Energy 88 (2015) 399e407

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Energy
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Hydrogen production from methanol partial oxidation over Pt/Al2O3

catalyst with low Pt content
Wei-Hsin Chen a, *, Chun-Ting Shen b, Bo-Jhih Lin a, Shih-Chun Liu b
a
b

Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan
Department of Greenergy, National University of Tainan, Tainan 700, Taiwan

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 20 January 2015
Received in revised form
4 May 2015
Accepted 16 May 2015
Available online 4 June 2015

(POM) Partial oxidation of methanol over a Pt/Al2O3 catalyst with low Pt content is studied where the
inuences of the (GHSV) gas hourly space velocity and oxygen-to-methanol molar ratio (O2/C) on the gas
formation, reaction temperature, and methanol conversion are evaluated. POM operations under cold
start and preheating are also examined. The results indicate that an increase in GHSV signicantly lowers
POM performance. Nevertheless, over 50% of methanol is consumed when the GHSV is as high as
20,000 h
1. The maximum H2 and CO concentrations are located at O2/C 0.7, yielding the optimum O2/
C ratio for POM. Compared to POM with cold start operation, preheating the catalyst bed at 150  C
obviously intensies POM performance, and 100% of methanol conversion is achieved at O2/C  0.6. This
reveals that the Pt/Al2O3 catalyst with low Pt content can be used to trigger POM for H2 production. The
methanol reaction under the combination of the Pt/Al2O3 catalyst and a Cu/ZnO/Al2O3 catalyst for
triggering POM followed by the methanol steam reforming is also investigated. The reaction temperature
under the two-stage reaction is lower than that under POM alone, but the methanol conversion and H2
production in the former are improved. This improvement is especially pronounced at high GHSVs.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Partial oxidation of methanol (POM)
Pt/Al2O3 catalyst
Cold start and preheating
Methanol steam reforming (MSR)
Hydrogen production

1. Introduction
The consumption of fossil fuels, such as oil, coal, and natural gas,
through combustion is the prime source for heat and power generation currently [1]. Seeing that the main elements in fossil fuels
are carbon and hydrogen, they are converted to carbon dioxide and
water after the fuels are burned. The emissions of anthropogenic
carbon dioxide into the atmosphere have become an obstacle for
environmental sustainability due to the deteriorated atmospheric
greenhouse effect and global warming [2]. Hydrogen is one of the
alternative fuels which can improve environmental pollution
problems because of its high power density and clean characteristics. In the last several decades, much progress has been made in
fuel cells [3], and this leads to the foreseeable future of power
generation from fuel cells. For example, Toyota will begin the sales
of (FCV) fuel cell vehicles in Japan before April 2015, and in the US
and Europe during the summer of 2015 [4]. Honda also expects to
launch the sales of (FCEV) fuel cell electric vehicles in 2015 [5].

* Corresponding author. Tel.: 886 6 2004456; fax: 886 6 2389940.

E-mail address: weihsinchen@gmail.com (W.-H. Chen).
http://dx.doi.org/10.1016/j.energy.2015.05.055
0360-5442/ 2015 Elsevier Ltd. All rights reserved.

A number of fuels, such as fossil fuels, methane, and ethanol, can

be used to produce hydrogen. From the perspective of small-scale
and on-board hydrogen production, methanol is a suitable
hydrogen carrier because of the following reasons: (1) methanol is
a liquid fuel and easy to be stored and delivered [6]; (2) it can be
reformed at low temperatures (200e300  C) [7]; (3) methanol has a
high atomic H/C ratio when compared to other hydrocarbons,
implying that more H2 can be produced from per mole of fuel [8];
(4) methanol doesn't have CeC bond, so less coke occurs on
catalysts during its reaction [9].
Several thermochemical methods, including direct decomposition [10,11], steam reforming [12,13], autothermal reforming
[14], and partial oxidation [15,16], can be adopted to produce
hydrogen from methanol. (MD) Methanol decomposition is an
endothermic reaction to produce H2 and CO. To enrich H2 in the
product gas, the water gas shift reaction is usually employed to
transform CO into CO2 [17]. (MSR) Methanol steam reforming is
also an endothermic reaction, so additional heat is required to
trigger the chemical reaction. This makes transient operation
difcult when bursts of energy are needed [18]. Unlike MD and
MSR, (POM) partial oxidation of methanol is an exothermic reaction in nature, so no additional heat is needed [19]. The addition

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W.-H. Chen et al. / Energy 88 (2015) 399e407

of steam into POM leads to the (ATR) autothermal reforming of

methanol [20]. In other words, methanol ATR is a combined
reaction of MSR and POM, and its H2 yield is between the two
reactions. The addition of steam in ATR intensies H2 production,
but lowers the reaction temperature and thereby the reaction rate.
On account of simultaneous addition of oxygen and steam in
methanol ATR, the thermal behavior and operating control
become more complicated and intractable.
In contrast to MSR and methanol ATR, relatively less H2 is
produced from POM. POM is expressed as

CH3 OH 0:5O2 /2H2 CO2 ;

DH0
192:3 kJ mol
1

(1)

By virtue of more heat released from POM being employed for

chemical reactions, POM is kinetically faster than MSR and
methanol ATR, implying that a smaller reactor is achievable for
POM [21]. Catalysts containing noble metals such as Au, Pd, and
Pt have been utilized in POM to reduce its activation energy and
aid in chemical reactions for H2 production. Huang et al. [22]
showed that the Cu/ZnO catalyst with the addition of Au
(4.3 wt%) could initiate POM at a lower temperature, and the
initiation temperature could be decreased with the increase of
gold content. Agrell et al. [23] suggested that Pd/ZnO catalysts
with 2 wt% of Pd were active for selective H2 production by POM,
and the Pd dispersion played a key role in determining the

rez et al. [24] showed that carbonproduct distribution. Ubago-Pe
supported Pt (2 wt%) catalyst with a lower O2/CH3OH molar ratio
resulted in a lower methanol conversion but higher H2 selectivity. At the highest O2/CH3OH molar ratio in their tested
conditions, the total oxidation of methanol was predominant due
to high water and CO2 selectivity. Moreover, increasing reaction
temperature caused an increase in methanol conversion as well
as H2 and CO selectivity.
The literature concerning the experimental studies of POM
using a variety of catalysts is summarized in Table 1 [9,22e28].
The table suggests that the weight percentages of noble metals in
catalysts were in the range of approximately 1e4.5 wt% and the
reaction temperature was controlled at 150e300  C. Reviewing
past literature indicates that very little research has been
performed on POM in association with catalysts containing
Pt [24,28]. Therefore, this study aims to investigate H2 production
from POM over a Pt/Al2O3 catalyst. The Pt content in the catalyst
is merely 0.2 wt% so that cost reduction in catalyst preparation
can be achieved. Though the Pt content is low, the catalyst is
able to induce POM under cold start. In addition, unlike past
studies in which the reaction temperature was set [9,16,19,25],
the transient reaction phenomena of POM from the start-up at
room temperature to the equilibrium temperature under the
steady-state reaction will be examined. The POM performance
affected by the gas hour space velocity (GHSV) and O2/CH3OH
molar ratio will be analyzed. At last, the combination of the
Pt catalyst and a CueZn-based catalyst for improving H2 yield
will be addressed.

2. Experimental
2.1. Catalyst characteristics
A commercial catalyst (Green Hydrotech Inc.) of platinum
(Pt, 0.2 wt%) supported on Al2O3 (99.8 wt%) was employed for POM
study. In brief, a Pt(NH3)2(NO3)2 solution was impregnated into
alumina pellets. Thereafter, the impregnated balls were dried at
100  C and then calcined at 400  C for 1 h [29]. The diameter of the
spherical catalyst was 5 mm, and the surface area of the catalyst
from BET analysis was 165.96 m2 g
1. The porosity of the catalyst
bed was 0.43 cm3 g
1. The X-ray diffraction (XRD, PA Nalytical
X'Pert PRO) pattern of the catalyst is shown in Fig. 1 where the
peaks of Pt and Al2O3 developed at 2q 33.3, 37.7, 46.7, and 67.4 ,
identifying the crystalline characteristics of Pt and Al2O3. These
angles are consistent with the observations of Noh et al. [30], Wan
et al. [31], and Banerjee et al. [32]. Fig. 2a shows the image of the
catalyst surface (  1000) using an ultrahigh resolution scanning
electron microscope (SEM, Carl Zeiss AURIGA). The SEM image
reveals that the holes on the surface were in the order of micrometer. Fig. 2b and c demonstrate the (EDS) energy dispersive
spectrometer maps of Pt and Al, respectively, and indicate that the
two elements were uniformly dispersed on the catalyst surface.
2.2. Reaction system
A schematic of the experimental system is sketched in Fig. 3. The
system could be partitioned into a feeding unit, a reaction unit, a
product gas treatment unit, and a gas analysis unit. The feeding unit

Fig. 1. XRD pattern of Pt/Al2O3 catalyst.

Table 1
Catalysts and operating conditions for partial oxidation of methanol.
Catalyst

Noble metal (wt%)

O2/C

Temperature ( C)

GHSV (h
1)

Reference

Au/CuO/ZnO
AueRu/Fe2O3
AueCu/TiO2eFe2O3
Au4.3CZ (CZ Cu,Zn)
Pd/ZnO
PdeZn/SBA-15
Pt/C
Pt/ZnO

Au (3)
Au (1) Ru (1)
Au (1)
Au (4.3)
Pd (2)
Pd (4.5)
Pt (2)
Pt (1)

0.5
0.5
0.3
0.1e0.5
0.5
0.32e0.38
0.2
0.5

150e275
150e250
175e300
190e250
230e300
240e300
150e230
100e200

e
e
48,000
60,000
e
e
e
e

[25]
[26]
[9]
[22]
[23]
[27]
[24]
[28]

W.-H. Chen et al. / Energy 88 (2015) 399e407

401

was made up of a gas and a liquid feeding subunits. The gas

feeding subunit comprised an air and a N2 steel cylinders, two
electric ow rate controllers (KD-4000), a controller readout
(Brooks 5850E), and a gas mixer. The liquid feeding subunit was a
syringe pump (Chemyx Fusion 200) where the syringe was lled
with methanol. The reaction unit consisted of a quartz tube
(22 mm i.d.), a vertical electric furnace, and a power controller. A
layer of glass ball (upper layer) and a layer of catalyst pellet (lower
layer) were packed in the tube, as shown in Fig. 3. The tube was
enclosed by the furnace, and the power of the furnace was
controlled by the power controller. A K-type thermocouple was
installed at the center of the catalyst bed to detect the reaction
temperature; the temperature was used to provide a reference for
the power controller. The gas treatment unit was composed of a
condenser and a dryer; they were employed to remove the
moisture in the product gas. The gas analysis unit included a gas
analyzer (GA, Fuji ZRJF5Y23-AERYR-YKLYYCY-A) and a gas
chromatography (GC, SRI 310C TCD) to measure the volumetric
concentrations of CO, CO2, CH4, and H2.
2.3. Experimental procedure
Air and N2 were supplied from the two steel cylinders and
blended in the gas mixer. Air was used as the oxidizer for triggering
POM. The volumetric ow rates of the two gases were individually
controlled by the electric ow rate controllers and the controller
readout. Meanwhile, the volumetric ow rate of methanol was
controlled by the syringe pump. The feed gas and methanol were
simultaneously sent into the reaction tube, and the ow rates of the
gas mixture and liquid were adjusted in accordance with the
desired operating conditions. The mass of the glass balls in each
experiment was xed at 20 g (3.5 cm in length), while the catalyst
mass was 6.6 g. The catalyst was uniformly packed as a catalyst bed
whose length was approximately 3 cm. When methanol past
through the layer of glass ball, it was uniformly dispersed. This was
conducive to the mixing of air and methanol in the catalyst bed
wherein POM was triggered. Two different initial states of the
catalyst bed were considered; that is, the operations of POM with
cold start and preheating were performed. When the preheating
case was carried out, the catalyst bed was preheated to 150  C
before the onset of POM experiment. When POM in association
with MSR was studied, 2 g (0.5 cm in length) of commercial Cu/
ZnO/Al2O3 catalyst (MDC-3, Sud-Chemie), in which CuO (42 wt%),
ZnO (47 wt%), and Al2O3 (balance) was contained, was used for the
methanol reforming [20]. The MDC-3 catalyst bed was below the
POM catalyst bed. The moisture of the product gas was removed via
condensation and drying in the condenser and dryer, respectively,
to avoid damaging the sensors installed in the gas analyzer. The
volumetric concentrations of CO, CO2 and CH4 were detected by
the GA, while the concentration of H2 was measured by the GC. The
measured data were recorded at a frequency of 3 min
1. The GA and
the GC were calibrated prior to performing experiments to ensure
the experimental quality. In each run, the experimental duration
was 90 min which was sufciently long to reach the steady-state
reaction.
2.4. Operating conditions

Fig. 2. (a) SEM image (  1000) and EDS maps of (b) Pt and (c) Al of the adopted
catalyst.

The (GHSV) gas hourly space velocity and the O2-to-methanol

molar ratio (i.e., the O2/C ratio) are two important factors affecting
the performance of POM; therefore, they were taken into account in
this study. In this study, the GHSV and O2/C ratio were in the ranges
of 5000e20,000 h
1 and 0.4e0.8, respectively. To provide a basis
for experiments, the ow rate of methanol was xed at
0.2 cm3 min
1 (at 25  C). On account of the controls of GHSV and

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W.-H. Chen et al. / Energy 88 (2015) 399e407

Fig. 3. A schematic of experimental system.

Table 2
Volumetric ow rates (mL min
1, 25  C) of feed gas, air, and N2 at various operating
conditions.
O2/C ratio

GHSV
(h
1)

Feed gas
(N2 air)

Air

N2

0.4

5000
10,000
20,000
10,000

235.8
471.6
943.1
471.6
471.6
471.6
471.6
471.6
943.1
943.1
943.1
943.1

230.5
230.5
230.5
230.5
288.1
345.7
403.3
460.9
230.5
288.1
345.7
403.3

5.3
241.1
712.6
241.1
183.5
125.9
68.3
10.7
712.6
655
597.4
539.8

0.4
0.5
0.6
0.7
0.8
0.4
0.5
0.6
0.7

20,000

O2/C ratio in the experiments, N2 was used as a balance gas to reach

the requirement of feed gas (air N2) ow rate. Within the
investigated ranges of GHSV and O2/C ratio, the volumetric ow
rates of air, N2, and feed gas are summarized in Table 2.

in the rst 20 min after the onset of experiment. When the

experimental time is 30 min, the temperature almost reaches the
steady state and the equilibrium temperature is around 430  C.
This reveals that the Pt/Al2O3 catalyst is able to trigger POM without
additional heat supply, even though the Pt amount in the catalyst is
as low as 0.2 wt%. The temporal distributions of H2, CO, CO2, and
CH4 concentrations (vol%) shown in Fig. 4b indicate that the gas
formation also almost reaches the steady state at the experimental
time of 30 min, except for CH4. The steady-state concentrations of
H2, CO, and CO2 are approximately 11.4, 6.1, and 5.2 vol%, respectively, while the CH4 concentration is around 5100 ppm. The higher
CO concentration than the CO2 one elucidates the insufcient reaction of POM, presumably due to the high GHSV (20,000 h
1)
which results in the lower residence time of reactants in the
catalyst bed. In addition to POM, the CH4 formation reveals that
methanation occurs in the catalyst bed as well through the
following process

CO 3H2 4CH4 H2 O;

DH0
205:9 kJ mol
1

(2)

3.2. Effect of GHSV

3. Results and discussion
3.1. Transient characteristics of POM
The transient reaction phenomena of POM with preheating
(150  C) at the conditions of GHSV 20,000 h
1 and O2/C 0.6 are
examined in Fig. 4. Fig. 4a depicts that the temperature rises rapidly

The steady-state proles of H2, CO, CO2, and CH4 concentrations

from POM at O2/C 0.4 and GHSV 5,000, 10,000, and 20,000 h
1
are shown in Fig. 5a where POM is triggered under the cold start
operation. Detailed ow rates of air and N2 at the three different
GHSVs are shown in Table 2. GHSV is the ratio of the void volume in
the catalyst (cm3) and the ow rate of the feed gas (cm3 h
1); it is

W.-H. Chen et al. / Energy 88 (2015) 399e407

Fig. 4. Temporal distributions of (a) temperature and (b) H2, CO, CO2, and CH4 concentrations for POM with preheating operation at GHSV 20,000 h
1 and O2/C 0.6.

also the reciprocal of the residence time of the feed gas in the
catalyst bed [33]. Physically, a higher GHSV stands for a faster
volumetric ow rate or a shorter residence time for the reactants in
the catalyst bed. Fig. 5a depicts that an increase in GHSV lowers gas
formation. Fig. 4b has indicated that the methanation reaction requires a longer time (40 min) to reach the steady state. This may be
the reason that the drop in CH4 concentration in Fig. 5a is more
pronounced than the other gases when GHSV increases from 5000
to 10,000 h
1. The concentrations of H2 are substantially higher
than those of CO and CO2, while the CO and CO2 concentrations are
in a comparable state. The formation of CO reects that not only
POM but also methanol decomposition (MD) occur in the catalyst
bed. MD is expressed by

CH3 OH42H2 CO;

DH0 90:1 kJ mol
1

(3)

Chang et al. [9] revealed that MD might be induced in POM

when the reaction temperature was beyond 523 K, leading to an
increase in H2 selectivity along with CO formation.

403

Fig. 5. Proles of (a) H2, CO, CO2, and CH4 concentrations and (b) reaction temperature
and methanol conversion for POM with cold start operation at O2/C 0.4.

The proles of reaction temperature and methanol conversion

shown in Fig. 5b depict that increasing GHSV lowers the reaction
temperature and methanol conversion. For the GHSV of 5000 h
1,
the steady-state temperature and methanol conversion are 368  C
and 71.8%, respectively, and they drop to 301  C and 56.4% when
the GHSV increases to 10,000 h
1. This implies that the temperature and conversion are reduced by 67  C and 15.4%, respectively,
when the ow rate of the feed gas is doubled. In a owing system
hler number can be utilized
with combustion reaction, the Damko
to represent the characteristic time ratio between the uid ow
and the chemical reaction [34,35]. In this study, an increase in
hler number, so the chemical reaction
GHSV causes a lower Damko
is abated. When the GHSV is further doubled to 20,000 h
1, the
reaction temperature and the methanol conversion are reduced to
266  C and 52.5%, respectively. Nevertheless, over 50% of methanol is consumed, even though the reaction temperature is as low
as 266  C.

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W.-H. Chen et al. / Energy 88 (2015) 399e407

3.3. Effect of O2/C ratio

The performance of POM at GHSV 10,000 h
1 and
O2/C 0.4e0.8 under the cold start operation is shown in Fig. 6.
The ow rates of air and N2 at the O2/C ratios are also given in
Table 2. The concentrations of H2, CO, and CO2 rise with
increasing O2/C ratio, as a consequence of enhanced methanol
combustion reaction. For the O2/C ratio between 0.5 and 0.7,
there is a signicant difference between the CO and CO2
concentrations, and the CO concentration is higher than the CO2
one. The higher CO concentration is presumably due to the
intensied reverse water gas shift reaction [15,19]. The reaction is
written as

DH0 41:2 kJ mol
1

CO2 H2 4CO H2 O;

(4)

The highest H2 and CO concentrations develop at O2/C 0.7

where the values are 21.1 and 12.1%, respectively. When the O2/C
ratio is 0.8, more oxygen is provided for methanol combustion. As a

(a)
30

10000

8000

20
6000
15
4000

CH 4 (ppm)

Concentration (%)

3.4. Effect of preheating

H2
CO
CO2
CH 4

25

10
2000

0
0.3

0.4

0.5

0.6

0.7

0.8

0
0.9

O2/C

(b)
500

100

400

80

300

60

200

40

100

20

0
0.3

0.4

0.5

0.6

0.7

0.8

CH 3OH conversion (%)

CH 3OH
Temperature

o
Temperature ( C)

consequence, the CO2 and H2O concentrations increase, whereas

the H2 and CO concentrations decrease [24]. The CO2 concentration
is close to the CO one. The CH4 concentration is raised notably when
the O2/C ratio increases from 0.4 to 0.5. Once the ratio is greater
than the stoichiometric ratio of POM (i.e., O2/C > 0.5), the CH4
concentration declines.
When the O2/C ratio is 0.4, the steady-state temperature is
around 301  C. On account of the relatively low temperature, the
methanol conversion is 56.4% (Fig. 6b). An increase in O2/C ratio
increases the reaction temperature, so the methanol conversion
is improved. This characteristic is especially signicant when the
O2/C ratio increases from 0.4 to 0.5 where the conversion is
lifted from 56.4 to 78.5 %. It follows that more oxygen provided is
conducive to driving POM from the room temperature (the cold
start). The reaction temperature is beyond 400  C when the O2/C
ratio is higher than or equal to 0.6. For the O2/C ratio of 0.8, the
reaction temperature and methanol conversion increase to
469  C and 90.4%, respectively. However, it should be illustrated
that the higher methanol conversion does not imply the higher
H2 production (Fig. 6a), stemming from more H2O and CO2
generated. The optimum operation is located at O2/C 0.7, from
the point of view of H2 and CO (or syngas) production.

0
0.9

O2/C
Fig. 6. Proles of (a) H2, CO, CO2, and CH4 concentrations and (b) reaction temperature
and methanol conversion for POM with cold start operation at GHSV 10,000 h
1.

The comparison of gas concentrations from POM between

the operations of cold start and preheating is presented in Fig. 7
where the GHSV is xed at 20,000 h
1. The ow rates of air and
N2 are also given in Table 2. Overall, the concentrations of H2,
CO, and CH4 from POM under preheating are higher than those
under cold start. This behavior is similar to the observations of
catalytic partial oxidation of methane with heat recovery [36],
and reects that preheating the catalyst bed facilitates POM
performance. Moreover, the H2 formation from POM with
preheating is less sensitive to the O2/C ratio. The proles of the
reaction temperature and methanol conversion under the two
operating modes are demonstrated in Fig. 8. Within the investigated range of O2 /C ratio, the reaction temperature under the
preheating operation is higher than that under the cold start
operation around 38e84  C. The minimum and the maximum
temperature differences are located at O2/C 0.4 and 0.6,
respectively. In view of the higher reaction temperature of
POM with preheating, the methanol conversion is also higher.
In particular, the methanol conversion under the preheating
operation at O2/C 0.6 or 0.7 is 100%. The values of the
conversion under cold start operation at O2/C 0.6 and 0.7 are
69.3 and 84.2%, respectively. It is thus gured out that
POM with preheating advantages methanol conversion and H2
yield. It is noted that when the O2/C ratio increases from 0.4 to
0.5 under the preheating operation, there is a dramatic
growth in methanol conversion in that the value goes up
from 59.1 to 93.9 %. Therefore, the O2/C ratio should be
controlled at larger than or equal to 0.5 for better POM
performance.

rez et al. [24], a Pt/C catalyst with
In the study of Ubago-Pe
2 wt% of Pt was employed for POM, and the reaction temperature
was controlled at 150e230  C. Their results suggested that the
methanol conversion at O2/C 0.5 was between 18 and 77%. Wan
et al. [28] utilized a Pt/ZnO catalyst to trigger POM where the
reaction temperature was between 100 and 200  C, and the
methanol conversion was between 72 and 88% at O2/C 0.5.
However, the values of GHSV were not provided in the two
studies. In the present study, for POM with preheating operation
at GHSV 20,000 h
1, the methanol conversion is 93.9% and the
equilibrium temperature is 360  C (Fig. 8b). The obtained

W.-H. Chen et al. / Energy 88 (2015) 399e407

405

Fig. 7. Proles of H2, CO, CO2, and CH4 concentrations for POM with (a) cold start
operation and (b) preheating operation at GHSV 20,000 h
1.

Fig. 8. Proles of reaction temperature and methanol conversion for POM with (a) cold
start operation and (b) preheating operation at GHSV 20,000 h
1.

conversion and the equilibrium temperature are higher than

those reported in the two studies [24,28]. Accordingly, despite
the low content of Pt in the catalyst, it is able to provide the
satised performance of POM reaction.

in the two catalyst beds, that is, POM is followed by MSR. A

comparison to Fig. 5a suggests that the two-stage reaction
(Fig. 9a) gives higher H2 and CO2 concentrations and a lower CO
concentration. MSR is expressed as

CH3 OH H2 O43H2 CO2 ;

DH0 49:5 kJ mol
1

(5)

3.5. Combination of POM catalyst and MSR catalyst

In Fig. 5, the performance of POM at GHSV 5,000, 10,000,
and 20,000 h
1 under the cold start operation has been examined. It can be seen that the CO and CO2 concentrations are in a
comparable state, while the methanol conversion decays significantly when the GHSV increases from 5000 to 10,000 h
1. It is
known that H2O will be produced from POM, and only partial
methanol is converted (Fig. 5b) [24]. To improve H2 formation
from methanol, its reaction under the combination of the Pt/
Al2O3 catalyst and the Cu/ZnO/Al2O3 catalyst (MDC-3, SudChemie) is analyzed. Methanol undergoes a two-stage reaction

The preceding reaction pertains to an endothermic reaction in

nature. This is the reason why the temperatures in Fig. 9b are
lower than those in Fig. 5b. Nevertheless, the two-stage reaction
or the combination of the catalysts leads to a higher methanol
conversion (Fig. 9b). For instance, corresponding to the GHSVs of
5,000, 10,000, and 20,000 h
1, the values of methanol conversion
in the single stage reaction (Fig. 5b) are 71.8, 56.4, and 52.5%,
respectively, whereas they are 75.6, 74.9, and 69.7% in the twostage reaction (Fig. 9b). Overall, the higher the GHSV, the more
signicant is the improvement of methanol conversion by the
two-stage reaction.

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W.-H. Chen et al. / Energy 88 (2015) 399e407

maximizing H2 and CO production develops at 0.7 in that a higher

O2/C ratio (>07) leads to the predominant mechanism of combustion. Compared to POM with cold start operation, preheating the
catalyst bed (at 150  C) obviously intensies the POM performance,
and 100% of methanol conversion can be achieved at O2/C  0.6.
Therefore, POM with preheating is recommended for H2 production. Because of H2O generated from POM, the study indicates
that methanol conversion and H2 formation from the two-stage
reaction (i.e., POM followed by MSR) are higher than those of the
singleestage reaction (i.e., POM alone). This improvement is
especially signicant when GHSV is high. From the adopted low
Pt-content catalyst, the present study has provided a useful insight
into the operation of POM for H2 production, while the catalyst
preparation with cost reduction can be achieved.
Acknowledgments
This research was nancially supported in part by the Ministry
of Science and Technology, Taiwan, R.O.C., under contract MOST
104-3113-E-042A-001-.
References

Fig. 9. Proles of (a) H2, CO, CO2, and CH4 concentrations and (b) reaction temperature
and methanol conversion from the combination of POM and MSR with cold start
operation at O2/C 0.4.

4. Conclusions
The reaction characteristics of partial oxidation of methanol
(POM) with the aid of a Pt/Al2O3 catalyst have been investigated
experimentally, and the inuences of the gas hourly space velocity
(GHSV) and oxygen-to-methanol molar ratio (O2/C ratio) upon the
performance of POM have been examined. The reaction characteristics of POM can be illustrated based on methanation, methanol
decomposition, reverse water gas shift reaction, and methanol
steam reforming. The results suggest that POM can be triggered for
hydrogen production, even though the Pt content in the catalyst is
as low as 0.2 wt% and the GHSV is as high as 20,000 h
1. An increase
in GHSV lowers the POM performance, as a consequence of shorter
residence time of reactants in the catalyst bed. Nevertheless, within
the investigated ranges of the parameters, the reaction temperature
is always higher than 244  C (at O2/C 0.4 and GHSV 20,000 h
1)
and over 50% of methanol is consumed. The optimum O2/C ratio for

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