Applied Catalysis A: General 278 (2004) 2535

www.elsevier.com/locate/apcata

Methanol steam reforming over Cu/ZnO/Al2O3 catalyst:

kinetics and effectiveness factor
Jin Kyung Lee, Jung Bong Ko, Dong Hyun Kim*
Department of Chemical Engineering, Kyungpook National University,
1370 Sankyukdong, Daegu 702-701, Republic of Korea
Received 24 March 2004; received in revised form 1 September 2004; accepted 16 September 2004

Abstract
Steam reforming of methanol over a commercial Cu/ZnO/Al2O3 catalyst was studied at atmospheric pressure and in a temperature range
between 160 and 260 8C. The reaction rate depended upon methanol and hydrogen partial pressures, and was independent of the partial
pressures of carbon oxides and water, which was in excess of the methanol partial pressure. Small amounts of carbon monoxide, less than 1%
in the product gas, were formed at high temperatures; the amounts were well below the equilibrium amounts of reverse watergas-shift
reaction (RWGS). This was in support of the reaction sequence of methanol steam reforming followed by the RWGS. A power-law and a
LangmuirHinselwood rate expression were developed for the reforming reaction by fitting the expressions to the experimental data. As the
data were found to be affected by internal diffusion at high temperatures, the effectiveness factor of the catalyst particle was estimated in the
fitting in order to obtain the intrinsic kinetics. Details of the estimation of the factor are elucidated. In order to predict a non-zero, finite rate in
the absence of hydrogen, the hydrogen partial pressure term in the power-law expression was corrected by a fitted constant to avoid an infinite
reaction rate, since the exponent of the hydrogen partial pressure was a negative number due to the hydrogen inhibition effect in the reforming;
in the reaction mechanism for the LangmuirHinselwood expression, it was necessary to assume two different kinds of active sites on the
catalyst: one for adsorbed methoxy and the other for adsorbed hydrogen. In addition, an excellent fitting of the data by the Langmuir
Hinselwood expression indicates that dehydrogenation of the adsorbed methoxy to the adsorbed oxymethylene is the rate-determining step
(RDS), and that adsorption of all the species other than methoxy and hydrogen on the active sites is negligible.
# 2004 Published by Elsevier B.V.
Keywords: Methanol steam reforming; Kinetics; Effectiveness factor; Carbon monoxide formation

1. Introduction
Hydrogen production from hydrocarbon steam reforming
is a cost-effective method in providing hydrogen for fuel
cells. In liquid fuel processing, methanol steam reforming is
a simple and efficient way of producing hydrogen on a small
scale:
CH3 OH H2 O ! CO2 3H2 ;
DH 57kJ=molat200 C

(1)

The reaction occurs at low temperatures in the range

between 200 and 300 8C over Cu-based catalysts; its
* Corresponding author. Tel.: +82 53 950 5617; fax: +82 53 950 6615.
E-mail address: dhkim@knu.ac.kr (D.H. Kim).
0926-860X/$ see front matter # 2004 Published by Elsevier B.V.
doi:10.1016/j.apcata.2004.09.022

products are mainly hydrogen and carbon dioxide with a

small amount of CO, usually less than 1%, as a by-product
[13]. Thus, methanol is sometimes referred to as a
hydrogen storage medium in liquid form. The product
gas, however, needs further purification, i.e. the removal of
CO, to be used in proton exchange membrane (PEM) fuel
cells, since the anode catalyst of the fuel cell is poisoned by
CO with a concentration as low as 10 ppm [4,5]. The
preferential oxidation of CO (PROX) with oxygen can be
used to remove CO in hydrogen [68]. In this respect, the
production of hydrogen with methanol for PEM fuel cells
consists of two reaction stages: steam reforming and PROX.
This may be compared with the fuel processing of other
liquid fuels, such as gasoline and diesel for hydrogen
production, in which steam reforming of the fuel, carried out

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J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

at high temperatures above 600 8C, produces typically more

than 10% CO in the product gas. Thus, a separate watergasshift (WGS) reaction stage which is normally carried out in
two steps (high-temperature shift and low-temperature shift) is
necessary to reduce the carbon monoxide content to about 1%
before the PROX stage [9,10]. Moreover, to remove sulfur
compounds in the fuels, a desulfurization step is additionally
needed [9]. From the standpoint of the complexity of the
processes involved, hydrogen production from methanol is the
simplest. Hence, it enables construction of a compact reformer
suitable for on-board hydrogen production [2,1113].
Recently, there was a successful demonstration of a fuel cell
vehicle (NECAR 5, DaimlerChrysler) operated on hydrogen
from an on-board methanol reformer [14].
When one designs methanol reformers, the kinetics of the
reforming reaction is important in sizing the reactor. Diverse
power-law and LangmuirHinselwood rate expressions have
been proposed in the literature. The proposed rate
expressions are briefly summarized in Table 1 and are
discussed in Section 1.1. It can be seen that there is little
agreement among the expressions even for the same kind of

catalysts, making it difficult to choose appropriate kinetics

for a reformer design. In this paper, we present a study on the
kinetics of methanol steam reforming over a recent
commercial catalyst Cu/ZnO/Al2O3 (Synetix 33-5). We
report LangmuirHinselwood and power-law kinetics of the
reforming. Also, we compare kinetic models in literature
and propose a reaction mechanism based on the experimental findings.
In addition to the kinetics, estimation of the effect of
intraparticle diffusion in catalyst particles is also important
in the design of the reformer. The use of small particles can
reduce the effect of the diffusion, but can increase the
pressure drop across the reactor. Keeping the pressure drop
within a given tolerable range may require a certain particle
size, and the influence of intraparticle diffusion on the
reaction rate may be considerable in the particles,
particularly at high temperatures. The diffusion effect can
be formally accounted for by the effectiveness factor of the
catalyst. Estimation of the factor involves solving the
governing equation for intraparticle diffusion and reaction in
the catalyst particle [15]:

Table 1
Methanol steam reforming rate expressions in the literature
Ref.

Rate expression

Catalyst

Activation energy (kJ/mol)

[19]

(T1)
rM
(T2)
rM
(T3)
rM
(T4)
rM
(T5)
rM

Cu/ZnO/Cr2O3/Al2O3

116.1

Cu/ZnO/Al2O3 (BASF)

102.6

Cu/ZnO (Girdler G66B)

96

[20]
[21]
[23]
[24]
[25]

p 1:3
PM PW PH

kKM PM =1 KM PM KW PW
kKM PM  k0 PCO P2M =1 KPCO
kK1 PM =

p
p
p
K3 PH =1 K1 PM = K3 PH 1= K3 PH 2

Cu/ZnO/Al2O3 (BASF S3-85)

110

Cu/ZnO/Al2O3 (BASF S3-85)

105

0:03 0:2
kP0:26
M PW PH

Below 190 8C
(T6)
rM kP0:04
M
(T7)
rM kPM  PC P3H =KE PW =1 KPM
Above 200 8C
(T8)
0:99
rM kP0:28
M PC
(T9)
rM kPM PW =PH  PC P2H =KE =1 KPM 4

Cu/MnO/Al2O3

79.7

Cu/MnO/Al2O3

77.3

Cu/MnO/Al2O3

77.7

Cu/MnO/Al2O3

116.6

[29]

(T10)
102.8
Cu/ZnO/Al2O3 (BASF K3-110)
p
rM kK1 PM = PH 1  P3H PC =KE PM PW =DEN
[28]
(T11)
83
Cu/ZnO/Al2O3
3
rM kP0:4
M 1  PC PH =KE PM PW
[30]
(T12)
Cu/ZnO/Al2O3 (BASF K3-110)
74
0:39 P0:23 P0:07
rM kP0:63
P
M
H
W
C
122.4
Cu/ZnO/Al2O3 (BASF K3-110)
(T10)
p
rM kK1 PM = PH 1  P3H PC =KE PM PW =DEN
[18]a
(T13)
Cu/ZnO/Al2O3 (Su d-Chemie)
76
0:4
rM kP0:6
M PW
h



i
p
p
M
W
K2 PC PH K3 pP
1 K4 PH
C, carbon dioxide; H, hydrogen; M, methanol; W, water; DEN 1 K1 pP
P
P
H

Internal diffusion limitations were present.

J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

Solutions can be numerically intensive if the rate expression

is not of a simple form such as a first-order reaction, or difficult
due to numerical problems inherent in the governing equation,
particularly when the rate expression is highly non-linear [16].
This difficulty may have compelled some researchers in recent
studies [17,18] to report only the apparent kinetics of the
reforming reaction, where the kinetic data have been under the
influence of intraparticle diffusion limitations. An efficient,
robust method of computing the effectiveness factor has been
developed recently [16]. The method enabled accurate
estimation of the effectiveness factor of the catalyst over
the entire range of the experimental conditions of this study. In
our experiments carried out over a wide range of temperatures,
the kinetic data were found to be free of the effects of the
internal diffusion at low temperatures, but were limited by the
diffusion at high temperatures. Nevertheless, with the method,
we could successfully analyze all the data together to obtain the
intrinsic kinetics of the reforming.
1.1. Kinetics of methanol steam reforming in the literature
There have been a number of studies on the kinetics and
the mechanism of the reaction. The proposed rate
expressions in the literature are listed in Table 1. Some
early studies proposed that the reaction sequence of the
steam reforming is methanol decomposition followed by
WGS reaction, and the decomposition step was thought to be
rate-determining [1921]:
CH3 OH ! CO 2H2

(2)

CO H2 O $ CO2 H2

(3)

Since, CO is produced first in the reaction sequence, the

CO concentrations in the products should be at least equal to
or greater than the concentration of the WGS equilibrium.
This, however, was not well supported in the experiments of
the studies that proposed the reaction sequence. Santacesaria
and Carra [20] observed negligible amounts of CO in the
products, which they thought to be an attainment of the
WGS equilibrium. Amphelett et al. [21], on the other hand,
found that their experimental concentration of CO was much
less than the equilibrium values and they suggested carbon
deposition on the catalyst as a possible explanation. Such an
explanation seems unreasonable because such carbon
deposition would soon completely deactivate the catalyst.
Later studies have proven experimentally that the reaction
between methanol and water occurs directly to produce carbon
dioxide and hydrogen [2226]. A methyl formate reaction
route has been suggested for the reaction [22,23]:
2CH3 OH ! CH3 OCHO 2H2

(4)

CH3 OCHO H2 O ! CH3 OH HCOOH

(5)

HCOOH ! CO2 H2

(6)

In this route, CO is not a primary product and does not

take part in the rate expression. Since, the Cu-based

27

reforming catalysts are also highly active in the WGS

reaction, CO has been thought to be produced by the reverse
watergas-shift reaction (RWGS) which uses the products of
the reforming reaction [17,18,27,28]:
CO2 H2 ! CO H2 O

(7)

The amount of CO produced was small and well below

the equilibrium of the RWGS in the product gas [17,23].
Every expression in Table 1 predicts an increasing
reforming rate with an increasing methanol partial pressure,
but the specific form of such dependence differs among the
expressions. Except for methanol, there is little agreement
regarding the components affecting the reaction rate. The
power-law rate by Idem and Bakhshi [25] for temperatures
above 200 8C (Eq. (T8) in Table 1) has a carbon dioxide
partial pressure term with an exponent of 0.99. This
indicates that carbon dioxide inhibits the reforming, which
appears to be incompatible even with their Langmuir
Hinselwood expression Eq. (T9), where the forward reaction
is inhibited by the hydrogen partial pressure.
Among the rate expressions, the power-law expression
with a negative order in the hydrogen partial pressure, Eqs.
(T1), (T5) and (T12), predicts an infinite reaction rate in the
absence of hydrogen. The feed to a methanol reformer is
normally absent of hydrogen and consists of methanol and
water only. In this case, the negative power in the hydrogen
partial pressure causes a numerical problem, such as division
by zero, in addition to an unrealistic reaction rate, at the
reactor inlet.
Jiang et al. [23,24] proposed a LangmuirHinselwood
rate expression Eq. (T4) based on a reaction route involving
methyl formate intermediate and a single kind of active sites.
If the expression is applied to the case of zero hydrogen
partial pressure, the expression yields a zero reaction rate;
thus, for a feed without hydrogen, it predicts no methanol
conversion, which is clearly inconsistent with what we
observe in practice. As long as dissociative hydrogen
chemisorption and a single type of active sites are assumed
in the mechanism, the inconsistency does not seem to
disappear irrespective of the assumed rate-controlling step.
By additionally assuming hydrogen adsorption on another
kind of sites and employing a similar reaction route
proposed by Jiang et al., Peppley et al. [29] arrived at a
LangmuirHinselwood rate expression Eq. (T10) which can
account for the inhibition effect of hydrogen and yields a
finite non-zero reaction rate in the absence of hydrogen.
Later, Samms and Savinell [30] adopted Peppleys expression to model their methanol steam reforming data.

2. Experimental
The Cu/ZnO/Al2O3 catalyst used in the kinetic experiment was a commercial catalyst, Synetix 33-5. Its chemical
composition and physical properties are listed in Table 2.
The catalyst was crushed, sieved to a size fraction between

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J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

Table 2
Properties of Synetix 33-5 methanol reforming catalyst
Chemical composition, reported by manufacturer
CuO (wt.%)
Al2O3 (wt.%)
ZnO (wt.%)
MgO (wt.%)
Catalyst density rP (kg/m3)
Catalyst pore mean radius r (m)
BET area (m2/g)
Void fraction eP
Particle size (mm)

dioxide, water and methanol and a Carboxen column

(Supelco) was used to separate carbon monoxide and carbon
dioxide. The reaction products were mainly hydrogen and
carbon dioxide, and the amount of carbon monoxide in the
product stream was negligible, usually less than 0.5%.

64
10
24
2
2400
8  109
66
0.47
0.30.425

0.3 and 0.42 mm, and 1 g of the catalyst particles was

packed into a 1/4 in stainless steel tube reactor. A K-type
thermocouple was placed in the middle of the reactor to
measure the reaction temperature. Before the reaction, the
catalyst was reduced under 10% hydrogen in nitrogen at
250 8C for 2 h. A methanol bubbler and a water bubbler were
used to feed the reactant vapors into the reactor.
Nitrogen, hydrogen or a mixture of the two gases was
used to carry the vapor from each bubbler into the reactor.
For this purpose, the flow rates of nitrogen and hydrogen
were separately controlled by two mass flow controllers
before each bubbler. Each mass flow controller was
individually recalibrated for the gas, nitrogen or hydrogen,
with a calibrator (Brandt Instruments Inc., DryCal DC-2M)
to ensure high accuracy in the flow control. The temperature
of each bubbler was controlled by a circulating water bath to
feed a prescribed amount of the reactant, determined by the
carrier gas flow rate and the vapor pressure. The two streams
from the bubblers were mixed together before the reactor,
and the total flow rate of the resulting vapor mixture was
fixed at 200 ml (STP)/min. The feed composition used in the
experiments is listed in Table 3. For each feed composition,
the methanol conversion was measured in approximately
10 8C increments from 160 to 260 8C. The product gas was
analyzed on-line with a gas chromatograph (HP 5890A) with
two thermal conductivity detectors (TCDs) and two
separating columns in a parallel configuration. A Porapak-Q column (Supelco) was used to separate carbon

3. Results and discussion

3.1. Catalyst aging
Fig. 1 shows methanol conversion with time on stream at
210 8C. Initially, the activity of the fresh catalyst declined
relatively quickly, and after around 50 h of operation it
became stable. During this period, it was thought that some
transient transformation to a stable form under the reaction
condition occurred in the catalyst. After this period, the
catalyst showed stable activity to 120 h. Purnama et al. [18]
also reported similar stabilization within the first 100 h of
steam reforming with a commercial Cu/ZnO/Al2O3 catalyst
from Su d-Chemie. All kinetic experiments in this work were
carried out with a catalyst, which had been on stream over
60 h in order to eliminate errors caused by catalyst
deactivation.
3.2. Influence of feed composition on methanol conversion
The effect of the water content in the feed on the
methanol conversion was studied for water/methanol feed
mole ratios of 1, 1.5 and 2; the results are shown in Fig. 2. In
the temperature range from 160 to 270 8C, there is little
change in methanol conversion at the feed mole ratios.
Similar results have been reported by Jiang et al. [24] over a
temperature range of 170250 8C. They obtained an
exponent of 0.03 for water partial pressure in their
power-law expression, Eq. (T5) and suggested that the
exponent 0.03 was simply the least square estimate and not
statistically different from zero. We conclude that the
reforming rate is not affected by water partial pressure as
long as the partial pressure exceeds the methanol partial
pressure.

Table 3
Feed composition
Feed

30M
30M
30M
45M
60M
30M
30M
30M

Composition (mol%)

60W
45W
30W
60W
60W
60W
60W
60W

110N
125N
140N
95N
80N
100N 10H
80N 30H
110H

CH3OH

H2O

N2

H2

15
15
15
22.5
30
15
15
15

30
22.5
15
30
30
30
30
30

55
62.5
70
47.5
40
50
40
0

0
0
0
0
0
5
15
55

M, methanol; W, water; N, nitrogen; H, hydrogen; feed flow rate, 200 ml

(STP)/min.

Fig. 1. Methanol conversion with time on stream (210 8C, feed: 30M 60W
110N).

J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

29

Fig. 2. Effect of water content in the feed on methanol conversion vs.

temperature.

Fig. 4. Effect of hydrogen content in the feed on methanol conversion vs.

temperature.

To examine the effect of methanol partial pressure on the

reforming rate, we fixed the water content in the feed at
30 mol%, and we varied the methanol content in the feed
from 15 to 30 mol%. Fig. 3 shows the methanol conversion
with respect to the temperature for the three feed
compositions. With an increase of the methanol partial
pressure in the feed, the methanol conversion decreased, but
if we estimate the amount of the reaction, that is the product
of the conversion and the methanol feed rate, from the figure,
it can be seen that the amount of the reaction increased with
increasing methanol content in the feed. If the methanol was
consumed by a first-order reaction, the conversion would
have been the same; if it was converted by a zero or negativeorder reaction, the conversion would have been half or less
than half of the conversion of the reference feed. In view of
this, the reaction order for methanol partial pressure would
be less than one but greater than zero. Non-negative reaction
orders for the methanol partial pressure in the range of 0.04
0.63 can be found in Table 1.
Fig. 4 shows the effect of hydrogen content in the feed on
the methanol conversion. The methanol conversion
decreased with an increase in the hydrogen partial pressure
in the feed, showing an inhibiting effect of the hydrogen on
the reaction. The inhibiting effect may be accounted for by a
negative reaction order in a power-law rate or by adsorption
terms in a LangmuirHinselwood rate. In power-law
kinetics, however, a negative order in the hydrogen partial

pressure gives rise to an infinite reaction rate in the absence

of hydrogen. Therefore, to avoid this difficulty in power-law
expressions, the term associated with the hydrogen partial
pressure may have to be corrected, such as (A + PH)b so as to
yield a finite rate in the absence of hydrogen, where A is a
constant, PH is hydrogen partial pressure and the exponent b
is a negative number.
Fig. 5 shows the effect of carbon dioxide content in the feed
on the methanol conversion. For each reaction temperature,
the methanol conversion remained constant as the carbon
dioxide concentration in the feed increased from 0 to
55 mol%, in agreement with the results in the work of Jiang
et al. [24]. Thus, carbon dioxide is concluded to have no effect
on the reaction rate. The carbon monoxide concentration in the
reactor effluent was at most 1% in our experiments, and the
reforming rate was experimentally shown to be unaffected by
the presence of carbon monoxide [22,24].
In summary, we have found that methanol partial pressure
and hydrogen partial pressure affect the reforming rate, and
that water, if present in excess of the stoichiometric ratio,
and carbon oxides have little effect on the rate.

Fig. 3. Effect of methanol content in the feed on methanol conversion vs.

temperature.

Fig. 5. Effect of carbon dioxide concentration in the feed on methanol

conversion at various temperatures.

3.3. Influence of feed composition on CO formation

CO was not detected in the experiments when the
reaction temperature was lower than 200 8C; its amount was
usually much less than 1 mol% when detected in our

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J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

Fig. 6. Variation of carbon monoxide concentration in the reactor effluent

(reverse watergas-shift equilibrium and experiment) with water concentration in the feed at 260 8C. Feed composition: 15 mol% methanol, water
(shown), balance nitrogen; 200 ml/min total flow rate.

experiments. Moreover, the equilibrium CO concentration,

calculated for the reactor effluent composition, was always
significantly greater than the experimentally measured CO
concentration, in support of the reaction sequence of steam
reforming followed by the RWGS reaction. Figs. 6 and 7
show the effect of reactant mol% in the feed on the reactor
effluent CO concentration. An increase in the feeds water
content decreased the effluent CO concentration, indicating
that water suppresses CO formation. On the other hand, the
CO concentration increased with an increase in the feeds
methanol concentration. This can be attributed to an
increased CO2 formation with an increase in the methanol
concentration, thus, promoting a CO formation by the
RWGS. Indeed, the addition of CO2 in the feed also
increased the effluent CO concentration as shown in Fig. 8. It
was shown in the previous section (Fig. 5) that the addition
of CO2 in the feed did not affect the methanol conversion.
Therefore, the methanol concentration profiles along the
integral reactor for the feed compositions in Fig. 8 must have
been identical with each other.

Fig. 7. Variation of carbon monoxide concentration in the reactor effluent

(reverse watergas-shift equilibrium and experiment) with methanol concentration in the feed at 260 8C. Feed composition: methanol (shown),
30 mol% water, balance nitrogen; 200 ml/min total flow rate.

Fig. 8. Variation of carbon monoxide concentration in the reactor effluent

(reverse watergas-shift equilibrium and experiment) with carbon dioxide
concentration in the feed at 260 8C. Feed composition: 15 mol% methanol,
30 mol% water, carbon dioxide (shown), balance nitrogen; 200 ml/min total
flow rate.

If CO was directly produced from methanol, for example,

by methanol decomposition as suggested by Peppely et al.
[29], the amount of CO produced would not have changed
with the increased CO2 content in the feed. In this respect,
Fig. 8 is thought to be a direct evidence that CO is formed by
the RWGS. Fig. 9 shows the effect of hydrogen concentration in the feed on the CO concentration. The measured CO
concentration remained constant with the increase in the
hydrogen concentration in the feed, in apparent contradiction with the expectation that the RWGS should be
promoted with an increase in the hydrogen partial pressure.
If we consider that hydrogen inhibited the reforming
reaction, as shown in Fig. 4, and therefore, the amount of
CO2 formed must have decreased with an increase in the
hydrogen partial pressure, we may see that hydrogen, in fact,
promoted the CO formation. Its promoting effect, however,
apparently has been offset by the effect of the reduced
amount of CO2 formed. Unless hydrogen promoted CO
formation, the effluent CO concentration would have
decreased.
In summary, the experimental results in Figs. 69 support
the conclusions that CO is formed from the RWGS as a

Fig. 9. Variation of carbon monoxide concentration in the reactor effluent

(reverse watergas-shift equilibrium and experiment) with hydrogen concentration in the feed at 260 8C. Feed composition: 15 mol% methanol,
30 mol% water, hydrogen (shown), balance nitrogen; 200 ml/min total flow
rate.

J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

secondary product, and that by increasing the water content,

CO production can be decreased by suppressing the RWGS.
3.4. Effectiveness factor, h
The application of the WeiszPrater criterion for internal
diffusion [31] to our data indicated no diffusion limitations
at temperatures below 200 8C (h = 1), but considerable
diffusion limitations at temperatures above 240 8C (h < 1).
Agrell et al. [17] experimentally observed the intraparticle
diffusion limitations at temperatures above 220 8C in the
methanol steam reforming over a commercial catalyst (Su dChemie G-66 MR) of the size 0.120.25 mm, approximately
half the size of the catalyst particles (0.30.42 mm) used in
this study. They fitted their rate constants variation with
temperature by a fifth degree polynomial. Purnama et al.
[18] also observed the diffusion limitations and reported
only apparent reforming kinetics.
To estimate the effectiveness factor, one should
determine the intraparticle concentration profiles of the
components, which affect the reaction rate. The concentration profiles depend on the effective diffusivities of the
components and on the reaction rate. We neglected carbon
monoxide in the reforming mixture, since its concentration
was insignificant. We considered that the reforming mixture
consisted of five components: methanol (M), water (W),
carbon dioxide (C), hydrogen (H) and nitrogen (N). Since,
the reaction rate has been found to depend on the partial
pressures of methanol and hydrogen, we need to obtain the
concentration profiles of the two components to evaluate the
effectiveness factor.
The effective diffusivity values of methanol and
hydrogen in the catalyst were estimated using the modified
MaxwellStefan equation [32] and the cross-linked pore
model [33], recommended by Haugaard and Livbjerg [34]
based on an experimental comparison of the pore-diffusion
models. The effective diffusivity of methanol DMe and
hydrogen DHe are given by:

eP yW  yM yC yM yH 3yM
DMe

t
DMW
DMC
DMH
1
yN
1

(8)
DMN DKM

eP yM yH =3 yW yH =3 yC  yH =3
DHe

DHM
DHW
DHC
t
1
yN
1

(9)
DHN DKH
eP is the porosity of the catalyst, t the tortuosity of pores in
the catalyst, yi the mole fraction of component i, Dij the
diffusivity for a binary mixture of i and j and DKM and DKH
the Knudsen diffusivity of methanol and of hydrogen,
respectively. The tortuosity factor t is a parameter, which
corrects deviations of the real pore structure from the ideal
cylindrical straight pores. We assumed t = 3, a theoretical

31

value for a random pore system [33]. The binary diffusivity

was estimated by the method of Reid et al. [35]. The
Knudsen diffusivities of methanol and hydrogen are:
r
r
T
T
;
DKH 9:7r
(10)
m2 =s
DKM 97r
32
2
where r is the mean pore radius (m) and T the reaction
temperature (K). The effective diffusivities DMe and DHe are
seen to depend on the mole fractions of all components of
the reaction mixture at a point in the catalyst. Schneider
[32,36] has shown that the change of the effective diffusivity
along the pores in the catalyst is not very marked even under
strong diffusion limitations, and that the effective diffusivity
evaluated at the outer surface of a catalyst particle can be
used throughout the particle without introducing any serious
error into the concentration profile. It has been pointed out,
however, that the dependence of the diffusivity on the
composition at the external surface cannot be neglected,
and hence, the effective diffusivity should be evaluated
along the axial position in the reactor, particularly when
the conversion throughout the reactor is considerable.
The concentration profile of methanol and hydrogen
inside a catalyst particle depend upon each other by the
following mutual relation:
3DMe
yH  yHS
yMS  yM
(11)
DHe
where yM and yH are the mole fraction of methanol and of
hydrogen at a point in the particle, respectively, and yMS and
yHS the corresponding mole fractions at the external surface
of the particle. For the relationship, we need to obtain only
the concentration profile of either methanol or hydrogen in
order to evaluate the effectiveness factor.
We define a dimensionless concentration of methanol in
the catalyst particle as z = CM/CMS or its equivalent z = yM/
yMS, which is a normalized concentration with respect to the
external concentration CMS. The dimensionless mass
balance for methanol in the catalyst can be written as:
d2 z 2 dz
f2 f z 0

dx2 x dx

(12)

The boundary conditions are:

z1 1

and

dz
0
dx

at x 0

(13)

x is the dimensionless radial variable in the catalyst, and

x = 0, 1 denotes the catalyst center and the external surface,
respectively. f is the Thiele modulus defined by:
s
rP rM T; PHS ; PMS
(14)
fL
CMS DMe
where L is the radius of the catalyst particle (m), rP the
catalyst density (kg/m3), RM the reaction rate (mol/kg/s) and

32

J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

PHS and PMS the methanol partial pressure and the hydrogen
partial pressure at the external surface (kPa). The linear
relation between the concentrations of methanol and hydrogen, Eq. (11), can be applied to express the reaction rate
within the particle in terms of the methanol concentration
alone, RM(T, PH, PM) = RM(T, PM). f(z) is the dimensionless
reaction rate, normalized with respect to the rate at the
external condition, as defined by:
rM T; PH ; PM
rM T; PHS ; PMS
The effectiveness factor is given by:

3 dz

h 2

f dx x1

f z

(15)

(16)

To estimate the effectiveness factor by Eq. (16), it is

necessary to solve the governing equation Eq. (12) to obtain
the dimensionless methanol concentration profile z(x). The
analytic solution of Eq. (12) is not feasible when f(z) is nonlinear, as in our case if we examine the rate expressions listed
in Table 1. Numerical instability may occur during the
numerical solution of Eq. (12). A robust, efficient numerical
method for computing the effectiveness factor has been
developed recently [16], and a FORTRAN subroutine of
the method is now available at the web site (http://cre.knu.ac.kr). Together with a separate function routine for the
evaluation of f(z), the routine returns the effectiveness factor
with input of the Thiele modulus. The proposed rate expressions of this study are discussed later in Section 3.6.
3.5. Analysis of experimental data
In the temperature range of the experiment, the methanol
conversion varied from a few percent to 100%. Usually,
when the conversion exceeds 10%, the composition change
along the length of the reactor should be accounted for in the
analysis of the reaction data. This approach is often called
the integral method as opposed to the differential method,
where the conversion is kept small so that an average
composition can be used in the data analysis.
The reactor is assumed as a plug-flow packed-bed reactor.
Its balance equation is:
0
FM

dX
rM h
dW

(17)

0 is the molar flow rate of methanol in the feed

where FM
(mol/s); X the fractional conversion of methanol in the range
of 0 and 1; W the variable of the catalyst weight (kg), running
from 0 to Wt (total weight of the catalyst in the reactor); rM
the reaction rate (mol/s/kg) at the catalyst outer surface and h
the effectiveness factor of the catalyst.
A rate expression contains a number of kinetic
parameters. If the expression is of a power-law type, the
pre-exponential factor, the activation energy and the
exponents of concentrations or partial pressures of the

components are the kinetic parameters. For a Langmuir

Hinselwood type expression, the adsorption equilibrium
constants of the components adsorbed on the active sites are
among the kinetic parameters. For a postulated rate
expression, the reaction rate also depends on the values
of the kinetic parameters in the expression, in addition to the
reaction condition, such as the partial pressures of the
components involved and the reaction temperature. For a
given feed and reaction temperature, the exit conversion,
which is calculated by integrating Eq. (17), will depend on
the set of parameter values in the postulated rate expression.
We fitted the predicted conversions of Eq. (17) to the
experimental conversions. To find the best fit, we defined an
objective function S, a mean square error,
S

N
1X
Xc;i  Xe;i 2
N i1

(18)

where N is the number of the experimental data, Xc,i the

predicted percent conversion calculated by integrating the
balance Eq. (17) from W = 0 to W = Wt for the experimental
condition (the reaction temperature, the feed composition
and the feed rate) of the ith data and Xe,i is the ith experimental conversion data. The set of the kinetic parameters at
the minimum of S was determined by the method of Kuester
and Mize [37], which was developed for the minimization of
an unconstrained multivariable non-linear function.
3.6. A reaction mechanism and the kinetics of methanol
steam reforming
Here, we develop a reaction mechanism that can explain
our experimental data. A notable difference in the proposed
reaction mechanisms is in the assumption on the active sites
for the adsorbed species. The mechanism proposed by Jiang
et al. [24] assumed that all adsorbed species compete on a
single kind of active sites on the surface of the catalyst,
whereas Peppley et al. [29] assumed two distinct types of
active sites, one type exclusively for hydrogen adsorption
and the other type for all other adsorbed species. Although,
the elementary reactions and the rate-determining step
(RDS) in the mechanisms are the same, the resulting rate
expressions differ in their predictions for a reaction mixture
which is absent of hydrogen. A zero rate is predicted by the
rate equation of Jiang et. al., Eq. (T4) (in Table 1), while a
finite rate is predicted by the rate equation of Peppely et al.,
Eq. (T10). A non-zero, finite reaction rate in the absence of
hydrogen is essential for the reaction to proceed with a feed
consisting of only methanol and water. The discrepancy in
the prediction of Eq. (T4) at a zero hydrogen partial pressure
can be seen to support the assumption that hydrogen adsorbs
on a distinct kind of sites, which is different from the kind of
sites for methanol adsorption. Incidentally, the adsorption
model proposed by Sloczynski et al. [38] distinguishes two
kinds of adsorption sites over a Cu/ZnO/Al2O3 catalyst: one
for reversible adsorption of H2, CO and CO2, and the other

J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

for reversible adsorption of methanol and water, on which

H2, CO and CO2 do not adsorb. As to the adsorption of CO
and CO2, this model does not agree with the model of
Peppley et al. It has been experimentally shown that
methanol dissociates into methoxy and hydrogen upon
adsorption on the surface of Cu catalysts [29]. In view of
this, the adsorption models of Peppley et al. and Sloczynski
et al. both indicate that the adsorbed methoxy and the
adsorbed hydrogen do not share the same kind of active sites.
In our experiments, only methanol and hydrogen partial
pressure have been shown to affect the reforming rate,
indicating that the partial pressure terms of other components in the reaction mixture may not appear in the rate
expression, and also that adsorption of the components other
than hydrogen and methanol may be insignificant. In light of
the above remarks, we assume that (1) there exist two kinds
of active sites on the catalyst, denoted as s1 and s2, and
hydrogen adsorbs on the s1 sites and methoxy on the s2 sites;
(2) adsorption of all other components and reaction
intermediates on either kind of sites is negligible and (3)
dehydrogenation of the adsorbed methoxy to the adsorbed
oxymethylene is the RDS. The third assumption is from the
reaction mechanism proposed by Jiang et al.[24]. We present
a part of the elementary reaction steps relevant to methanol
and hydrogen adsorption, and RDS.
CH3 OH s1 s2 $ CH3 Os1 Hs2equilibrium

(19)

CH3 Os1 s2 ! CH2 Os1 Hs2

RDS

(20)

equilibrium

(21)

H2 2s2 $ 2Hs2

From the adsorption equilibrium of methanol, Eq. (19),

the concentration of the adsorbed methoxy CH3O(s1) is
given by:
K10 PM Cv;s1

CCH3 O p
(22)
K 2 P H2
Cv,s1 is the concentration of the vacant s1 sites. Neglecting
all other species except the methoxy on s1, the site balance
for s1 is:
!
0
1 K1 PM
CT;s1 Cv;s1 p
(23)
K2 PH2
and the site balance for s2 is:
p
CT;s2 Cv;s2 1 K2 PH2
(24)
where CT,s1 and CT,s2 are the total concentration of the site s1
and s2, respectively.
The reaction rate is then given by Eq. (20):
rM k0 CCH3 O Cv;s2

p
kK1 PM = PH2
p
p

1 K1 PM = PH2 1 K2 PH2

(25)

p
where K1 K10 = K2 and k = k0 CT,s1CT,s2. The same rate
equation can also be obtained by deleting all the adsorption

33

terms other than the ones for methoxy and hydrogen in the
Peppley et al. rate expression, Eq. (T10). The temperature
dependence of the constants in Eq. (25) are:




ER
DH1
;
K1 K10 exp 
;
k k0 exp 
RT
RT


DH2
(26)
K2 K20 exp 
RT
Thus, the rate expression Eq. (25) has k0, ER, K10, DH1,
K20 and DH2 as its kinetic parameters. Based on values
reported in the literature, Peppley et al. [29] suggested 20
and 50 kJ/mol for DH1 and DH2, respectively. Adopting
the suggestion leaves four adjustable parameters, k0, ER,
K10, and K20, in Eq. (25).
We fitted the parameters to 82 experimental conversion
data, ranging from a few percent to 100%, by the method
described in Section 3.5. The four-parameter fitting with the
prescribed values for DH1 and DH2 resulted in:


111 kJ=mol
mol=kg=s;
k 3:13  1010 exp 
RT


20 kJ=mol
kPa0:5 ;
K1 3:75  103 exp
RT


50 kJ=mol
(27)
K2 6:34  107 exp
kPa1
RT
The mean square deviation S, defined in Eq. (18), was 2.1,
which is equivalent to an average deviation of 1.45%
between the experimental conversion and the predicted
conversion, indicating an excellent agreement; also, the
assigned values for DH1 and DH2 were quite reasonable. In
fact, we also fitted all six parameters to the data and
obtained:


111 kJ=mol
k 3:37  1010 exp 
;
RT


20:1 kJ=mol
;
K1 3:54  103 exp
RT


51:3 kJ=mol
(28)
K2 4:18  107 exp
RT
The mean square S of this fitting was 2.1, identical to the
four-parameter fitting, indicating no further improvement in
the six-parameter fitting with the two additional adjustable
parameters. In particular, the fitted adsorption heats of
20.1 and 51.3 kJ/mol were in excellent agreement with
the suggested values of 20 and 50 kJ/mol, respectively,
reconfirming that the suggested values of Peppley et al. can
be used without causing any serious error in the kinetics. The
excellent agreement between the predicted conversion with
the rate expression, Eqs. (25) and (27), and the experimental
conversion may validate the assumptions made in the
derivation of Eq. (25) under our experimental conditions.
In addition to the mechanistic modeling of the rate,
power-law expressions were also investigated. A critical part

34

J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

of the power-law kinetics is how to incorporate the hydrogen

inhibition effect into the rate expression. If incorporated, the
reaction order for the inhibition effect should become a
negative number, which gives rise to an infinite reaction rate
in the absence of hydrogen. To avoid this difficulty, we used
a power-law expression of the following form:


Ea
rM ka exp 
(29)
Pa A PH b
RT M
In this form, the reaction rate at zero hydrogen partial
pressure is finite with parameter A, and the effect of hydrogen on the rate can also be described with a negative
exponent b. The expression has five adjustable kinetic
parameters, ka, Ea, a, b and A. For the same data set, we
fitted the five parameters by the method in Section 3.5 and
obtained:


103 kJ=mol 0:564
rM 2:19  109 exp 
PM
RT
 11:6 kPa PH 0:647

mol=kg=s

Fig. 11. Effectiveness factor of the catalyst particle at the reactor inlet vs.
temperature for various feed compositions.

estimation of the effectiveness factor allowed us to extend

the temperature range for the kinetic experiments above
200 8C without having to reduce the catalyst particle size.

(30)

The mean square error S was 1.2, about 1.1% average

deviation between the experimental conversion and the
predicted conversion. Fig. 10 shows a comparison between
the predicted conversion with the rate expressions, Eqs. (25)
and (30), and the experimental conversion. As expected
from the small values of S, the predictions of both rate
expressions are in excellent agreement with the experimental data.
The effectiveness factor estimated during the least-square
fitting is shown in Fig. 11. The effectiveness factor was
calculated along the reactor in integration of Eq. (17), and a
profile of the factor was generated for each feed composition
and temperature. To demonstrate that the factor can be
appreciably less than one, the effectiveness factor at the
reactor inlet condition, the same as the feed condition, is
plotted against the temperature in Fig. 11. For the various
feed compositions without hydrogen, the effectiveness plots
virtually coincided with each other, whereas in the presence
of hydrogen the plots showed an increased effectiveness
factor with an increased hydrogen concentration. In fact, the

Fig. 10. Parity plot of experimental conversion and predicted conversion

with the power-law kinetics Eq. (30) and the LangmuirHinselwood
kinetics Eqs. (25) and (27).

4. Conclusions
We carried out a kinetic study of methanol steam
reforming over a commercial catalyst CuO/ZnO/Al2O3 at
atmospheric pressure and at temperatures in the range from
160 to 260 8C. The reaction rate increased with an increase
in the methanol partial pressure but decreased with an
increase in the hydrogen partial pressure, indicating
hydrogen inhibition. Carbon dioxide partial pressure and
water partial pressure, when it was in excess of methanol
partial pressure, did not affect the reaction rate. The products
were almost exclusively hydrogen and carbon dioxide, but a
small amount of CO was also produced at high temperatures;
its concentration in the product gas was less than 1% and was
always well below the equilibrium CO concentration of the
RWGS, in support of the reaction sequence of methanol
steam reforming followed by the RWGS.
A power-law rate expression and a LangmuirHinselwood rate expression were fitted to the experimental data.
Since, internal diffusion limitations were present for the
particle size of the catalyst when the reaction temperature
increased above 200 8C, the effectiveness factor of the
catalyst particle was also estimated during the fitting to
obtain the intrinsic kinetics of the reaction. Details of
computing the effectiveness factor have been elucidated.
There was an excellent agreement between the predicted
conversion by the rate expressions and the experimental
results over the full range of conversion between 0 and
100%.
Usually, the feed to methanol reformers consists only of
the reactants, methanol and water. Addition of hydrogen is
unnecessary for the reforming to proceed. Accordingly, the
rate expressions should predict finite rates for the reaction
mixtures without hydrogen. For this, in the power-law
model, hydrogen partial pressure was corrected by a fitted
constant to avoid an infinite reaction rate in the absence of

J.K. Lee et al. / Applied Catalysis A: General 278 (2004) 2535

hydrogen, since the exponent associated with the hydrogen

partial pressure was a negative number to take into account
the effect of hydrogen inhibition in the reforming. On the
other hand, in the reaction mechanism for the Langmuir
Hinselwood expression, it was necessary to assume two
different kinds of active sites on the catalyst, one for
adsorbed methoxy and the other for adsorbed hydrogen, in
order to derive an expression predicting a finite non-zero
reaction rate in the absence of hydrogen. The reaction
mechanism additionally assumed dehydrogenation of the
adsorbed methoxy to the adsorbed oxymethylene as the RDS
and negligible adsorption of all other species on the active
sites. The resulting rate expression based on the mechanism
well described all the experimental results.

Acknowledgements
The authors gratefully acknowledge MOCIE (Ministry of
Commerce, Industry and Energy, Korea) for their financial
support through the project Infra-technology development
for automotive components.

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