Applied Catalysis A: General 213 (2001) 233–237

The kinetics of methanol decomposition: a part of autothermal

partial oxidation to produce hydrogen for fuel cells
Peter Mizsey1 , Esmond Newson∗ , Than-binh Truong, Peter Hottinger
Paul Scherrer Institut, CH-5232 Villigen-PSI, Switzerland
Received 26 June 2000; received in revised form 8 December 2000; accepted 8 December 2000

Abstract
Methanol is considered as a renewable energy source for fuel processor–fuel cell systems. The determination of the kinetics
of methanol autothermal partial oxidation can be simplified if the problem is divided into subproblems. As a first step, the
kinetics of methanol decomposition (Me) are studied. To describe this subproblem, a reaction system consisting of four
reactions is assumed. The reactions are: Me, dimethyl ether (DME) formation, steam reforming, and water gas shift (WGS)
which are studied on a commercial copper containing catalyst (5 wt.% copper on alumina). The dehydration of methanol
to DME is a second order reaction and essentially provides an excess of water over the whole reactor allowing first order
kinetic assumptions for steam reforming and WGS. The WGS reaction proves to be slow, compared to the other reactions,
and equilibrium limited. The activation energies (kJ/mol) are estimated: Me 76 (±4%), DME formation 117 (±2%), steam
reforming 81 (±7%), WGS 50 (±25%). Turnover frequencies for Me are estimated based on copper surface areas determined
by the nitrous oxide pulse reduction method. At 220◦ C, values of 0.05 s−1 are estimated compared to a literature value of
0.019 s−1 at 200◦ C. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Methanol decomposition; Kinetics; Fixed bed reactor; Fuel cell

1. Introduction be catalytically converted to produce clean hydrogen

Fuel processor–fuel cell systems offer a cleaner al-
ternative to internal combustion engines for mobile
systems based on well-to-wheel analysis but only the
fuel reformer–fuel cell power train using methanol has
the advantage that the methanol could be derived from
a renewable energy source (biomass). This case has
the lowest environmental impact, is CO2 neutral, and
offers a sustainable energy solution. The methanol can
∗ Corresponding author. Tel.: +41-56-310-2640;
fax: +41-56-310-2199.
E-mail address: newson@psi.ch (E. Newson).
1 Present address: Department of Chemical Engineering, Techni-
cal University of Budapest, H-1521 Budapest, Hungary.
for the fuel cell. The exothermic partial oxidation of
methanol in a fixed bed “hot spot” reactor has been al-
ready proposed [1]. Higher hydrogen production from
methanol can be achieved if autothermal partial oxi-
dation is applied:
4 CH3 OH + 3 H2 O + 21 O2 → 11 H2 +4 CO2 (1)
Developments in the kinetics of autothermal partial
oxidation [2] and reactor start-up dynamics [3] have
shown advantages over the endothermic steam reform-
ing of methanol [4]. An analysis of full fuel cycle ef-
ficiencies has shown [5] that the fuel processor–fuel
cell subsystem must reach an energy efficiency of 40%
so that the full fuel cycle efficiency (24%) exceeds
comparable values of 18% for internal combustion

0926-860X/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 9 0 7 - 8
234 P. Mizsey et al. / Applied Catalysis A: General 213 (2001) 233–237
Nomenclature
A pre-exponential factor (mol/g cat s kPax )
DME symbol for dimethyl ether formation
E activation enthalpy (kJ/mol)
k reaction rate constant
Keq equilibrium coefficient
Me symbol for the methanol decomposition
reaction
P partial pressure
r rate of reaction (mol/g cat s)
R gas coefficient, 8.314 (J/mol K)
SR symbol for the steam reforming reaction
T temperature
WGS symbol for the water gas shift reaction
x sum of the stoichiometric coefficients in
the rate equation

HR0 standard heat of reaction (kJ/mol)
engines in mobile systems. With a 50% efficiency for
the polymer electrolyte fuel cell, an 80% efficiency of
the fuel processor is required which is determined by
the catalyst kinetics and reaction engineering of the
subsystem.
The understanding of the kinetics of the methanol
autothermal partial oxidation can be simplified if the
reaction system is studied following a step-by-step
methodology. As a first step, the kinetics of Me
is studied and the data obtained will be used later
for the determination of the kinetics of autother-
mal partial oxidation [2]. In addition, Me is one
possible reaction which produces carbon monoxide
to which low temperature fuel cells are extremely
sensitive. Recent literature on the comprehensive
kinetics of methanol-steam reforming over a com-
mercial shift catalyst [6–8] suggested that the rate
determining step for both steam reforming and de-
composition was the dissociation of formate species
to hydrogen and carbon dioxide, the formate de-
rived from adsorbed methoxy species on active
copper metal sites. To include reactions containing
carbon monoxide, water gas shift (WGS) was con-
sidered non-negligible in contrast to earlier work
[9].
The purpose of this paper is to determine the
applied kinetics for methanol decomposition (Me)
using a commercial copper on alumina catalyst as
part of more comprehensive kinetics for autothermal
methanol partial oxidation. Preliminary work with
the commercial catalyst on Me showed that four re-
actions are necessary to describe the reaction system
(Table 1).
The solution of the kinetics of the four-reaction-
system can be further simplified if the reactions could
be studied individually. For such an individual study
only the WGS reaction can be considered with the
assumption that the presence of the other compo-
nents, e.g. methanol, has negligible impact on the
kinetics.
2. Experimental
The experimental system consists of three major
parts: feed, reactor, and analytical (Fig. 1).
The system is fully computer controlled for con-
tinuous operation and safety features. Flows, pres-
sure, and temperature parameters are controlled (FC,
PC, TC). The methanol is vaporised and contacted
in a static mixer with the diluent nitrogen accord-
ing to requirements. The system allows the study of
other cases, e.g. if oxygen and/or hydrogen are also
used for experiments, methanol feed quality is analy-
sis grade (99.8%) and gas purities are 99.995%. The
feed mixture enters the microreactor, which has an in-
ternal diameter of 4 mm and a total length of 130 mm.
The length of the isothermal catalyst bed is 14 mm,
containing 100 mg of crushed, commercial catalyst
in the particle size range of 0.25–0.5 mm. The cat-
alyst, supplied by Johnson–Matthey plc, UK, under
a confidentiality agreement, contained 5 wt.% copper
on alumina. Characterisation for copper surface area
is made by using the nitrous oxide pulse reduction
method.
The product of the reactor is analysed by a GC (HP
6980) having three different columns and two different
detectors (FID, TCD). The water content in the con-
denser is analysed by a 737KF Coulometer. The tem-
perature ranges between 220 and 300◦ C, the weight
hourly space velocities of methanol (WHSV) go up
from 5 till 40 h−1 , at 300◦ C even till 100 h−1 . The
pressure is constant at 3 bar. Thirty-seven independent
isothermal points were measured and evaluated, the
C, H, O balances were within ±5–10%.
 P. Mizsey et al. / Applied Catalysis A: General 213 (2001) 233–237 235

Reaction 4: Steam reforming (SR)


−56087
Keq,SR = 1.849E+10 exp (5)
RT
The kinetics are significantly influenced by the WGS
equilibrium, less so for DME and Me, and insignificant
for SR, that is the production of methanol in the reverse
reactions can be practically excluded.
The kinetics of the WGS reaction can be studied
individually. In separate experiments a reformate gas
mixture (2% CO, 10% CO2 , 20% H2 , 68% N2 ) was
used to determine the kinetics of the WGS reaction.
The measurements at different temperatures, water
compositions (water contents: 4.2, 20, and 30% of the
total mixture), and conversion rates show that the rate
of reaction of WGS depends both on the water (PH2 O )
and the carbon monoxide composition (PCO ) and can
Fig. 1. Experimental apparatus for methanol decomposition. be described by the following equation:


50000
rWGS = 2.25E − 3 exp − PCO PH2 O
3. Results and discussion RT
×EqWGS (mol/g cat s) (6)
For the kinetic model, each reaction is first studied
where the partial pressures are in kPa, and EqWGS is
to determine if equilibrium limitation is significant.
Based on Gibbs free energies, the equilibrium coeffi- PCO2 PH2
EqWGS = 1 − (7)
cients (Keq ) are determined. Keq,WGS PCO PH2 O
Reaction 1: Dimethyl ether formation (DME)

 In these separate experiments, the WGS reaction has a
21858 first order dependence on the partial pressure of water
Keq,DME = 0.106 exp (2)
RT but in the global evaluation of the four reactions, due to
water rapidly produced from the DME reaction, zero
Reaction 2: Methanol decomposition (Me)
order dependence on the partial pressure of water is


−95418 assumed.
Keq,Me = 1.718E+14 exp (3) During the evaluation of the experimental data for
RT
the whole four-reaction-system, it is found that the
Reaction 3: Water gas shift (WGS) WGS reaction rate is one to three orders of magnitude

 less than those of the other reactions, and therefore,
39876
Keq,WGS = 9.543E − 3 exp (4) this reaction can be neglected at the conditions studied
RT

Table 1
The four reactions considered to describe the methanol decomposition system
Name Reaction
HR0 (kJ/mol)

DME formation 2CH3 OH ⇔ CH3 OCH3 + H2 O −21

MeOH decomposition CH3 OH ⇔ CO + 2H2 +91
Water gas shift (WGS) CO + H2 O ⇔ CO2 + H2 −41
Steam reforming (SR) CH3 OH + H2 O ⇔ CO2 + 3H2 +50
236 P. Mizsey et al. / Applied Catalysis A: General 213 (2001) 233–237

Table 2
Pre-exponential factors and activation energies for methanol decomposition
Reaction Activation energy (kJ/mol) Pre-exponential factor (mol/g cat s kPax )

DME 117 (±2%) 2040 (±15%)

MeOH decomposition (Me) 76 (±4%) 1.12 (±12%)
WGS (individually determined) 50 (±25%) 0.0023 (±32%)
SR 81 (±7%) 6.75 (±34%)

and only a three-reaction-system (DME, Me, SR 4. Steam reforming (SR)

reactions) is to be solved for the kinetic model of Me.
The measured isothermal data points are evalu-
ated with the SIMUSOLV software package [10].
Arrhenius temperature dependence is assumed dur-
ing the evaluation, the activation energies and the
pre-exponential factors are determined by the multidi-
mensional optimisation method of gradient type, part
of the SIMUSOLV program. The results of the evalu-
ation of the measured data show that the second-order
dehydration of methanol to dimethyl ether (DME)
can be described with a second order mechanism.
This reaction proves to be much faster than the others
and essentially provides an excess of water over the
whole reactor allowing first order kinetic assumptions
for Me, and steam reforming. The rates of reactions
can be written in the following form:
1. DME formation
r1 = k1 PMeOH
2
EqDME
2. MeOH decomposition
r2 = k2 PMeOH EqMe
3. Water gas shift (WGS), neglected
r3 = k3 PCO PH02 O EqWGS
r4 = k4 PMeOH EqSR (11)
The pre-exponential factors and activation energies are
summarised in Table 2. The standard deviations are
also indicated in percentages of the actual values.
The confidence of the parameter estimation com-
pleted for the three-reaction-system is also tested. The
correlation matrix is shown in Table 3. The correla-
tion matrix shows that there is a strong correlation
between the pre-exponential factor and the activation
energy of each individual reaction but intercorrela-
tions of kinetic constants are insignificant.
Turnover frequencies for Me for the commercial
copper containing catalyst are determined based on
copper surface areas. A copper surface area value of
5.2 m2 /g catalyst was measured by pulsing nitrous ox-
ide over the sample at 80◦ C. Turnover frequencies for
(8) Me at 220◦ C were estimated at 0.05 s−1 compared to
literature values of 0.019 s−1 at 200◦ C for a 15 wt.%
Pd/ZrO2 catalyst [11].
The accuracy of the kinetic model is tested, by com-
(9)
parison of the predicted and observed rate of reaction
for the Me (Fig. 2). The agreement is within ±10%
which is the error expected from the mass balances
(10) and the standard deviations of the kinetic constants

Table 3
Correlation matrix of the three-reaction-system for methanol decompositiona
ADME EDME AMe EMe ASR ESR

ADME 1.000
EDME 0.9988 1.000
AMe 9.2138E−02 8.4791E−02 1.000
EMe −9.1063E−02 −8.3176E−02 0.9966 1.000
ASR 0.2013 0.2067 −0.5884 −0.5834 1.000
ESR 0.2041 0.2110 −0.5788 −0.5745 0.9972 1.000
a A: pre-exponential factor; E: activation energy.
 P. Mizsey et al. / Applied Catalysis A: General 213 (2001) 233–237
Fig. 2. Comparison of observed (robs ) and predicted rates of re-
action (rpred ) for Me (mol CH3 OH/g cat s).
and shows that the kinetic model can be used for the
description of Me.
The activation energy for DME formation is similar
to the value obtained for ␥-Al2 O3 [12], and consistent
with the high alumina content (94%) of the catalyst
used in this study. Using non-isothermal temperature
scanning methods with a commercial low temperature
shift catalyst, activation energies of 70/102/81 kJ/mol
were obtained by Peppley et al. [6–8], for Me, steam
reforming and WGS, respectively. Corresponding val-
ues from this work (Table 2) are comparable especially
for decomposition and steam reforming.
4. Conclusions
The kinetics of the Me reaction system with
a commercial copper on alumina catalyst are
237
determined. Four reactions were considered, DME for-
mation, steam reforming and WGS, in addition to
Me, which produces carbon monoxide and hydrogen.
Auxiliary experiments show that the WGS reaction
is negligible with this catalyst. The activation ener-
gies for DME formation, reforming and decomposi-
tion (117/81/76 kJ/mol, respectively) are comparable
to literature values. Turnover frequencies (0.05 s−1 )
are similar to a Pd/ZrO2 catalyst (0.019 s−1 ) from lit-
erature.
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