international journal of hydrogen energy 34 (2009) 12921300

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Autothermal reforming of methane to synthesis gas:

Modeling and simulation
M. Zahedi nezhada, S. Rowshanzamira,b,*, M.H. Eikanic
a

Green Research center, Iran University of Science and Technology, Tehran, Iran
School of Chemical Engineering, Iran University of Science and Technology, Narmak, Tehran 16846-13114, Iran
c
Department of Chemical Industries, Iranian Research Organization for Science & Technology (IROST), Tehran, Iran
b

article info

abstract

Article history:

Autothermal reforming (ATR), that is the combination of non-catalytic partial oxidation

Received 10 August 2008

and adiabatic steam reforming, is an important process to produce synthesis gas (syngas)

Received in revised form

from natural gas. The main scope of this work is proposing a mathematical model

15 November 2008

considering an autothermal reformer consisting of two distinct sections; a combustion

Accepted 25 November 2008

section and a catalytic bed section. In the combustion section, temperature and compo-

Available online 4 January 2009

sition were predicted using 108 simultaneous elementary reactions considering 28 species.
The results were considered as initial conditions for the catalytic bed section. A one-

Keywords:

dimensional heterogeneous reactor model was used for kinetic simulation of the second

Autothermal reforming

section. Results of the model were compared by ATR process published data.

Modeling

2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights

Synthesis gas

1.

Introduction

Synthesis gas is a mixture of hydrogen and carbon monoxide

used in a variety of petrochemical and metallurgical process.
Syngas is used primarily for the synthesis of methanol and
oxochemicals [1].
There are three major thermochemical reforming techniques used to produce syngas from hydrocarbon fuels, i.e.
steam reforming (SR), partial oxidation (POX), and autothermal reforming (ATR). Autothermal reforming combines
partial oxidation and steam reforming (Fig. 1) [2]. ATR is
a stand-alone process, in which the entire hydrocarbon
conversion is completed in one reactor [1].
In general, there are two types of ATR systems. The first
one is compact and useful for fuel cell applications. It has
just a catalyst bed in which combustion and steam reforming
reactions occur on it simultaneously. The second one has
two separate sections, in the first section non-catalytic

reserved.

partial oxidation occurs using burner (flame mode) and

steam reforming reactions takes place in the catalyst bed.
The latter one is ideally proper for gas to liquid (GTL)
applications.
For the first type, several modeling efforts can be found in
literature. Bieshenvel and Kramer [3] carried out 1-D modeling
of catalytic autothermal reforming of gaseous hydrocarbon
fuel to synthesis gas. The model defines two subsequent
sections in the reactor; an upstream oxidation section and
a downstream reforming section. This model does not
describe mass transfer to the catalyst surface or reaction at
the catalyst surface in any detail, but is based on effective rate
equations expressed in gas-phase properties which make it
more straightforward to arrive at a thermodynamically
consistent reactor model.
Other researchers such as Avel et al. [4], Lin et al. [5], and De
Groote and Froment [6] also have developed kinetic models to
simulate the catalytic autothermal reforming.

* Corresponding author. Green Research center, Iran University of Science and Technology, Tehran, Iran. Tel.: 98 21 77491223; fax: 98
21 77491242.
E-mail address: rowshanzamir@iust.ac.ir (S. Rowshanzamir).
0360-3199/$ see front matter 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2008.11.091

international journal of hydrogen energy 34 (2009) 12921300

Nomenclature
heat capacity of bulk gas, kJ/kg K
mole fraction
gas diffusivity, m2/s
activation energy, kJ/kmol ( j 46)
superficial mass flow rate, kg/m2 s
enthalpy of species in combustion section, kJ/
kmol
mass transfer coefficient between gas and
hDi
catalyst, m/s
adsorption enthalpy of species i, kJ/kmol
DHi
heat of reaction j ( j 46), kJ/kmol
DHj
Colburn factor
JD
rate constant of reaction j ( j 46)
kj
constant
koj
equilibrium constant of reaction j ( j 46)
Kej
adsorption constant of species i
Ki
constant
Koi
kcat,g,m heat conduction coefficient of catalyst, gas and
bulk, w/m K
L
number of reactions in combustion section
M
molecular weight, kg/kmol
_
m
mass flow rate, kg/s
N
number of species in combustion section
PH2 , CH4,. partial pressure of H2., bar
rate of reaction j in catalyst section, kmol/kg cat. h
Rj
rate of reaction j in combustion section, kmol/h
R0j
R
universal gas constant, kJ/kmol K
Re
Reynolds number
Cp
C
D
Ej
G0
hi

Hagh [7] developed a framework for theoretical interpretation of reforming reactions that is developed using an atomic
balance approach. ATR feed is assumed to be pure methane but
the approach can also be applied to other hydrocarbon feeds.
This theoretical framework is used to determine the boundaries of possible solutions for data analysis (i.e. reforming
reaction space) and maximum monolith temperature. Finally,
H2 yield is determined based on energy and material balance
coupled with chemical equilibrium requirements.
In another work, Chan and Wong [8] in addition to development of a 1-D, unsteady modeling of a catalytic autothermal methanol reformer; a complete thermodynamic
analysis have described, too.
Hoang and Chan [9] developed a 2-D unsteady modeling of
catalytic autothermal reforming of methane. The model
covers all aspect of major chemical kinetics and heat and
mass transfer phenomena in the reformer.
Lattner and Harold [10] evaluated several reactor types for
the (ATR) of hydrocarbon fuels for the production of hydrogen
in PEM fuel cell systems. Each ATR reactor is integrated into an
overall process model including the fuel cell, heat integration
exchangers, and water recycle.
Lin et al. [11] developed a dynamic model for a methane
fuel processor and different control structures can be evaluated based on the disturbance rejection capability.
Barrio et al. [12] investigated catalytic partial oxidation
(CPO) reactions of methane in the presence of steam (low

ri
Scat
S
Sc
T
t
u
yi
z

1293

conversion rate of species i, kmol/kg cat. h

catalyst area per volume of catalyst bed, m2/m3
cross-section area, m2
Schmidt number
temperature, K
time, S
superficial gas velocity, m/s
mole fraction of species in combustion section
axial distance in catalyst bed

Greek symbols
3
void fraction of catalyst bed
effectiveness factor of reaction j ( j 46)
hj
catalyst density, kg/m3
rcat
rg
gas density, kg/m3
rm
catalyst bed bulk density, kg/m3
j
constant
dynamic viscosity of gas, kg/m s
mg
vjk v00jk  v0jk difference between stoichiometric
coefficients of backward and foreword reaction in
combustion section
Subscript
cat
g
i
j
s

catalyst
gas phase
gas species
reaction index
solid phase

Superscript
in
inlet

temperature CPO, LTCPO) over a noble metal catalyst. A quasihomogeneous one-dimensional model was developed in
order to model a lab-scale fixed-bed reactor to produce syngas.
These model calculations can contribute to the optimization

Fig. 1 Diagram of an ATR reactor [2].

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international journal of hydrogen energy 34 (2009) 12921300

of the process with respect to the formation of important hot

spots.
Chan and Ding [13] improved their previous 2-D kinetic
model by including the diffusion of gas species into the catalysts, non-plug flow gas velocity profile and non-uniform
catalyst porosity in the reformer.
Choi et al. study [14] investigates (ATR) of fuel cell-grade
methanol as a method for producing hydrogen for transportation applications. The model of the autothermal
reforming reaction is developed based on equilibrium product
calculations.
Ersoz [15] discussed the effects of reforming operation
parameters on the product distribution and conversion efficiency of hydrocarbon mixtures. The ASPEN-HYSIS 3.2
process simulation software code has been utilized for the
calculations of the whole fuel processing systems.
Tan et al. [16] investigated design of a catalytic methaneto-proton exchange membrane fuel cell (PEMFC) grade
hydrogen conversion system consisting of indirect partial
oxidation (IPOX), watergas shift (WGS) and preferential
carbon monoxide oxidation (PROX) reactors using modeling
and simulation techniques. Steady-state simulation, design
and sizing of reactors, which are considered to be packed-bed
tubular type, are carried out for twelve different feed compositions and PEMFC power output configurations. These results
are then used as boundary conditions to estimate the catalyst
weights in each reactor via simulations conducted using
a one-dimensional pseudo-homogeneous reactor model.
At the other hand, regarding to the second type, there is not
enough published paper describing modeling and simulation
close to this type, Yong [17] developed a simulation program of
secondary reformer in the ammonia plant. In this model
oxygen-rich air is used as a feed of secondary reformer.
In the present work, temperature and gas composition in
the combustion section have been determined by the 108
simultaneously elementary reactions and their kinetic equations proposed by Karim et al. [18]. The temperature profiles of
the gas and catalyst surface as well as the gas composition
have been predicted with a 1-D heterogeneous catalytic
reaction model. The kinetic model suggested by Xu and Froment [19] has been used to simulate catalytic bed section.

2.

1. Closed system like that does not perform mass transfer

from its boundary.
2. Reactants are well-premixed gases that combusted after an
ignition delay time spontaneously.
3. In this system, there are no hydrodynamic and mass
transfer limitations, and only chemical kinetic is controlling the reaction rate.
4. The temperature of each species is equal to total temperature of combustion mixture.
5. Rate of elementary reactions is limited and can be calculated by corrected Arenious equations.
6. The number of present species is 29 with Ar as diluents.
7. Gas mixture arises from combustion have the same
manner with an ideal gas.

Kinetic model

Two separate models were used to study partial oxidation and

catalytic steam reforming simultaneously. As follows, each of
them was described.

2.1.

mechanism of reactions is based on multi-dimensional

continuous stirred tank reactor (CSTR) and batch adiabatic
reactor models. Multi-dimensional CSTR model with premixed flow of fuel and oxidant assumption forms a set of
differential equations for conservation of mass and energy for
all of the species [20]. In these kinetic models it is always tried
to eliminate another effective parameters on process. In this
manner, it is possible to consider an ideal closed system as
a combustion zone with no mass transfer. Premixed fuel and
oxidant as reactants get ready for combustion in the
combustion zone, which usually supposed a batch reactor, at
specified volume, temperature, and pressure.
After enough time, components of mixture reach to equilibrium concentration and do not change the temperature,
pressure and density of the gas. There are some methods to
explain these problems which are classified by different
process thermodynamic conditions [21].
To set kinetic mechanism of methane partial oxidation,
the most extensive and exact ones has been used. The
chemical kinetic reaction mechanism employed in this
investigation was based on the model introduced by Karim
et al. which considered partial oxidation of methane under
isothermal conditions [18]. The complete mechanism for
simulating the oxidation of methane consists of 108 singlestep elementary reactions in which 28 species are involved.
The adiabatic system is in isobaric state, the condition that
is near to industrial reactors. Assumptions of model are as
follows:

Mathematical description of partial oxidation mechanism

with selection of kinetic model and determination of input
data, by using mass and energy balance equations, lead to a set
of ordinary differential equations (ODEs) [22]. Mass conservation equation of species for all models is the same and is

Simulation of partial oxidation section

woi

Simultaneous study of the fluid hydrodynamic and kinetics of

the combustion reactions in the industrial reactors, which
always have turbulent diffusion flames, is very complicated.
To solve these problems using some simple assumptions may
be useful. Assuming that the rate of chemical reactions in the
combustion zone is independent of hydrodynamic of the
system is a proper theory to determine the released heat,
concentration of species and reaction temperature in the
combustion section. This theory with a reliable kinetic

L
X

nij R0j

j 1; 2; .; N

(1)

j1

Energy equation for the considered kinetic model is selected

on the basis of first law of thermodynamics. For adiabatic and
isobaric system it is

Cp

N
X
dT
hi woi Mi 0
n
dt
i1

where

(2)

international journal of hydrogen energy 34 (2009) 12921300

Cp

yi Cp;i

(3)

i1

None-adiabatic systems need the models for description of

heat transfer inside and outside of the combustion zone and
so lead to more complicated energy equations.
To complete kinetic simulation, the set of differential
equations which consist of N mass balance equation of
species and energy balance were solved by numerical method.
This kind of equations is initial value problem and need to
determine initial conditions. Initial condition of model can be
determined by calculating initial value of reactants and diluents by operating conditions (total pressure of the system,
initial temperature, equivalence ratio, water to methane ratio,
CO2 to methane ratio and percentage of diluents).
The used numerical method in this model is based on
multi-step BDF-TR method that allocated with NDF method
for simulation of stiff equations of chemical kinetic.

2.2.

Simulation of catalytic bed section

2.2.1.

Chemical reaction scheme

As the same as previous section, mass balance of species and

energy conservation was considered. The gas mixture
produced in the first section was assumed to be the feed gas
entering into the catalytic bed section. It was also assumed
that only main components such as methane, steam, carbon
dioxide, carbon monoxide and hydrogen enter into the catalytic bed and the other components were ignored because of
their negligible quantities. In the catalyst bed, only the reactions with significant rates were considered. In this section
three main reactions are as follows:
CH4 H2 O4CO 3H2
CO H2 O4CO2 H2

DH298 206; 000 kJ=kmol

DH298 41; 000 kJ=kmol

CH4 2H2 O4CO2 4H2

DH298 165; 000 kJ=kmol



k2
pH pCO2
1
pCO pH2 O  2

pH2
Ke5
DEN2

R6

p4H pCO2
k3
pCH4 p2H2 O  2
3:5
Ke6
pH2

!


DEN 1 KCO pCO KH2 pH2 KCH4 pCH4

As a consequence, the conversion rates of the individual

species are as follows:
rCH4 h4 R4  h6 R6

(11)

rCO2 h5 R5 h6 R6

(12)

rCO h4 R4  h5 R5

(13)

rH2 O h4 R4  h5 R5  2h6 R6

(14)

rH2 3h4 R4 h5 R5 4h6 R6

(15)

(6)

(9)

where ri is the conversion rate of gas species i (i CH4, O2,.); hj

is the effectiveness factor of reaction j whose values are taken
from Ref. [6].

2.2.2.

Mathematical model

Reforming reactor was considered as a cylinder filled with

catalyst. Specifications of the catalyst are shown in Table 4. To
simplify the model, it was assumed that the gas properties
and flow were uniform at the inlet cross-section of the reactor.

Table 1 Kinetic parameters of Eqs. (7)(9).

Reaction

where
KH O pH2 O
2
pH2

h
re Observed effective rate; averaged over the pellet volume
rb Intrinsic chemical rate; under bulk fluid phase conditions

(5)

(8)

DEN2

Rj (kmol/kg cat. h) is the rate of reaction j ( j reactions (4)(6));

pCH4 , pO2 , etc. are partial pressures of gas species CH4, O2, etc.,
kj koj  eEj =RT is the kinetic rate constant of reactions j
( j reactions (4)(6)), in which k2k4 are from Xu and Froment
[19]. The kinetic data are shown in Table 1. koj is constant, Ej
(kJ/kmol) is the activation energy, R (kJ/kmol K) is the universal
gas constant; T (K) is the gas temperature in the reaction zone;
Kej is the equilibrium constant of reaction j ( j reactions (4)
(6)) presented in Table 2; Ki Koi  eDHi =RT is the adsorption
constant of species i (i CO, H2, .) in the reforming reactions
in equations (46) can be found in Table 3.
The rate of consumption or formation of an individual gas
species based on the reactions in Eqs. (4)(6) is determined by
summing up the reaction rates of those species in the three
reactions. It should be noted that, to extract the kinetic data
from a standard industrial catalyst pellet filled reactor (other
than fine catalyst powder used in laboratory), one has to
consider the intraparticle mass transport limitations [23],
which significantly reduce the reaction rates in the Equations
(7)(9) with kinetic data shown in Tables 13. To account for
this shortcoming, average reaction rates were suggested by De
Groote and Froment [6], were determined by multiplying the
rates (Eqs. (7)(9)) with various effectiveness factors h4 0.07,
h5 0.7 and h6 0.06, respectively. The effectiveness factor is
used as a measure for diffusional resistances, for ith reaction
and is defined by

(4)

Since soot formation can be avoided by using a specific

burner design and through controlling the operating condition, all reactions related to carbon deposition and carbon
gasification can be ignored.
Most of catalysts used for ATR reactors are Ni-based. A
Nickel catalyst supported by a magnesiumalumina spinel
carrier has shown high stability and activity for ATRs [1].
Kinetic rate equations for steam reforming and watergas
shift reactions (Eqs. (4)(6)) are adopted from Xu and Froment
[19]. The kinetic rate equations are as follows:
!
p3H2 pCO
k1
1

(7)
R4 2:5 pCH4 pH2 O 
Ke4
pH2
DEN2
R5

1295

(10)

4
5
6

koj(kmol/kg cat. h)
6

1

1.955  10 bar
1.020  1015 bar0.5
5.852  1017 bar1.5

Ej (kJ/kmol)
67130
243,900
204,000

1296

international journal of hydrogen energy 34 (2009) 12921300

Table 2 Equilibrium constants of Eqs. (7)(9).

Reaction

Table 4 Specifications of the catalyst.

Equilibrium constant Kej

12

4
5
6

5.75  10 exp (11476/T ) (bar )

1.26  102 exp (4639/T )
7.24  1010 exp (21646/T ) (bar2)

Also it was assumed that the reactor was adiabatic and

temperature of catalyst surface was equal to gas phase. The
supposed phenomena in the reactor were chemical reactions
on the catalyst surface and heat and mass transfer in the axial
direction of the reactor in the solid and gas phase.
In this model, temperature and concentration changes in
the radial direction were ignored. From design point of view, it
is desired to have a homogenous gas and temperature distribution at catalyst bed entrance [1] and minimum height of
catalyst bed. Therefore elimination of change in radial direction does not make noticeable error in final results. Usually for
prevention of catalyst damage against heat radiation from the
burner flame and uniform distribution of products of
combustion zone on catalyst bed, heat resistant catalysts and/
or inert alumina balls may be used at the above of the bed.
The basic equations of the model are based on the mass
and energy balance for the gas and solid phases of the
reformer.
Mass balance equation in the gas phase is
 2 


vCi
vCi
v Ci
hDi Scat Csi  Ci
u
Di
3
vt
vz
vz2

(16)

By assuming occurring chemical reactions on the catalyst

surface, concentration difference inside of solid phase will be
neglected and related terms equal zero. Thus, mass balance
equation in the solid phase is
rcat ri

Active metal:
Active metal content:
Metal distribution:
Type:
Support:
Surface area:
Mean particle size:
Bulk density:
Crush strength:
Length of catalytic bed:



M
hDi Scat Csi  Ci
rg

(17)

where
hDi JD

Sci

(18)

rg Sci 2=3

mg
rg Di

(19)

j
JD 0:91Re
JD 0:61Re0:41 j
Re G0 dp

Re < 50
Re > 50

(20)

.

1  3  mg

(21)

where hD (m/s) is mass transfer coefficient between catalyst

and gas, Sc is Schmidt number, Di (m2/s) is the gas diffusivity of

Table 3 Adsorption constants of Eq. (10).

Species
CH4
CO
H2
H2O

species i, which can be calculated with the SlatteryBird

formula [24]:
b

T
DAB a  p PCA PCB 1=3 TCA TCB 5=12
TCA TCB
(22)
1=2 .

1
1


P
MA MB
j is a coefficient depending on the particle shape; for spherical
particle j has a value of 1; G0 (kg/(m2 s)) is the superficial mass
_ divided by the
flow rate, which is defined as mass flow rate m
cross-section area S, of the reformer:
G0

_
m
S

(23)

In this model it is assumed that the medium of catalyst bed is

isotropic i.e. radiative effects, viscous dissipation and the
work done by pressure changes are negligible. Thus, there is
local thermal equilibrium and so, Ts Tg T, where Ts and Tg
are the temperatures of the solid and gas phases, respectively.
It is also assumed that heat conduction in the solid and fluid
phases take place in parallel so that there is no net heat
transfer from one phase to the other [25].
With this assumption, energy balance in this system is
 2 
4
X


vT
vT
v T
1  3
(24)
DHj hj Rj
rcm rcf u Km
2
vt
vz
vz
j1
where:

G0

0:51

Nickel
9.8% on dry basis
Edge
Reduced; dry
Alumina spheres
155 m2/g
2.2 mm
0.55 g/cm3
2.52 kg
350 mm

Koi (/bar)

DHi (kJ/kmol)

6.65  104
8.23  105
6.12  109
1.77  105 bar

38280
70650
82900
88680

rcp


m

 
 
1  3 rcp cat 3 rcp g

km 1  3kcat 3kg

(25)
(26)

At above, i denotes the gas species; j denotes reaction index;

rg, rcat and rm(kg/m3) are the densities of gas, catalyst and
catalyst bed bulk, respectively; Cpg and Cpm (J/kg K) are the
specific heats of gas and of catalyst bed, respectively; 3 is the void
fraction of catalyst bed; T (K) is the temperature of gas and solid
phase; Csi and Ci are the fractions of gas species i on the catalyst
surface and in the gas phase respectively; Scat (m2/m3) is the
catalyst surface area per volume of catalyst bed; dHj (J/mol) is the
heat of reaction j; K (w/m K) is the heat conduction coefficient; u
(m/s) is the superficial gas velocity that is equal to the ratio of
volume flow rate to the cross-section area of the reformer.
Equations (15), (16) and (23) form a set of 11 simultaneous
partial differentixtal equations for CH4, H2O, H2, CO, CO2; with
the following initial and boundary conditions:

at t 0; T T0 & Ci Cin
i

(27)

1297

international journal of hydrogen energy 34 (2009) 12921300

T Tin & Ci Cin

i

(28)

2000

at z L;

vCi
vT
0 &
0
vz
vz

(29)

1750

These equations were solved for the temperature and gas

concentration along the reformer using finite difference
method.

3.

Results and discussion

Temperature (K)

at z 0;

1500

1250

1000

To compare the results of the model with experimental data

published by Christensen and Primdahl [1], the same initial
operating conditions were selected as O2/CH4 0.59 (equivalence ratio 3.38), CO2/CH4 0.12, H2O/CH4 0.6 and
T 700 K, and P 21 bar. In these conditions, the results of
partial oxidation section are shown in Figs. 2 and 3. Figs. 2 and
3 show changes of mole fraction and temperature profiles vs.
time, respectively. Fig. 2 shows trend of change of some stable
species for an adiabatic and isobaric process. An inspection of
the species profile in this figure suggests that there are three
distinct reaction zones named inductive, heat release and
equilibrium. Inductive zone is a short time which spends in
preparing the species for beginning of the combustion reactions. Along this time, while concentration of initial reactants
such as O2 and CH4 almost remain without change, concentration of unstable chemicals such as O, H, OH, CH3 radicals
increase to start the partial oxidation reaction from zero to
noticeable quantity. After that, called ignition delay time,
immediately heat release step begins with rapid increasing
of temperature and change of species concentration rate. In
this step mole concentration of intermediate and unstable
species reach to maximum quantity and then rapidly
decrease. As a result of rapid improvement of exothermic
combustion reactions, in this step, temperature of the mixture
achieves its maximum quantity, Fig. 3. With rapid decrease of
mole fraction of oxygen and methane, concentration of stable
products such as CO and H2 were increased and get close to
the final quantity. When species of intermediate radicals

750
0

0.25

0.5

0.75

Time (Second)
Fig. 3 Profile of temperature vs. time in the POX section.
At H2O/CH4 [ 0.6, CO2/CH4 [ 0.12, O2/CH4 [ 0.59,
P [ 21 bar, T [ 700 K.

reach to maximum quantity, heat release zone was finished

with consumption of the rather entire oxygen and then,
equilibrium step begins.
In equilibrium zone, concentrations of the intermediate
radical species decrease rapidly and get close to its small
equilibrium quantities. Concentration of the stable species
goes ahead with mild slip to their equilibrium quantities.
Temperature decreases as a result of occurrence of endothermic reactions and finally reaches to a fixed value. Extension of each of these zones depend to the applied operating
conditions in the kinetic simulation, for example, use of
higher initial temperatures and lower equivalence ratios lead
to shorter inductive zone and significantly decrease the time
required to reach to equilibrium. As can be seen in Fig. 2, at
first, production of CO and H2 delayed until the formation of
H2O. The production of H2 begins with reaction progress and
temperature increase. It shows that the partial oxidation of
1650

0.5
1600

0.4

H2

Temperature (K)

Mole fraction of species

CH4

H2O

0.3

H2O
CO

O2
0.2

0.1

CH4

CO2

1550

1500

1450

CO2
0

0.25

0.5

0.75

Time (Second)
Fig. 2 Mole fraction of species vs. time in the POX section
at H2O/CH4 [ 0.6, CO2/CH4 [ 0.12, O2/CH4 [ 0.59,
P [ 21 bar, T [ 700 K.

1400

0.25

0.5

0.75

Relative Length
Fig. 4 Profile of temperature along the catalyst bed at H2O/
CH4 [ 0.6, CO2/CH4 [ 0.12, O2/CH4 [ 0.59, P [ 21 bar.

1298

international journal of hydrogen energy 34 (2009) 12921300

0.5

Table 6 Comparison between the results of the model

with experimental data.
Species
CH4
H2
CO2
CO
H2O

Mole fraction

0.4

0.3

H2
N2
CO
CO2
Ar
CH4
H2O
H2/CO
Pressure (bar)
Temperature (K)

0.2

0.1

0.25

0.5

0.75

Mole fraction on dry basis

Relative Length
Fig. 5 Mole fractions of species along the catalyst bed, at
H2O/CH4 [ 0.6, CO2/CH4 [ 0.12, O2/CH4 [ 0.59, P [ 21 bar,
T [ 700 K.

methane has two steps. It means that before the production of

H2O and CO2 as a result of total combustion of methane with
oxygen, conversion of methane with steam and carbon
dioxide will not begin. After reacting all oxygen with methane,
steam concentration takes its maximum quantity. After that,
reaction progress will follow by decreasing of the steam
concentration and consequently, increasing the CO and H2
concentrations. Final temperature and product composition
achieved in the first combustion section was considered as the
feed conditions for the next section, i.e. catalytic bed.
In Figs. 4 and 5, the results of kinetic model of catalytic bed
are shown. As it is expected the temperature along the bed
was reduced because of endothermic reactions of steam
reforming. As can be seen, through 75% of relative length of
the bed there are no remarkable changes in temperature and
mole fraction of species. Therefore, in this condition 75% of
the length of the bed is sufficient to reach the defined design
purposes. In Tables 5 and 6, results of the model in comparison to the published experimental data have been presented.

Experimental results [1]

This model

39.0
0.2
39.0
21.7
0
0.1
28.0
1.0
25
1298

32.07

41.01
26.9
0
0.004
33.0
0.782
25
1510

As said before, it was assumed that the reactor was adiabatic,

but at real experimental conditions occurring heat transfer
between surrounding and reactor is possible. Therefore, the
difference between predicted temperature and experimental
value may be explained. Negligible differences between
product compositions may be the result of feed composition,
considering only methane in the model, but natural gas in
experimental conditions.
Effects of feed temperature and pressure on the H2/CO ratio
in produced syngas have been shown in Figs. 6 and 7. In the
specified operating conditions in Fig. 6, at temperature 690 K,
combustion reactions were not considerable and methane
conversion was very low. Higher feed temperature up to 750 K
gives rise to higher methane conversion and so higher syngas
production. At the higher temperatures H2/CO ratio increases
slightly but around 750 K, there is an optimum feed temperature. It should be mentioned that higher temperatures may
have undesirable effects on the catalyst structure and also
increase the operating costs.
The effect of pressure is not as notable as temperature on
the H2/CO ratio. The proper range of pressure considering
Fig. 7 is in between 20 and 25 bar.
Changes of H2/CO ratio at different H2O/CH4 ratio together
with methane conversion are shown in Fig. 8. However with
increasing of the steam content of feed H2/CO ratio may be

1.72
1.7

Table 5 Comparison between the results of the model

with experimental data.

H2
N2
CO
CO2
Ar
CH4
H2O
H2/CO
Pressure (bar)
Temperature (K)

Mole fraction on dry basis

Experimental results [1]

This model

62.1
0
31.1
6.4
0
0.4
19.5
1.99
21
1323

58.44

35.13
6.4

0.04
24.6
1.66
21
1437

1.68

H2 /CO

Species

1.66
1.64
P : 21 bar
H2O/CH4 : 0.6
CO2/CH4 : 0.12
O2/CH4 : 0.59
Ar : 0

1.62
1.6
1.58
700

750

800

Temperature (K)
Fig. 6 Effect of temperature on the H2/CO ratio.

850

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international journal of hydrogen energy 34 (2009) 12921300

0.475

1.69

H2
CO
H2/CO

0.45
0.425

Mole fraction

1.67
T : 700 K
H2O/CH4 : 0.6
CO2/CH4 : 0.12
O2/CH4 : 0.59
Ar : 0

1.66

20

25

30

99.96

1.74

1.64

99.95
99.94
99.93

0.4

99.92
99.91

0.6

0.7

0.8

99.9

1.72
1.7
1.68

H2/CO

Mole fraction

1.76

H2
CO
H2/CO
CH4 Conversion

99.97

Conversion of Methane (

0.8

0.5

1.55

0.1

0.12

0.14

0.16

0.18

0.2

1.5
0.22

CO2/CH4
Fig. 9 Effect of CO2/CH4 on the H2/CO ratio. H2O/CH4 [ 0.6,
O2/CH4 [ 0.59, P [ 21 bar, T [ 750 K.

Autothermal reforming of methane in a Ni/Mg-Al2O4 catalyst

reformer has been kinetically modeled. For kinetic modeling,
reformer were divided in two sections, upper non-catalytic
partial oxidation and lower catalytic steam reforming.
To be confident of feed conversion 1700 K temperature is
needed. Higher temperature increase rate of reactions and
reduce time of getting to equilibrium. The problem of getting
close to equilibrium conversions lead to reduce of relative
production of H2 and CO, because wide portion of methane
convert to undesired products such as H2O and CO2.

0.4

1.6
0.325

35

Conclusion

0.3

0.35

0.25

increased, but on the other hand, conversion of methane and

quantity of hydrogen and carbon monoxide are decreased too.
Considering the role of CO2 in suggested kinetics, it can be
seen that it does not a remarkable influence on the methane
conversion, but high CO2 content in the feed may give rise to
higher H2/CO ratio. This Effect is shown in Fig. 9.

0.2

1.65
0.375

0.275

Fig. 7 Effect of pressure on the H2/CO ratio.

0.6

0.4

0.3

Pressure (bar)

4.

1.7

H2/CO

H2/CO

1.68

1.75

1.66

1.62

H2O/CH4
Fig. 8 Effect of H2O/CH4 on the conversion of methane and
H2/CO ratio. CO2/CH4 [ 0.12, O2/CH4 [ 0.59, P [ 21 bar,
T [ 750 K.

Methane to oxygen ratio, in the entrance feed, has a direct

effect on the reaction temperature. To have higher temperature and reaction rate, concentration of oxygen in the feed
should be increased until released more heat as a result of
reaction of methane with oxygen. But increasing the oxygen
concentration, in addition of reducing the relative production
of H2 and CO, reduces the H2/CO ratio, too. Therefore since
temperature is the most effective parameter on reaction rate,
the way of supply of proper heat is very important.
The results of this model have a good agreement with the
experimental data. The two parts proposed model is suitable
for ATR modeling. At the considered conditions the suitable
feed temperature and pressure, and also feed compositions
have been determined. Also, in this study, effective length
of catalyst bed using the results of the model has been shown.

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