n Xj i ¼ 1; :::; Ng þ Ns (9) CH(s) þ Rh(s) /C(s) þH(s) 3.7E þ 21 21
n¼1 j¼1 C(s) þ H(s) /CH(s) þRh(s) 3.7E þ 21 172.8
CH4(s) þ O(s) /CH3(s) þOH(s) 1.7E þ 24 80.34
The temperature dependence of the reaction rate coefficients is CH3(s) þ OH(s) /CH4(s) þO(s) 3.7E þ 21 24.3
given by a modified Arrhenious equation CH3(s) þ O(s) /CH2(s) þOH(s) 3.7E þ 24 120.3
CH2(s) þ OH(s) /CH3(s) þO(s) 3.7E þ 21 15.06
Ns CH2(s) þ O(s) /CH(s) þOH(s) 3.7E þ 24 114.5
Ean Y εi;n Qi
kf ;n ¼ AT b;n exp Q4;n exp (10) CH(s) þ OH(s) /CH2(s) þO(s) 3.7E þ 21 36.82
RT i¼1 i RT CH(s) þ O(s) /C(s) þOH(s) 3.7E þ 21 30.13
C(s) þ OH(s) /CH(s) þO(s) 3.7E þ 21 136.00
For adsorption reactions, the sticking coefficients are commonly a
Value sticking coefficient. Total available site density is for cata-
used, which are converted to the conventional rate coefficients by lystG¼2.72109 mol/cm2.
2.3.2. LangmuireHinshelwood kinetic model

This study utilized the kinetics obtained by Richardson and 37641
KCO2 ¼ 2:64 103 exp (20)
Paripatyadar (Richardson and Paripatyadar, 1990) for DR on a Rh/ Rg Tg
Al2O3 catalyst. The reaction is the DR reaction of methane with
carbon dioxide (Verykios, 2003): 40684
KCH4 ¼ 2:63 103 exp (21)
Rg Tg
CH4 þCO2 42H2 þ2CO DH298 ¼ 247 kJ=mol (14)
and the reverse water-gas shift reaction: 2.4. Solution scheme
In this study for solving reacting flow equations with the detailed
CO2 þH2 4H2 OþCO DH298 ¼ 41:1 kJ=mol (15) reaction mechanism and LangmuireHinshelwood model, the
commercial CFD package of FLUENT 6.3.26 has been used. The
The reaction rate expressions developed by Jianquo and Fro-
equations of gas flow were solved using FLUENT solver in both cases,
ment (Xu and Froment, 1989) was used to estimate the individual
while the surface and volumetric reactions from CHEMKIN output
reaction rates. The functional forms of these expressions are (Chen
file in case 1 and provided LHK file are imported and coupled with
and Elnashaie, 2005; Jarosch et al., 2002; Prabhu et al., 2000):
FLUENT. The grid was finer at the catalytic surface due to the larger
" # gradients of temperature and species concentration. The first order

KCO2 KCH4 PCO2 PCH4 PCO PH2 2 upwind method was utilized with a convergence criterion of 106
RA ¼ kA 2 1 for each scaled residual component (i.e., continuity, x-velocity, r-
1 þ KCO2 PCO2 þ KCH4 PCH4 kA PCH4 PCO2
velocity, energy, and species). According to geometry, single
(16) microchannel is axisymmetric, so half of single channel is selected
for solving transport, energy, and kinetic equations. Total of 48 cases
were designed for the modeling to study the effect of three pa-
P P
RB ¼ kB PCO2 1 CO H2 O (17) rameters including (TWall), (CH4/CO2), (CH4/CO2/H2), (CH4/CO2/CO),
kB PCO2 PH2 (CH4/CO2/H2O), and microreactor pressure. Table 2 contains main
conditions that were applied to these cases.
The rates constant of reaction routes (15) and (16) are (Prabhu
Methane and carbon dioxide conversions are an important
et al., 2000):
characteristic for DR and are defined as:

102065 ðCH4 Þin ðCH4 Þout
kA ¼ 1290 exp (18) Methane conversion ð%Þ ¼ 100 (22)
Rg Tg ðCH4 Þin
ðCO2 Þin ðCO2 Þout

73105 Carbondioxide conversion ð%Þ ¼ 100
kB ¼ 1:856 10 5
exp (19) ðCO2 Þin
Rg Tg
(23)
and absorption equilibrium constants of CO2 and CH4 are:
Table 4
Total results of influence of selected parameters on CH4 and CO2 conversion and H2/CO of dry reforming process in a microreactor (LHK model).
Exp. No. Total CH4 Total CO2 H2/CO Exp. No. Total CH4 Total CO2 H2/CO
Conversion (%) Conversion (%) Conversion (%) Conversion (%)
Exp.1 21 21 2 Exp.26 94 94 2
Exp.2 73 73 2 Exp.27 97 97 2
Exp.3 89 89 2 Exp.28 97 97 2
Exp.4 89 89 2 Exp.29 97 97 2
Exp.5 3 3 2 Exp.30 97 97 2
Exp.6 21 21 2 Exp.31 95 95 2
Exp.7 35 35 2 Exp.32 21 21 2
Exp.8 97 97 2 Exp.33 21 21 2
Exp.9 96 96 2 Exp.34 19 19 2
Exp.10 93 93 2 Exp.35 29 29 2
Exp.11 100 74 2 Exp.36 24 24 2
Exp.12 97 97 2 Exp.37 97 97 2
Exp.13 66 99 2 Exp.38 97 97 2
Exp.14 50 100 2 Exp.39 97 97 2
Exp.15 40 100 2 Exp.40 96 96 2
Exp.16 34 100 2 Exp.41 95 95 2
Exp.17 21 21 2 Exp.42 89 89 2
Exp.18 29 29 2 Exp.43 86 86 2
Exp.19 41 41 2 Exp.44 89 89 2
Exp.20 20 20 2 Exp.45 35 35 2
Exp.21 26 26 2 Exp.46 2 2 2
Exp.22 97 97 2 Exp.47 89 89 2
Exp.23 97 97 2 Exp.48 100 100 2
Exp.24 96 96 2 Exp.49 21 21 2
Exp.25 94 94 2
90 100
LHK Model-T=900K
MK Model-T=900K LHK Model
80 90
LHK Model-T=500K MK Model
MK Model-T=500K
70 80
60
70
Total CH4 Conversion(%)

CH4 Conversion(%)
60
50
50
40
40
30
30
20
20
10
10
0
0
-10
0 10 20 30 40 50 60 70 80 90 100
-10
1 1.5 2 2.5 3
Channel Length(mm) (CH4/CO2) Ratio
Fig. 2. Comparison of LHK and MK models at different temperature. Fig. 4. Effect of (CH4/CO2) ratio on total methane conversion in both kinetic models.
3. Results and discussions
In this section comparison of “LangmuireHinshelwood” kinetic

and “Microkinetic” models and the effect of six important param-
eters on the performance of microreactor that is depicted in Table 2,
are studied. All detailed results are considered in Table 4.
3.1. Comparison of LangmuireHinshelwood kinetic and

microkinetic models
Methane conversion along microreactor by using of Lang-

muireHinshelwood kinetic (LHK model) and Microkinetic (MK
model) models has been shown in Fig. 2. As shown in this figure, all
values of methane conversion at temperature of 900 K in LHK
model are higher than MK model. For example, in length of 50 mm
of microchannel, methane conversion is 70% in MK model and 10%
in LHK model. Also, two models were applied for second level of
temperature (T ¼ 500 K). For the sake of endothermally of DR re-
action, it seems that increasing of temperature has positive effect
100
90
80
Total CH4 Conversion(%)
70
60
50
40
30
20
P=10bar; CH4:CO2=0.5:0.5
P=5bar; CH4:CO2=0.5:0.5
10
0
500 1000 1500 2000
Wall Temperature(K)
Fig. 5. Effect of (CH4/CO2/H2) ratio on total methane conversion along channel in: (A)
Fig. 3. Effect of wall temperature on total methane conversion in LHK kinetic model. MK model; (B) LHK model.
on methane conversion. But results show two models have

different behavior. According to prediction, methane conversion
along microchannel has increased in LHK model, but has decreased
in MK model. So it seems LHK model has better results than MK
model in this step.Fig. 3
3.2. Effect of wall temperature
In previous section, results represented that an increase in

temperature will increase methane conversion or increase pro-
ductivity in LHK model. So for detailed review of effect of tem-
perature, total methane conversion (at end of microchannel length)
in different temperatures has been calculated. This evaluation is
considered at two pressures (5 and 10 bar). The values of total
methane conversion increases with temperature at both pressure
levels. Also, the maximum total methane conversion observes in
1200 K in both cases. Therefore, the optimum temperature must be
found for maximizing of the total methane conversion in each case. Fig. 7. Effect of (CH4/CO2/CO) ratio on total methane conversion along channel in both
kinetic models (T ¼ 1200 KeCH4:CO2: CO ¼ 0.35:0.35:0.3).
3.3. Effect of methane to carbon dioxide ratio

on methane conversion along microchannel in MK model. Three
One of the main effective parameters on hydrogen to carbon
cases in same temperature (1200 K), pressure (10 bar), and (CH4/
monoxide ratio (H2/CO) at synthesis gas product is methane to
CO2) ratio of 1, but in different hydrogen mole fraction (0.1, 0.2, and
carbon dioxide ratio (CH4/CO2). Increasing of methane to carbon
0.3) have been studied. Results show that along microchannel at
dioxide ratio in steam reforming process feed causes decreasing H2/
each length, the case with lower hydrogen content has higher
CO, but results show that ratio of (CH4/CO2) has not effect on H2/CO
methane conversion or productivity. Therefore, hydrogen repre-
ratio in DR process. Effect of (CH4/CO2) has been depicted in Fig. 4.
sents negative effect on microreactor performance in MK model.
As shown in this figure, methane conversion decreases with
On the other hand, effect of hydrogen composition at feed
increasing (CH4/CO2) ratio. As the same trend in Section 3.1, the
stream was studied in LHK model (Fig. 5-B). But, in this model
total methane conversions of LHK model are higher than MK
increasing of hydrogen mole fraction shows no significant effect on
model. For example, in ratio of 1, total methane conversions are 98%
methane conversion.
and 59% in LHK and MK models, respectively.
3.4. Effect of hydrogen composition at feed stream 3.5. Effect of carbon monoxide composition at feed stream
In industrial case, natural gas use as feed stock for reforming Similar to study of hydrogen composition effect on microreactor
plants. Natural gas feed stream usually consists of methane, carbon function, the influence of carbon monoxide composition was
dioxide, carbon monoxide, hydrogen, hydrogen sulfide, and other studied at four levels (0.05, 0.1, 0.2, and 0.3). In all cases the ratio of
components. So study of presence of these components in feed is (CH4/CO2) is equal to 1. Results in Fig. 6-A show that carbon mon-
important. Fig. 5-A shows effect of hydrogen existence in feed flow oxide composition changes have a little effect on methane
100
100
90
80
80
70
CH4 Conversion(%)
60
CH4 Conversion(%)
60
T=1200K-CH4:CO2:CO=0.5:0.5:0.0
50 T=1200K-CH4:CO2:CO=0.475:0.475:0.05 40
T=1200K-CH4:CO2:CO=0.45:0.45:0.1
40 T=1200K-CH4:CO2:CO=0.4:0.5:0.2
T=1200K-CH4:CO2:CO=0.35:0.35:0.3 20
30
20 T=1200K-CH4:CO2:CO=0.5:0.5:0.0
0 T=1200K-CH4:CO2:CO=0.475:0.475:0.05
10 T=1200K-CH4:CO2:CO=0.45:0.45:0.1
T=1200K-CH4:CO2:CO=0.4:0.4:0.2
T=1200K-CH4:CO2:CO=0.35:0.35:0.3
0 -20
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Channel Length(mm) Channel Length(mm)
Fig. 6. Effect of (CH4/CO2/CO) ratio on methane conversion along channel in: (A) LHK model; (B) MK model.
conversion in LHK model, whereas in MK model increase in carbon 97.5

monoxide composition increase the methane conversion along
microchannel length (Fig. 6-B).
For more detailed analysis, a comparison was made between the 97
two models in T ¼ 1200 K, P ¼ 10 bar, and (CH4/CO2/
Total Methane Conversion(%)

CO) ¼ 0.35:0.35:0.3. As can be seen in Fig. 7, the methane conver-
96.5
sion in each length of microchannel in LHK model is higher than
MK model. So it can be concluded that the overall behavior of
microreactor in these models does not change by varying carbon
96
monoxide composition in the feed stream.
3.6. Effect of water composition at feed stream

95.5
Among the compounds in natural gas, steam is always there.

Therefore it is necessary to examine its effect on reactor perfor- 95
mance. As shown in Fig. 8, unlike the effect of carbon dioxide on
methane conversion in the present models, influence of steam on
methane conversion in LHK model is more significant. But it is 94.5
0 0.05 0.1 0.15 0.2 0.25 0.3
noteworthy that increasing steam content in feed stream shows a
double act. The methane conversion increase along microchannel (CH4/CO2/H2O) Ratio
length up to 40 mm, but then began to decline. It seems that this
Fig. 9. Effect of (CH4/CO2/H2O) ratio on total methane conversion in LHK model
dual behavior is due to the water-gas-shift (WGS) reaction. Fig. 9
(T ¼ 1200 KeP ¼ 10 bar).
represents steam effect on the total methane conversion in LHK
model. As shown in this figure, the total methane conversion de-
creases by increasing this ratio from 97% to 95%.
3.7. Effect of microreactor pressure As mentioned above, these two factor act in the opposite di-
rection. As shown in Fig. 10, LHK model covers these trends but MK
Reactor pressure acts a key role in gas phase reactions. Pressure model is unable to predict. As shown in Fig. 11, methane conversion
effect on microreactor can be considered from two perspectives: increase up to 90% in 60 mm length but then it started to decrease.
So, it can be concluded that LHK model is better for showing of
1) With increasing pressure in constant wall temperature or pressure effect on DR in a microreactor.
adiabatic state, based on the ideal gas law, temperature of gas Fig. 11 presents the total methane conversion versus channel
bulk will increase. These factors will help conversation of pressure in both models. In the LHK model, total methane con-
methane to increase with increasing pressure. version increased slightly, after 10 bar began to decline. In this
2) According to reaction stoichiometric coefficient of DR (Equation model the methane conversion is equal to 20% at pressure of 10 bar.
(1)), based on the ”Le Chatelier's” principle, with increasing However, total methane conversion increased ongoing in MK
pressure the occurrence of reverse reaction is more possible. model.
70 100
90
60
80
50 70
CH4 Conversion(%)
CH4 Conversion(%)
60
40
50
30
40
20 30
T=700K-CH4:CO2:H2O=0.5:0.5:0.0
T=700K-CH4:CO2:H2O=0.5:0.5:0.0
T=700K-CH4:CO2:H2O=0.475:0.475:0.05 20
T=700K-CH4:CO2:H2O=0.475:0.475:0.05
10 T=700K-CH4:CO2:H2O=0.45:0.45:0.1
T=700K-CH4:CO2:H2O=0.40:0.40:0.2 10 T=700K-CH4:CO2:H2O=0.45:04.5:0.1
T=700K-CH4:CO2:H2O=0.35:0.35:0.3 T=700K-CH4:CO2:H2O=0.40:0.40:0.2
0 0
0 20 40 60 80 100 0 10 20 30 40 50 60 70 80 90 100
Channel Length(mm) Channel Length(mm)
Fig. 8. Effect of (CH4/CO2/H2O) ratio on methane conversion along channel in: (A) LHK model; (B) MK model.
100 100
P=3bar
90 P=5bar
P=8bar
80
80 P=10bar
P=12bar
70 P=16bar
CH4 Conversion(%)
CH4 Conversion(%)
60
P=20bar
60
50 40
P=1bar
40 P=3bar
P=5bar 20
30 P=8bar
P=10bar
20
P=12bar 0
P=16bar
10
P=20bar
0 -20
0 10 20 30 40 50 60 70 80 90 100 0 20 40 60 80 100
Channel Length(mm) Channel Lenght(mm)
Fig. 10. Effect of channel pressure on methane conversion along channel in: (A) LHK model; (B) MK model.
reactor was studied. The catalytic reaction takes place at the surface
of microchannel wall. Microchannel wall temperature has consid-
erable effect on methane conversion. Methane conversion is
increased fast by increasing wall temperature in LHK model and in
contrast, is decreased in MK model. Therefore, concentration of
favorable product such as hydrogen and carbon monoxide is
decreased in both axial and radial directions in LHK model.
Additional numerical modeling cases of microchannel suggest
that microchannel pressure, methane to carbon dioxide, and
hydrogen, carbon monoxide, and steam compositions in feed
stream have different effects on performance of DR. All results have
been shown in Table 5. According to results, it seems that provided
C code for LangmuireHinshelwood Kinetic model of DR suggests
more rational and appropriate responses than microkinetic model.
References
Fig. 11. Effect of channel pressure on total methane conversion: LHK model; MK model
Bird, R.B., Stewart, W.E., Lightfoot, E.N., 2006. Transport Phenomena. Wiley.
(T ¼ 1200 KeCH4:CO2 ¼ 0.4:0.4).
Bitter, J.H., Seshan, K., Lercher, J.A., 1997. The State of Zirconia supported platinum
catalysts for CO2/CH4reforming. J. Catal. 171, 279e286.
Chen, Z., Elnashaie, S.S.E.H., 2005. Bifurcation and its implications for a novel
autothermal circulating fluidized bed membrane reformer for the efficient pure
hydrogen production. ChEnS 60, 4287e4309.
In Table 5, brief results of effective parameters increasing on Chen, J., Yao, C., Zhao, Y., Jia, P., 2010. Synthesis gas production from dry reforming
methane conversion of DR process in a microreactor have been of methane over Ce0.75Zr0.25O2-supported Ru catalysts. IJHE 35, 1630e1642.
presented. Conant, T., Karim, A., Datye, A., 2007. Coating of steam reforming catalysts in non-
porous multi-channeled microreactors. Catal. Today 125, 11e15.
Corthals, S., Witvrouwen, T., Jacobs, P., Sels, B., 2011. Development of dry reforming
catalysts at elevated pressure: D-optimal vs. full factorial design. Catal. Today
4. Conclusion 159, 12e24.
Delsman, E.R., Laarhoven, B.J.P.F., De Croon, M.H.J.M., Kramer, G.J., Schouten, J.C.,
2005. Comparison between conventional fixed-bed and microreactor technol-
The effect of six key parameters Microchannel wall temperature, ogy for a portable hydrogen production case. Chem. Eng. Res. Des. 83,
microchannel pressure, CH4/CO2, hydrogen, carbon monoxide, and 1063e1075.
steam concentration in feed stream on DR of a microchannel Ding, S., Wu, C., Cheng, Y., Jin, Y., Cheng, Y., 2010. Analysis of catalytic partial
oxidation of methane on rhodium-coated foam monolith using CFD with
detailed chemistry. ChEnS 65, 1989e1999.
Table 5 Erdohelyi, A., Cserenyi, J., Solymosi, F., 1993. Activation of CH4 and its reaction with
Brief results of influence of selected parameters on methane conversion of dry CO2 over supported Rh catalysts. J. Catal. 141, 287e299.
reforming process in a microreactor Foo, S.Y., Cheng, C.K., Nguyen, T.-H., Adesina, A.A., 2012. Syngas production from
CH4 dry reforming over CoeNi/Al2O3 catalyst: coupled reaction-deactivation
Parameter Twall CH4/CO2 CH4/CO2/H2 CH4/CO2/CO CH4/CO2/H2O P kinetic analysis and the effect of O2 co-feeding on H2:CO ratio. Int. J. Hydrog.

Name ( C) (bar) Energy 37, 17019e17026.
MK Model Y Y Y [ Effectless [ Gao, J., Hou, Z., Liu, X., Zeng, Y., Luo, M., Zheng, X., 2009. Methane autothermal
reforming with CO2 and O2 to synthesis gas at the boundary between Ni and
LHK Model [ Y Effectless Effectless Y [Y
ZrO2. IJHE 34, 3734e3742.
Guo, J., Gao, J., Chen, B., Hou, Z., Fei, J., Lou, H., Zheng, X., 2009. Catalytic conversion Xu, J., Froment, G.F., 1989. Methane steam reforming, methanation and water-gas
of CH4 and CO2 to synthesis gas on Ni/SiO2 catalysts containing Gd2O3 pro- shift: I. Intrinsic kinetics. AICHE J. 35, 88e96.
moter. IJHE 34, 8905e8911. Yin, L., Wang, S., Lu, H., Ding, J., Mostofi, R., Hao, Z., 2007. Simulation of effect of
He, S., Wu, H., Yu, W., Mo, L., Lou, H., Zheng, X., 2009. Combination of CO2 reforming catalyst particle cluster on dry methane reforming in circulating fluidized beds.
and partial oxidation of methane to produce syngas over Ni/SiO2 and NieAl2O3/ Chem. Eng. J. 131, 123e134.
SiO2 catalysts with different precursors. IJHE 34, 839e843.
Jarosch, K., El Solh, T., de Lasa, H.I., 2002. Modelling the catalytic steam reforming of
methane: discrimination between kinetic expressions using sequentially
designed experiments. ChEnS 57, 3439e3451. Nomenclature
Kolb, G., Hessel, V., 2004. Micro-structured reactors for gas phase reactions. Chem.
Eng. J. 98, 1e38.
Lebens, P.J.M., Heiszwolf, J.J., Kapteijn, F., Sie, S.T., Moulijn, J.A., 1999a. Gaseliquid Acronyms
mass transfer in an internally finned monolith operated countercurrently in the
film flow regime. Chem. Eng. Sci. 54, 5119e5125.
Lebens, P.J.M., Stork, M.M., Kapteijn, F., Sie, S.T., Moulijn, J.A., 1999b. Hydrodynamics 2D: Two Dimensional
and mass transfer issues in a countercurrent gas-liquid internally finned CFD: Computational Fluid Dynamic
monolith reactor. Chem. Eng. Sci. 54, 2381e2389. MK: Microkinetic
Lebens, P.J.M., Kapteijn, F., Sie, S.T., Moulijn, J.A., 1999c. Potentials of internally fin- LHK: LangmuireHinshelwood
ned monoliths as a packing for multifunctional reactors. Chem. Eng. Sci. 54, UDF: User Defined Function
1359e1365. WGS: Water-Gas-Shift
Lee, S.-H., Cho, W., Ju, W.-S., Cho, B.-H., Lee, Y.-C., Baek, Y.-S., 2003. Tri-reforming of DR: Dry Reforming
CH4 using CO2 for production of synthesis gas to dimethyl ether. Catal. Today 87,
133e137. Notation
McGuire, N.E., Sullivan, N.P., Deutschmann, O., Zhu, H., Kee, R.J., 2011. Dry reforming
of methane in a stagnation-flow reactor using Rh supported on strontium-
substituted hexaaluminate. Appl. Catal. A 394, 257e265. A: Pre-exponential coefficient in mol, m, s,K
Meshkani, F., Rezaei, M., 2010. Nanocrystalline MgO supported nickel-based CP: Specific heat capacity, J kg1 K1
bimetallic catalysts for carbon dioxide reforming of methane. IJHE 35, Di,m: MaxwelleStefan diffusivity of speciesi, m2 s1
10295e10301. Di,T: Thermal diffusivity of speciesi, m2s1
Osaki, T., Mori, T., 2001. Role of potassium in carbon-free CO2 reforming of methane Ea: Activation energy, J mol1
on K-Promoted Ni/Al2O3 catalysts. J. Catal. 204, 89e97. Ji,r: Radial mass flux of speciesi, kg m2 s1
Pompeo, F., Nichio, N.N., Souza, M.M.V.M., Cesar, D.V., Ferretti, O.A., Schmal, M., Ji,x: Axial mass flux of speciesi, kg m2 s1
2007. Study of Ni and Pt catalysts supported on a-Al2O3 and ZrO2 applied in k: Thermal conductivity, W m1 K1
methane reforming with CO2. Appl. Catal. A 316, 175e183. kf,n: Forward reaction rate for reactionn, in mol, m, s
Prabhu, A.K., Liu, A., Lovell, L.G., Oyama, S.T., 2000. Modeling of the methane Mi: Molecular weight of speciesi, kg.mol1
reforming reaction in hydrogen selective membrane reactors. J. Membr. Sci. 177, Ng: Total number of gas species
83e95. Ns: Total number of absorbed species
Richardson, J.T., Paripatyadar, S.A., 1990. Carbon dioxide reforming of methane with P: Pressure, Pa
supported rhodium. Appl. Catal. 61, 293e309. r: Radial coordinate, m
Rostrup-Nielsen, J.R., Christiansen, L.J., 1995. Internal steam reforming in fuel cells R: Universal gas constant, J K1 mol1
and alkali poisoning. Appl. Catal. A 126, 381e390. Si: Formation or consumption rate of speciesi, mol m2 s1
Roy, S., Bauer, T., Al-Dahhan, M., Lehner, P., Turek, T., 2004. Monoliths as multiphase t: Time, s
reactors: a review. AIChE J. 50, 2918e2938. T: Temperature, K
Ruckenstein, E., Hu, Y.H., 1995. Carbon dioxide reforming of methane over nickel/ u: Axial velocity, m/s
alkaline earth metal oxide catalysts. Appl. Catal. A 133, 149e161. y: Radial velocity, m/s
Sadykov, V.A., Gubanova, E.L., Sazonova, N.N., Pokrovskaya, S.A., Chumakova, N.A., x: Axial coordinate, m
Mezentseva, N.V., Bobin, A.S., Gulyaev, R.V., Ishchenko, A.V., Krieger, T.A., ½Xj : Molar concentration of speciesj, mol m3
Mirodatos, C., 2011. Dry reforming of methane over Pt/PrCeZrO catalyst: kinetic Yi: Mass fraction of species i
and mechanistic features by transient studies and their modeling. Catal. Today
171, 140e149. Greek Letters
Serrano-Lotina, A., Martin, A.J., Folgado, M.A., Daza, L., 2012. Dry reforming of
methane to syngas over La-promoted hydrotalcite clay-derived catalysts. Int. J. b: Temperature exponent
Hydrog. Energy 37, 12342e12350.
g: Sticking coefficient
Shang, R., Guo, X., Mu, S., Wang, Y., Jin, G., Kosslick, H., Schulz, A., Guo, X.-Y., 2011. G: Site density, mol m2
Carbon dioxide reforming of methane to synthesis gas over Ni/Si3N4 catalysts. ε: Coverage correction energy, J mol1
IJHE 36, 4900e4907. Q: Surface site fraction
Verykios, X.E., 2003. Catalytic dry reforming of natural gas for the production of m: Dynamic viscosity, Pa s
chemicals and hydrogen. IJHE 28, 1045e1063.
r: Mass density, kg/m3
Wang, S., Lu, G.Q., 1998. Role of CeO2 in Ni/CeO2eAl2O3 catalysts for carbon dioxide yi,n: Stoichiometric coefficient of speciesi for reactionn
reforming of methane. Appl. Catal. B 19, 267e277. 4: Coverage exponent
Wei, J.-M., Xu, B.-Q., Li, J.-L., Cheng, Z.-X., Zhu, Q.-M., 2000. Highly active and stable
Ni/ZrO2 catalyst for syngas production by CO2 reforming of methane. Appl.
Catal. A 196, L167eL172.

28-3-62-Modeling of Microreactor For Methane Dry Reforming - Comparison of Langmuir-Hinshelwood Kinetic and Microkinetic Models

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

28-3-62-Modeling of Microreactor For Methane Dry Reforming - Comparison of Langmuir-Hinshelwood Kinetic and Microkinetic Models

Uploaded by

Copyright:

Available Formats

Journal of Natural Gas Science and Engineering 20 (2014) 99e108

Contents lists available at ScienceDirect

Journal of Natural Gas Science and Engineering

Modeling of microreactor for methane dry reforming: Comparison of

1. Introduction current criticism on DR, pointing to the lack of competitiveness of

Variables Twall (K) CH4/CO2 CH4/CO2/H2 CH4/CO2/CO CH4/CO2/H2O P(atm)

Level-1 500 0.75 0.5/0.5/0.0 0.5/0.5/0.0 0.5/0.5/0.0 1.0

Exp. No. Twall (K) CH4/CO2 CH4/CO2/H2 CH4/CO2/CO CH4/CO2/H2O P(atm)

Exp.1 500 1.0 No exist H2 No exist CO No exist H2O 5.0

The local dynamic viscosity is obtained based on the Chapman-

(5) Chemical reactions on the wall of the catalytic reactor lead to a

2.3.2. LangmuireHinshelwood kinetic model

and the reverse water-gas shift reaction: 2.4. Solution scheme

ðCO2 Þin ðCO2 Þout

Total CH4 Conversion(%)

3. Results and discussions

In this section comparison of “LangmuireHinshelwood” kinetic

3.1. Comparison of LangmuireHinshelwood kinetic and

Methane conversion along microreactor by using of Lang-

on methane conversion. But results show two models have

3.2. Effect of wall temperature

In previous section, results represented that an increase in

3.3. Effect of methane to carbon dioxide ratio

conversion in LHK model, whereas in MK model increase in carbon 97.5

two models in T ¼ 1200 K, P ¼ 10 bar, and (CH4/CO2/

Total Methane Conversion(%)

3.6. Effect of water composition at feed stream

Among the compounds in natural gas, steam is always there.

You might also like