ARTICLE IN PRESS

Chemical Engineering Science ( ) –

www.elsevier.com/locate/ces

Selective production of hydrogen via oxidative steam reforming

of methanol using Cu–Zn–Ce–Al oxide catalysts
Sanjay Patel a,b , K.K. Pant a,∗
a Department of Chemical Engineering, Indian Institute of Technology, Hauz Khas, New Delhi 110016, India
b Department of Chemical Engineering, Institute of Technology, Nirma University of Science and Technology, Ahmedabad 382481, India

Received 15 June 2006; received in revised form 19 January 2007; accepted 29 January 2007

Abstract
The oxidative steam reforming of methanol (OSRM) was carried out to produce the hydrogen selectively for polymer electrolyte membrane
(PEM) fuel cell applications over Cu–Zn–Ce–Al oxide and Cu–Zn–Al oxide catalysts of varying compositions prepared by co-precipitation
method. Catalyst performance was evaluated in a packed bed reactor over a wide range of operating conditions, and reaction parameters were
optimized in order to maximize the hydrogen production with minimum carbon monoxide formation. The incorporation of ceria in Cu–Zn–Al
oxide catalysts enhanced the activity greatly compared to without it. The Cu/Zn/Ce/Al:30/20/10/40 exhibited 100% methanol conversion and
244 mmol s−1 kg−1cat hydrogen rate at 553 K with carbon monoxide as low as 995 ppm, which reduces the load on preferential oxidation of CO
to CO2 significantly before feeding the hydrogen rich stream to the PEM fuel cell as a feed. Ceria had improved the dispersion and specific
surface area of copper in multi-component Cu–Zn–Ce–Al oxide catalysts which were confirmed by the physicochemical properties, X-ray
diffraction (XRD), temperature programmed reduction (TPR) and CO chemisorption studies. The chemisorption studies were performed at
193 K in order to hinder the spillover of carbon monoxide to ceria. The time-on-stream stability test had shown Cu–Zn–Ce–Al oxide catalysts
as more stable compared to Cu–Zn–Al oxide catalysts. The amount of carbon deposited onto the catalysts was determined using TG/DTA
thermogravimetric analyzer and the type of carbon species were identified using C1s X-ray photoelectron spectroscopy (XPS) spectra.
䉷 2007 Elsevier Ltd. All rights reserved.

Keywords: Hydrogen; OSRM; Ceria; PEM fuel cell

1. Introduction dimethyl ether (Semelsberger et al., 2006), etc. Methanol offers

Hydrogen is expected to play a major role in the future as
a carbon free energy carrier. Its use in the vehicles via poly-
mer electrolyte membrane (PEM) fuel cells can offer the non-
toxic tail-pipe emissions and high over all efficiency compared
to conventional internal combustion engines (Edwards et al.,
1998; Bowers et al., 2006). The on-board storage of hydro-
gen with high energy density is facing some technical prob-
lems (Breen and Ross, 1999; Raimondi et al., 2002). One
promising solution to this can be an on-board production of
hydrogen using liquid hydrocarbons like methanol (Patel and
Pant, 2006c; Yan et al., 2006), ethanol (Sahoo et al., 2007),
several advantages for the hydrogen production compared to
other liquid organics (Velu et al., 2001; Patel and Pant, 2006a).
There are different routs available for the hydrogen production
from methanol as follows. One is partial oxidation of methanol
(POM),
CH3 OH + 0.5O2 ←→ 2H2 + CO2 , H 0 = −192 kJ mol−1 .
(1)
This is a highly exothermic reaction which leads to the problem
of heat removal and reactor temperature control, and also pro-
duces significant amount of CO (Wang et al., 2003). Another
route is the steam reforming of methanol (SRM),

∗ Corresponding author. Tel.: +91 11 26596172; fax: +91 11 26581120. CH3 OH + H2 O ←→ 3H2 + CO2 , H 0 = 49.5 kJ mol−1 .
E-mail address: kkpant@chemical.iitd.ac.in (K.K. Pant). (2)
0009-2509/$ - see front matter 䉷 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.01.066

Please cite this article as: Patel, S., Pant, K.K., Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide
catalysts. Chemical Engineering Science (2007), doi: 10.1016/j.ces.2007.01.066
 ARTICLE IN PRESS
2 S. Patel, K.K. Pant / Chemical Engineering Science
SRM can produce H2 /CO2 in the molar ratio of 3/1. It pro-
duces relatively small amount of carbon monoxide, usually less
than 1%, as a by-product over copper-based catalysts (Choi and
Stenger, 2002; Lindstrom et al., 2003; Patel and Pant, 2006b).
But it is highly endothermic and has a slow rate of reaction.
The limitations of partial oxidation and steam reforming of
methanol for the hydrogen production for PEM fuel cell appli-
cations could be overcome by combining them as an oxidative
steam reforming of methanol (OSRM) that can be performed
auto-thermally with idealized reaction stoichiometry.
CH3 OH + (1 − 2a)H2 O + aO2 ←→ (3 − 2a)H2 + CO2 ,
H 0 = (49.5 − 241.8 ∗ 2a) kJ mol−1 , 0 a 0.5,
where a is an oxygen to methanol (O/M) molar ratio. For
a = 0.125 OSRM can be operated auto-thermally at 573 K. The
limited work in the field of OSRM has been reported over the
different catalysts like CuO/ZnO/Al2 O3 (Murcia-Mascaros
et al., 2001; Turco et al., 2004a,b), Cu/Zn/Zr/Al oxide (Velu
et al., 2001), Ce/CuO (Shan et al., 2004), Pd/ZnO (Liu et al.,
2003), Pd–Zn/Cu–Zn–Al (Chen et al., 2007), etc. Turco
et al. (2004b) observed the 100% methanol conversion at a
temperature greater than 623 K. They observed the methane
and other oxygenates in addition to H2 , CO2 and CO over
CuO/ZnO/Al2 O3 . The copper–ceria based catalysts have been
used widely for the preferential oxidation of carbon monoxide
(PROX) (Wang et al., 2002; Papavasiliou et al., 2006). Also
ceria is known to improve the stability of catalysts (Mattos
et al., 2002). Therefore, in the present study we have devised
the incorporation of ceria in Cu–Zn–Al oxide catalysts in order
to improve the catalyst performance in OSRM process in terms
of methanol conversion, hydrogen selectivity, suppression of
CO formation and deactivation compared to Cu–Zn–Al oxide
catalysts. The detailed characterization and activity study of
Cu–Zn–Ce–Al as well as Cu–Zn–Al oxide catalysts have been
carried out over the wide range of operating conditions of
OSRM process.
2. Experimental
All the Cu–Zn–Ce–Al oxide and Cu–Zn–Al oxide catalysts,
abbreviated as CZCeAi and CZAi , respectively, were prepared
by co-precipitation method as follows. The 1.25 M solutions
of Cu(NO3 )2 3H2 O, Zn(NO3 )2 6H2 O, Ce(NO3 )3 6H2 O and
Al(NO3 )3 9H2 O were prepared separately and then mixed in a
volume proportion corresponding to the final composition of
the catalysts to be obtained. The resulting solution was stirred
and heated to 343 K in a round-bottomed flask. The aqueous
0.5 M Na2 CO3 solution was added drop-wise to the nitrate
solution under vigorous stirring until pH 7 was attained at a
temperature of 343 K. The precipitate was allowed to age for
2 h at temperature 343 K with stirring. The excess solution was
removed by filtration. The precipitate was washed three times
by double distilled water at a temperature of 343 K followed
by several times by double distilled water at room temperature
in order to remove the sodium salts. The drying was carried
out at 383 K for 12 h. This material was the catalyst precursor,
Please cite this article as: Patel, S., Pant, K.K., Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide
catalysts. Chemical Engineering Science (2007), doi: 10.1016/j.ces.2007.01.066
( ) –
which was crushed to a fine powder and subsequently the
catalyst was produced by calcination in the presence of air at
673 K for 4 h. The pellets of 3 mm size from fine catalyst pow-
der were made in an automatic palletizing press Techno Search
AP-15 and subsequently crushed and sieved to a size of 20/25
mesh. The same procedure was followed for the preparation
of Cu–Zn–Al oxide catalysts. The final elemental composition
was determined using atomic absorption spectroscopy (AAS)
Varian AA420FS. Surface area and pore volume of catalysts
were measured using ASAP 2010 Micromeritics micro-pore
surface area analyzer. The copper surface area, dispersion and
particle size were measured by CO chemisorption at 193 K
(3) using Micromeritics Pulse Chemisorption ChemiSorb 2720
for Cu–Zn–Ce–Al oxide catalysts (Holmgren and Anderson,
1998; Holmgren et al., 1999; Cheekatamarla et al., 2005). It
has been reported that the spillover of CO from metal onto the
ceria support gives a higher dispersion of metal than the actual
metal dispersion. Chemisorption of CO at 193 K alleviates this
phenomenon. A 0.5 g catalyst was reduced in the stream of
9.9% H2 /Ar with the flow of 30 cc min−1 at 533 K for 3 h with
a final temperature achieved by 10 K min−1 ramp rate. Then
the sample was flushed with N2 for 30 min and subsequently
cooled to room temperature at a ramp rate of 10 K min−1 . Then
193 K temperature of sample was achieved by immersing the
sample holder in the dewar of iso-propanol gel that was pre-
pared by quenching it with liquid nitrogen. At this temperature,
0.2 ml pulses of CO were injected periodically in the stream
of nitrogen in order to find out the total CO uptake. Tem-
perature programmed reduction (TPR) of calcined catalysts
was carried out using Pulse Chemisorption ChemiSorb2720,
Micromeritics. Different crystalline phases were identified by
means of Philips X’PERT PRO PW 3040/60 (PANalytical)
powder diffractometer using monochromatic Cu-K 1.5418 Å
radiation at a current of 30 mA with diffraction angle ranging
from 10–60◦ . The amount of carbon deposited on catalysts
was determined by oxidizing it in the air by means of ther-
mogravimetric analyzer (TGA, Seiko TG/DTA 32 SSC 5100).
Surface analysis of post reaction catalysts was done by X-ray
photoelectron spectroscopy (XPS) using Perkin Elmer-1257.
Catalyst performance was evaluated in a fixed bed reactor
assembled with electrically heated furnace and PID con-
trollers. All the catalysts were reduced in situ in the stream
of 10% H2 /N2 mixture before OSRM reaction. The reduction
of Cu–Zn–Ce–Al oxide catalysts was carried out at a ramp of
10 K min−1 with final temperature of 500 K and dwelled for
1 h; on the other hand Cu–Zn–Al oxide catalysts dwelled at
530 K for 1 h. A mixture of methanol and water vapor gener-
ated in an evaporator was passed through a preheating zone
along with oxygen and nitrogen prior to entering the reactor.
The stainless steel reactor was used which consisted of a cylin-
drical cup of 19 mm diameter and 30 mm length, perforated on
the bottom with orifices of 0.5 mm diameter to enable the flow
of gases. The catalyst was retained by a plug of glass wool.
An equal amount of inert quartz particles of 20/25 mesh were
mixed with the catalyst to dilute the heat transfer effects. A
thermowell passed through the catalyst bed so that temperature
could be measured at different positions along the bed using
 ARTICLE IN PRESS
S. Patel, K.K. Pant / Chemical Engineering Science ( ) – 3

thermocouple. Product effluent was passed through the con-
denser and separator in order to separate the unconverted
methanol and water from the product gases. Operating tem-
perature, contact time (W/F) and oxygen to methanol (O/M)
molar ratio varied from 473 to 573 K, 3 to 15 kgcat s mol−1
and 0.1 to 0.5, respectively, with steam to methanol (S/M)
molar ratio = 1.5 and pressure P = 1 atm being kept con-
stant. Reaction products were analyzed by Nucon-5700 Gas
chromatograph, equipped with thermal conductivity detector
having carbosphere column for gaseous product concentration
measurement and flame ionization detector with silica–alumina
fused capillary column for unconverted liquid reactants. The
very low concentration of CO was determined using molec-
ular sieve-5A followed by methanizer installed with flame
ionization detector.
3. Results and discussion
3.1. Catalyst characterization
The specific surface area and pore volume of various cat-
alyst samples shown in Table 1 were measured according to
the Brunauer–Emmett–Teller (BET) method by nitrogen ad-
sorption at 77 K after degassing the samples at least for 12 h
at 523 K. There is no significant difference in the BET sur-
face area was observed among the catalysts. The surface area,
dispersion and particle size of copper in the catalyst samples
shown in Table 1 were calculated assuming atomic adsorption
of CO on a copper site and the site density of copper to be
0.069 nm2 atm−1 . All the copper particles were assumed to
be spherical for calculating the mean particle size of copper.
Stoichiometrically one atom of CO is adsorbed on each copper
atom site. The CO chemisorption was carried out at 193 K
in order to hinder the spillover of CO to the ceria that was
confirmed by comparing the chemisorption results of catalysts
which were obtained at room temperature 302 K. Holmgren
and Anderson (1998) have confirmed the CO spillover to
the ceria support by performing CO chemisorption at 298 K
followed by temperature programme desorption (TPD) over
Pt/CeO2 catalyst. However, they observed that the spillover
of CO to ceria support could be hindered by performing CO
chemisorption at 195 K. The catalysts containing Ce exhibited
higher copper surface area and better dispersion, and hence
the smaller copper particle size compared to those containing
only Cu–Zn–Al oxides. However, optimum loading of Ce was
required as shown in Table 1. The alumina and ceria enhanced
the dispersion of copper oxide species by stabilization of iso-
lated Cu2+ ions in their matrix and moderately by formation
of spinal like CuAl2 O4 . This is in agreement with the work of
Fernandez-Garcia et al. (1997) who confirmed that the ceria
increases the copper dispersion by reducing the particle size of
copper in the CuO/CeO2 /Al2 O3 catalysts compared to only
CuO/Al2 O3 catalysts. XRD spectra of catalyst precursors dis-
played in Fig. 1(a) exhibit mainly hydrotalcite (HT)-like lay-
ered double hydroxide (LDH; (CuZn)6 Al2 (OH)16 CO3 · 4H2 O;
JCPDS file No. 38-487) with other phases such as aurichal-
cite (AC; (CuZn)5 (CO3 )2 (OH)6 ; JSPDS file No. 7-743) and
bayerite (AH; Al(OH)3 ; JCPDS file No. 20-11). At pH of
precipitates higher than 7 during catalyst preparation, aurichal-
cite was the dominated phase of catalyst precursors, and on
the other hand at pH lower than 7, the hydroxynitrates were
dominated. At pH 7 HT-like LDH phase was dominant which
exhibited the higher catalytic activity. The calcination of these
precursors resulted in the catalyst comprising copper, zinc,
cerium and aluminum oxide. When catalysts were reduced in
the stream of hydrogen at the beginning of activity test, CuO
converted into copper where as zinc, cerium and aluminum
remained in oxide form as shown in Fig. 1(b). A small peak of
spinal CuAl2 O4 was also observed in the XRD spectra. As per
the Scherrer formula the crystal size is inversely proportional to
the peak width at constant diffraction angle and monochromatic
wavelength. The peak width of copper for a CZCeA2 catalyst
is broader than that for the CZA2 catalyst (Fig. 1(b)), which re-
sulted in a smaller copper crystallite size. The smaller the crys-
tallite sizes, the better the copper dispersion and the more the
copper surface area for CZCeA2 catalyst compared to CZA2
catalyst. The reducibility of copper species in catalysts was
investigated by TPR experiments, and profiles are displayed in

Table 1
Physiochemical properties of catalysts

CZA1 CZA2 CZCeA1 CZCeA2 CZCeA3

Cu/Zn/Al Cu/Zn/Al Cu/Zn/Ce/Al Cu/Zn/Ce/Al Cu/Zn/Ce/Al

Preparative composition (wt%) 30/30/40 30/20/50 30/25/5/40 30/20/10/40 30/10/20/40

Final composition (wt%) 29/26/45 29/19/52 30/24/6/40 29/18/10/43 29/10/19/42
BET surface area (m2 g−1 ) 92 106 96 108 101
Pore volume (cm3 g−1 ) 0.26 0.32 0.28 0.34 0.29
Cu dispersion (%) 9.4 12.8 10.2 19.6 14.8
Cu surface area (m2 g−1 ) 18.3 25.1 20.2 38.6 29.3
Cu particle size (Å) 108 80 101 52 69
Methanol conversiona (%) 60 77 69 100 90
H2 ratea (mmol s−1 kg−1
cat ) 132 180 160 244 217
CO formationa (ppm) 9400 3400 1400 995 1240
a Results at T = 553 K, S/M = 1.5 M, O/M = 0.15 M and W/F = 11 kgcat mol−1 s.
Please cite this article as: Patel, S., Pant, K.K., Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide
catalysts. Chemical Engineering Science (2007), doi: 10.1016/j.ces.2007.01.066
 ARTICLE IN PRESS
4 S. Patel, K.K. Pant / Chemical Engineering Science ( ) –

LDH
AH
AC
(003) (012) (015)
(006)
Intensity (a.u.)

CZCeA2

CZA2

10 15 20 25 30 35 40 45 50 55 60
2θ

Cu
CuO
ZnO
Al2O3
CeO2
Intensity (a.u.)

CuAl2O4
Fig. 3. Catalytic activity in terms of methanol conversion for different catalysts
as a function of temperature (W/F = 11 kgcat s mol−1 methanol , O/M = 0.15 M,
CZCeA2
S/M = 1.5 M, P = 1 atm).

attributed to the reduction of CuO into Cu whereas the peak

CZA2
at 459 K might be due to spinal CuAl2 O4 . But it is expected
that the limited amount of surface CuAl2 O4 species contribute
10 15 20 25 30 35 40 45 50 55 60
to the TPR signals; therefore, the peak at 459 K might be a
2θ
composite peak of CuAl2 O4 and Cu2 O reduction. The forma-
Fig. 1. (a) X-ray diffraction patterns of catalysts precursors. Layered dou-
tion of Cu2 O is also confirmed by Lindstrom et al. (2002) and
ble hydroxide (LDH) (CuZn)6 Al2 (OH)16 CO3 · 4H2 O; aurichalcite (AC): Reitz et al. (2001) in which they found two step reduction of
(CuZn)5 (CO3 )2 (OH)6 ; bayerite (AH): Al(OH)3 . (b) X-ray diffraction pat- copper: Cu(II) → Cu(I) → Cu(0). For CZCeA2 catalyst three
terns of reduced catalysts. composite peaks were observed with shoulders at 443, 463 and
488 K. The lower valent Cu species cause structural defects of
ceria lattice. However, cerium sublattice is not strongly per-
turbed by these defects, which instead cause the formation of
a defective oxygen sublattice (Shan et al., 2004). In this way
many oxygen vacancies are generated with the formation of
solid solutions. Therefore, oxygen vacancies of CZCeA2 cata-
lyst were reduced at a low temperature of 443 K during TPR to
give first peak. The peak at temperature 463 K was attributed
to spinal CuAl2 O4 and Cu2 O, and a peak at 488 K was due to
CuO reduction to Cu. Breen and Ross (1999) and Agrell et al.
(2001) reported that the highly dispersed CuO gave the TPR
signals at lower temperature than the bulk CuO. Dow et al.
(2000) and Liu and Flyzani-Stephanopoulos (1996) found that
strong interaction occurs at the interface between highly dis-
persed copper oxide and ceria (interfacial metal oxide–support
interaction (IMOSI)) due to their close contact with each other
that leads to the low temperature reduction of copper oxide.
Fig. 2. TPR profiles of calcined catalysts. This is also observed in the present study with the catalyst
CZCeA2 for which CuO was reduced at lower temperature than
Fig. 2. All the catalysts exhibited composite peaks, with two that of CZA2 due to better dispersion of copper in CZCeA2 .
or three unresolved signals. These might be due to reduction
of different Cu(II) species such as, CuO, CuAl2 O4 and Cu2+ 3.2. Effect of ceria over catalysts performance
ions incorporated in octahedral sites of the alumina phase. The
pure CuO sample had shown a single large peak at 613 K. For Figs. 3 and 4 clearly depict that the addition of ceria in
CZA2 catalyst two peaks were observed, the peak at 513 K is CZAi catalysts improved the performance greatly in terms
Please cite this article as: Patel, S., Pant, K.K., Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide
catalysts. Chemical Engineering Science (2007), doi: 10.1016/j.ces.2007.01.066
 ARTICLE IN PRESS
S. Patel, K.K. Pant / Chemical Engineering Science
Fig. 4. Catalytic activity in terms of hydrogen production rate for differ-
ent catalysts as a function of temperature (W/F = 11 kgcat s mol−1methanol ,
O/M = 0.15 M, S/M = 1.5 M, P = 1 atm).
of methanol conversion as well as hydrogen production. The
CZCeA2 exhibited 100% methanol and 244 mmol s−1 kg−1 cat hy-
drogen rate at 553 K whereas 50% and 112 mmol s kg−1 −1
cat
given by CZA1 . The methanol conversion was increased as a
function of temperature for all the catalysts. The enhanced ac-
tivity of CZCeA2 could be due to higher copper surface area and
better copper dispersion (Table 1 and XRD spectra of Fig. 1(b)).
Cheekatamarla et al. (2005) observed the better copper disper-
sion in ceria promoted copper–alumina catalyst than catalyst
without it. The addition of zinc oxide and ceria caused the syn-
ergistic effect to give the activity enhancement. Ceria has been
widely used as a promoter in three-way catalysts for removal of
carbon monoxide, nitrogen oxides and hydrocarbons under con-
ditions with rich-lean air/fuel in automotive exhaust (Golunski
et al., 1995). It has also been widely studied for PROX to clean
the hydrogen rich feed stream for PEM fuel cell applications
(Wang et al., 2002; Pillai and Deevi, 2006) and methane par-
tial oxidation (Pantu and Gavalas, 2002). This is because ceria
has a fluorite-like cubic structure in which each cerium site is
surrounded by eight oxygen sites in fcc arrangement and each
oxygen site has a tetrahedron of cerium sites. Under various
redox conditions, the oxidation state of cerium may vary be-
tween 3+ and 4+. The better redox properties than those CeO2
alone can be obtained by the incorporation of metal ions into
the CeO2 lattice forming Ce1−x Mx Oy solid solutions (Shan
et al., 2004). Surface oxygen and oxygen vaccines are involved
in the catalytic activity. This enhanced oxygen-mobility facili-
tates the occurrence of redox process like OSRM at lower tem-
perature. Therefore, enhanced performance of Cu–Zn–Ce–Al
oxide catalysts in terms of methanol conversion, high hydro-
gen production rate and low CO formation was observed in the
present study. It can be seen that optimum loading of ceria was
required among the Cu–Zn–Ce–Al oxide catalysts. The 15%
and 5% Ce catalysts had given lower methanol conversion and
Please cite this article as: Patel, S., Pant, K.K., Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide
catalysts. Chemical Engineering Science (2007), doi: 10.1016/j.ces.2007.01.066
( ) – 5
Fig. 5. Comparison of CO formation for different catalysts as a function
of temperature (W/F = 11 kgcat s mol−1
methanol , O/M = 0.15 M, S/M = 1.5 M,
P = 1 atm).
corresponding H2 rate compared to 10% Ce catalyst as shown in
Figs. 3 and 4. The carbon monoxide formation was raised dras-
tically at a temperature greater than 513 K for all the Cu–Zn–Al
oxide catalysts, whereas for the 10% and 15% ceria-based cat-
alysts it was increased gradually as a function of temperature
as shown in Fig. 5. The CO concentration of 10% and 15%
Cu–Zn–Ce–Al oxide catalysts was in the range of 0.05–0.1%,
which is quite low. Incorporation of ceria leads to the inhibition
of CO formation envisaged due to the oxygen storage–release
ability of ceria; this was expected because copper–ceria based
catalysts have been used for the CO oxidation and PROX. Pillai
and Deevi (2006) reported that catalytic activity of CuO/ZnO
could be improved significantly by incorporating CeO2 for the
carbon monoxide oxidation. The CuO/ZnO/CeO2 based cata-
lysts have also been quite active for the PROX in hydrogen rich
stream for the PEM fuel cell applications (Jung et al., 2004;
Cheekatamarla et al., 2005).
3.3. Effect of contact time and oxygen to methanol molar
ratio on catalyst performance
The effect of contact time (W/F) on the methanol conver-
sion and CO formation at a temperature of 553 K is shown
in Fig. 6. The methanol conversion reached 100% at contact
time more than 11 kgcat s mol−1 . The CO formation increased
from 300 ppm at contact time 3 to 2400 ppm at contact time
15 kgcat s mol−1 . The contact time 11 kgcat s mol−1 is the opti-
mum because the 100% methanol conversion with CO forma-
tion as low as 995 ppm was obtained with it.
It was found that as contact time was increased the hydro-
gen selectivity marginally decreased. The concentration of car-
bon monoxide for all the catalysts was always below 1% at all
the operating conditions, which is well below the equilibrium
concentration of water gas shift reaction. At a temperature less
 ARTICLE IN PRESS
6 S. Patel, K.K. Pant / Chemical Engineering Science
Fig. 6. Effect of contact time over methanol conversion and CO formation
for CZCeA2 catalyst (T = 553 K, O/M = 0.15 M, S/M = 1.5 M, P = 1 atm).
than 473 K and contact time 3 kgcat s mol−1 there was no CO
detected; therefore it can be postulated that the carbon monox-
ide is not a primary product. All these suggest that the CO
formation takes place through reverse water gas shift reaction
(rWGS: Eq. (4)), which uses the hydrogen and carbon dioxide
produced by reforming reaction (Eq. (3)).
H2 + CO2 ←→ CO + H2 O.
It can be seen in from Fig. 4 that at 573 K temperature H2 rate
is lower than that at 553 K even if methanol conversion was
100% at both the temperatures. This was because of conversion
of hydrogen into carbon monoxide via WGS reaction as it was
accelerated at higher temperature. Various routes have been
proposed for the formation of CO in the literature of methanol
reforming. Santacesaria and Carra (1983) have suggested the
decomposition/water gas shift reaction sequence:
CH3 OH → CO + 2H2 ,
CO + H2 O ←→ H2 + CO2 .
Jiang et al. (1993) proposed the kinetic model for steam re-
forming of methanol in which they suggested CO formation
via decomposition of methyl formate:
2CH3 OH → CH3 OCHO + 2H2 ,
CH3 OCHO + H2 O → HCOOH + CH3 OH,
HCOOH → CO2 + H2 .
Peppley et al. (1999) reported that the methanol decomposi-
tion is much slower than the steam reforming methanol reaction
but it must be included in the overall reaction scheme compris-
ing methanol steam reforming, methanol decomposition and
water gas shift reactions. Horng et al. (2006) reported the CO
formation via WGS (Eq. (6)) for the auto-thermal reforming
of methanol. Breen et al. (1999) have done extensive study
to understand the CO formation mechanism through DRIFT
Please cite this article as: Patel, S., Pant, K.K., Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide
catalysts. Chemical Engineering Science (2007), doi: 10.1016/j.ces.2007.01.066
( ) –
Fig. 7. Effect of oxygen to methanol molar ratio over methanol conversion
and hydrogen production for CZCeA2 catalyst (W/F = 11 kgcat s mol−1
methanol ,
T = 553 K, S/M = 1.5 M, P = 1 atm).
analysis as well as kinetic studies. They confirmed that the CO
formation over CuO/ZnO/ZrO2 /Al2 O3 catalyst for steam re-
forming of methanol occurs via rWGS (Eq. (4)). Recently, many
researchers have also proposed the CO formation via rWGS
reaction (Eq. (4)) (Agrell et al., 2001; Purnama et al., 2004;
(Reuse et al., 2004; Horny et al., 2007).
The O/M molar ratio is expected to have a strong influence
on the catalytic performance because the OSRM is a combi-
(4) nation of POM and SRM reactions. The data were collected
by keeping the steam to methanol molar ratio at 1.5 as shown
in Fig. 7. The methanol conversion and hydrogen production
rate increased with increasing O/M ratio and attained maximum
corresponding values at O/M = 0.15. With further increase in
O/M ratio the methanol conversion was 100% but the rate of
H2 production declined drastically up to O/M = 0.25 due to the
increase in CO formation rate by rWGS and also due to some
extent of methanol partial oxidation (Eq. (1)). At O/M ratio
greater than 0.25 both methanol conversion and hydrogen pro-
(5) duction decreased steeply because methanol partial oxidation
(Eq. (1)) was the dominant reaction. The high exothermicity
(6) of POM resulted in inefficient heat removal and consequently
decline of methanol conversion. The S/M molar ratio 1.5 was
kept constant in the present study based on our previous study
(Agarwal et al., 2005). The excess steam retarded the methanol
decomposition by providing sufficient amount of steam for the
(7) methanol reforming reaction (Eq. (2)), suppressed the CO for-
mation by inhibiting the rWGS reaction (Eq. (4)) to proceed
(8) toward the right side and also reduced the catalyst deactivation.
(9)
3.4. Reaction pathway
The OSRM involves the following reactions in addition to
the OSRM reaction Eq. (3). The POM (Eq. (11)) and SRM
(Eq. (12)) are expected to occur simultaneously at the entry
of reactor, while at the downstream side of reactor the major
reaction may be the SRM.
CH3 OH + 0.25O2 ←→ 2H2 + 0.5CO2 + 0.5CO, (10)
 ARTICLE IN PRESS
S. Patel, K.K. Pant / Chemical Engineering Science
Fig. 8. Time on stream (TOS) stability test of catalysts
(W/F = 11 kgcat s mol−1
methanol , T = 553 K, O/M = 0.15 M, S/M = 1.5 M,
P = 1 atm).
CH3 OH + 0.5O2 ←→ 2H2 + CO2 ,
CH3 OH + H2 O ←→ 3H2 + CO2 ,
CH3 OH ←→ 2H2 + CO,
CO + 0.5O2 ←→ CO2 ,
H2 + 0.5O2 ←→ H2 O,
CH3 OH + 0.25O2 ←→ HCHO + 0.5H2 O + 0.5H2 ,
The experimental hydrogen selectivity (moles of hydro-
gen produced per mole of methanol converted) was observed
slightly lower than that stoichiometrically given by Eq. (3).
The selectivity of carbon dioxide decreased with tempera-
ture, whereas that of carbon monoxide was increased. These
above all suggest the occurrence of rWGS reaction (Eq. (4)),
and also the possibility of some hydrogen produced via Eqs.
(10) and (13). For the OSRM process, benefit in reduction
of CO concentration might be obtained due to conversion of
CO to CO2 via oxidation reaction (Eq. (14)). The formation
of formaldehyde via Eq. (16) was prevented by operating the
OSRM at higher space velocities (Velu et al., 2001). The ceria-
based Cu–Zn–Ce–Al oxide catalysts enhanced the activity
that facilitated the complete methanol conversion at relatively
lower temperature of 553 K so that there was no formation of
methane and other oxygenates which were observed by Turco
(et al. (2004b).
3.5. Stability of catalysts
The Cu/Zn/Al2 O3 catalysts face the great problem of deac-
tivation (Agarwal et al., 2005). The CZA2 catalyst deactivated
greatly by a magnitude of 26% methanol conversion over a
72 h TOS stability test as shown in Fig. 8. On the other hand
the activity of CZCeA2 catalyst declined only by a magni-
tude of 8%. For a CZCeA2 catalyst activity declined initially
and then became nearly constant. This initial decline in the
Please cite this article as: Patel, S., Pant, K.K., Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide
catalysts. Chemical Engineering Science (2007), doi: 10.1016/j.ces.2007.01.066
( ) – 7
catalytic activity might be due to some transient transforma-
tion to a stable form under the reaction condition that occurred
in the catalyst. Catalyst CZCeA2 containing ceria was found
to be quite durable because ceria promoter has high oxygen
storage–release capacity, which inhibits the coke deposition
significantly by coke gasification. The higher amount of lat-
tice oxygen near the metal particles promotes the mechanism
of carbon removal from the metallic surface (Fernandez-Garcia
et al., 1997; Mattos et al., 2002, Patel and Pant, 2006a). They
also reported that ceria improves the stability against sinter-
ing of metallic copper phase formed during the reaction. The
amount of coke deposited on the catalysts obtained using TGA
was 0.18 and 1.55 wt% for the CZCeA2 and CZA2 catalysts,
respectively. The C1s XPS spectra of spent catalysts revealed
that the graphite carbon –C–C– (284 eV, BE) and oxidized car-
bon CO3 (288 eV, BE) were present on the catalyst surface.
4. Conclusion
(11)
In the present study to investigate the effect of Ce loading
(12) on the performance of Cu–Zn–Al oxide catalysts for OSRM,
the optimum 10 wt% doping of cerium improved the catalyst
(13)
performance greatly in terms of methanol conversion, hydro-
gen production rate and CO suppression. The 100% methanol
(14)
conversion with CO formation as low as 995 ppm was obtained
(15) that reduce the load on preferential oxidation of CO to CO2
(PROX) before feeding the hydrogen rich stream as a feed for
(16) the PEM fuel cells. The optimum operating parameters could
be suggested as reaction temperature 553 K, contact time (W/F)
11 kgcat s mol−1 , oxygen to methanol (O/M) molar ratio 0.15
and steam to methanol molar (S/M) ratio 1.5. The spillover of
carbon monoxide to ceria can be hindered by performing the
CO chemisorption over ceria-based catalysts at low tempera-
ture of 193 K. The CO chemisorption, TPR and XRD studies
have revealed that the incorporation of Ce in Cu–Zn–Al oxide
catalysts improved the copper dispersion by reducing the par-
ticle size of copper, and also facilitated catalyst reduction at
lower temperature. The incorporation of ceria greatly improved
the stability of Cu–Zn–Al oxide catalysts.
References
Agarwal, V., Patel, S., Pant, K.K., 2005. H2 production by steam reforming
of methanol over Cu/ZnO/Al2 O3 catalysts: transient deactivation kinetics
modeling. Applied Catalysis A: General 279, 155–164.
Agrell, J., Hasselbo, K., Jansson, K., Jaras, S.G., Boutonnet, M., 2001.
Production of hydrogen from methanol over Cu/ZnO catalysts promoted
by ZrO2 and Al2 O3 . Applied Catalysis A: General 211, 239–250.
Bowers, B.J., Zhao J.L., Ruffo, M., Khan, R., Dattatraya, D., Dushman, N.,
Beziat, J., Boudjemaa, F., 2006. Onboard fuel processor for PEM fuel cell
vehicles. International Journal of Hydrogen Energy, in press. Available
online at sciencedirect.com.
Breen, J.P., Ross, J.R.H., 1999. Methanol reforming for fuel-cell applications:
development of zirconia-containing Cu–Zn–Al catalysts. Catalysis Today
51, 521–533.
Breen, J.P., Meunier, F.C., Ross, J.R.H., 1999. Mechnistic aspects of the steam
reforming of methanol over a CuO/ZnO/ZrO2 /Al2 O3 catalyst. Chemical
Communications, 2247–2248.
 ARTICLE IN PRESS
8 S. Patel, K.K. Pant / Chemical Engineering Science
Cheekatamarla, P.K., Epling, W.S., Lane, A.M., 2005. Selective low-
temperature removal of carbon monoxide from hydrogen-rich fuels over
Cu–Ce–Al catalysts. Journal of Power Sources 147, 178–183.
Chen, G., Li, S., Yuan, Q., 2007. Pd −Zn/Cu −Zn −Al catalysts prepared for
methanol oxidation reforming in micro channel reactors. Catalysis Today
120, 63–70.
Choi, Y., Stenger, H.G., 2002. Fuel cell grade hydrogen from methanol on a
commercial Cu/ZnO/Al2 O3 catalyst. Applied Catalysis B: Environmental
38, 259–269.
Dow, W., Wang, Y., Huang, T., 2000. TPR and XRD studies of yttria-
doped ceria/g-alumina-supported copper oxide catalyst. Applied Catalysis
A: General 190, 25–34.
Edwards, N., Ellis, S.R., Frost, J.C., Golunski, S.E., Keulen, A.N.J.,
Lindewald, N.G., Reinkingh, J.G., 1998. On-board hydrogen generation
for transportation applications: the HotSpot methanol processor. Journal
of Power Sources 71, 123–128.
Fernandez-Garcia, M., Rebollo, E.G., Ruiz, A.G., Conesa, J.C., Soria,
J., 1997. Influence of ceria on the dispersion and reduction/oxidation
behavior of alumina-supported copper catalysts. Journal of Catalysis 172,
146–159.
Golunski, S.E., Hatcher, H.A., Rajaram, R.R., Truex, T.J., 1995. Origins
of low-temperature three-way activity in Pt/CeO2 . Applied Catalysis B:
Environmental 3, 367–376.
Holmgren, A., Anderson, B., 1998. Oxygen storage dynamics in
Pt/CeO2 /Al2 O3 catalysts. Journal of Catalysis 178, 14–25.
Holmgren, A., Anderson, B., Duprez, D., 1999. Interactions of CO
with Pt/ceria catalysts. Applied Catalysis B: Environmental 22,
215–230.
Horng, R., Chou, H., Lee, C., Tsai, H., 2006. Characterisation of hydrogen
produced by partial oxidation and auto-thermal reforming in a small
methanol reformer. Journal of Power Sources 161, 1225–1233.
Horny, C., Renken, A., Kiwi-Minsker, L., 2007. Compact string reactor for
autothermal hydrogen production. Catalysis Today 120, 45–53.
Jiang, C.J., Trimm, D.L., Wainwright, M.S., Cant, N.W., 1993. Kinetic
mechanism for the reaction between methanol and water over a
Cu–ZnO–Al2 O3 catalyst. Applied Catalysis A: General 97, 145–158.
Jung, C.R., Han, J., Nam, S.W., Lim, T.H., Hong, S.A., Lee, H.I., 2004.
Selective oxidation of CO over CuO–CeO2 catalyst: effect of calcination
temperature. Catalysis Today 93–95, 183–190.
Lindstrom, B., Pettersson, L.J., Menon, P.G., 2002. Activity and
characterization of Cu/Zn, Cu/Cr and Cu/Zr on -alumina for methanol
reforming for fuel cell vehicles. Applied Catalysis A: General 234,
111–125.
Lindstrom, B., Agrell, J., Pettersson, L.J., 2003. Combined methanol
reforming for hydrogen generation over monolithic catalysts. Chemical
Engineering Journal 93, 91–101.
Liu, S., Takahashi, K., Ayabe, M., 2003. Hydrogen production by oxidative
steam reforming of methanol on Pd/ZnO catalyst: effects of Pd loading.
Catalysis Today 87, 247–253.
Liu, W., Flyzani-Stephanopoulos, M., 1996. Transition metal-promoted
oxidation catalysis by fluorite oxides: a study of CO oxidation over
Cu–CeO2 . The Chemical Engineering Journal and the Biochemical
Engineering Journal 64, 283–294.
Mattos, L.V., Oliveira, E.R., Resende, P.D., Noronha, F.B., Passos, F.B., 2002.
Partial oxidation of methane on Pt/Ce–ZrO2 catalysts. Catalysis Today
77, 245–256.
Murcia-Mascaros, S., Navarro, R.M., Gomez-Sainero, L., Costantino, U.,
Nocchetti, M., Fierro, J.L.G., 2001. Oxidative methanol reforming reactions
on CuZnAl catalysts derived from hydrotalcite-like precursors. Journal of
Catalysis 198, 338–347.
Pantu, P., Gavalas, G.R., 2002. Methane partial oxidation on Pt/CeO2 and
Pt/Al2 O3 catalysts. Applied Catalysis A: General 223, 253–260.
Papavasiliou, J., Avgouropoulos, G., Ioannides, T., 2006. In situ
combustion synthesis of structured Cu–Ce–O and Cu–Mn–O catalysts
for the production and purification of hydrogen. Applied Catalysis B:
Environmental 66, 168–174.
Please cite this article as: Patel, S., Pant, K.K., Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide
catalysts. Chemical Engineering Science (2007), doi: 10.1016/j.ces.2007.01.066
( ) –
Patel, S., Pant, K.K., 2006a. Activity and stability enhancement of
copper–alumina catalysts using cerium and zinc promoters for the selective
production of hydrogen via steam reforming of methanol. Journal of Power
Sources 159, 139–143.
Patel, S., Pant, K.K., 2006b. Influence of preparation method on performance
of Cu(Zn)(Zr)–alumina catalysts for the hydrogen production via steam
reforming of methanol. Journal of Porous Materials 13, 381–386.
Patel, S., Pant, K.K., 2006c. Production of hydrogen with low carbon
monoxide formation via catalytic steam reforming of methanol. ASME
Journal of Fuel Cell Science and Technology 3, 369–374.
Peppley, B.A., Amphlett, J.C., Kearns, L.M., Mann, R.F., 1999.
Methanol–steam reforming on Cu/ZnO/Al2 O3 catalysts. Part 2. A
comprehensive kinetic model. Applied Catalysis A: General 179, 31–49.
Pillai, U.R., Deevi, S., 2006. Copper–zinc oxide and ceria promoted
copper–zinc oxide as highly active catalysts for low temperature oxidation
of carbon monoxide. Applied Catalysis B: Environmental 65, 110–117.
Purnama, H., Ressler, T., Jentoft, R.E., Soerijanto, H., Schlogl, R.,
Schomacker, R., 2004. CO formation/selectivity for steam reforming of
methanol with a commercial CuO/ZnO/Al2 O3 catalyst. Applied Catalysis
A: General 259, 83–94.
Raimondi, A., Geissler, K., Wambach, J., Wokaun, A., 2002. Hydrogen
production by methanol reforming: post-reaction characterisation of a
Cu/ZnO/Al2 O3 catalyst by XPS and TPD. Applied Surface Science 189,
59–71.
Reitz, T.L., Lee, P.L., Czaplewski, K.F., Lang, J.C., Popp, K.E., Kung, H.H.,
2001. Time-resolved XANES investigation of CuO/ZnO in the oxidative
methanol reforming reaction. Journal of Catalysis 199, 193–201.
Reuse, P., Renken, A., Hass-Santo, K., Gorke, O., Schubert, K., 2004.
Hydrogen production for fuel cell application in an autothermal micro-
channel reactor. Chemical Engineering Journal 101, 133–141.
Sahoo, D.R., Vajpai, S., Patel, S., Pant, K.K., 2007. Kinetic modeling of
steam reforming of ethanol for the production of hydrogen over Co/Al2 O3
catalyst. Chemical Engineering Journal 125, 139–147.
Santacesaria, E., Carra, S., 1983. Kinetics of catalytic steam reforming of
methanol in a CSTR reactor. Applied Catalysis 5, 345–358.
Semelsberger, T.A., Ott, K.C., Borup, R.L., Greene, H.L., 2006. Generating
hydrogen-rich fuel-cell feeds from dimethyl ether (DME) using Cu/Zn
supported on various solid–acid substrates. Applied Catalysis A: General
309, 210–223.
Shan, W., Feng, Z., Li, Z., Zhang, J., Shen, W., Li, C., 2004. Oxidative
steam reforming of methanol on Ce0.9Cu0.1Oy catalysts prepared by
deposition–precipitation, coprecipitation, and complexation–combustion
methods. Journal of Catalysis 228, 206–217.
Turco, M., Bagnasco, G., Costantino, U., Marmottini, F., Montanari, T.,
Ramis, G., Busca, G., 2004a. Production of hydrogen from oxidative
steam reforming of methanol I. Preparation and characterization of
Cu/ZnO/Al2 O3 catalysts from a hydrotalcite-like LDH precursor. Journal
of Catalysis 228, 43–55.
Turco, M., Bagnasco, G., Costantino, U., Marmottini, F., Montanari, T.,
Ramis, G., Busca, G., 2004b. Production of hydrogen from oxidative steam
reforming of methanol II. Catalytic activity and reaction mechanism on
Cu/ZnO/Al2 O3 hydrotalcite-derived catalysts. Journal of Catalysis 228,
56–65.
Velu, S., Suzuki, K., Kapoor, M.P., Ohashi, F., Osaki, T., 2001. Selective
production of hydrogen for fuel cells via oxidative steam reforming of
methanol over CuZnAl(Zr)-oxide catalysts. Applied Catalysis A: General
213, 47–63.
Wang, J.B., Tsai, D., Huang, T., 2002. Synergistic catalysts of carbon
monoxide oxidation over copper oxide supported on samaria-doped ceria.
Journal of Catalysis 208, 370–380.
Wang, Z., Xi, J., Wang, W., Lu, G., 2003. Selective production of hydrogen by
partial oxidation of methanol over Cu/Cr catalysts. Journal of Molecular
Catalysis A: Chemical 191, 123–134.
Yan, X., Wang, S., Li, X., Hou, M., Yuan, Z., Li, D., Pan, L., Zhang, C.,
Liu, J., Ming, P., Yi, B., 2006. A 75-kW methanol reforming fuel cell
system. Journal of Power Sources 244, 1–9.