Fuel 86 (2007) 13311336

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Micro-channel reactor for steam reforming of methanol

Arunabha Kundu *, J.M. Park, J.E. Ahn, S.S. Park, Y.G. Shul, H.S. Han
Department of Chemical Engineering, Yonsei University, 134 Shinchon, Sudeamun-Ku, Seoul 120-749, Republic of Korea

Received 22 February 2006; received in revised form 3 August 2006; accepted 3 August 2006
Available online 1 September 2006

Abstract

Micro-channel reactor for steam reforming of methanol seems to be attractive for portable application as one part of fuel processor in
fuel cell. In the present study, steam reforming of methanol was performed in one stainless steel micro-channel reactor coated with com-
mercial catalyst. The dierent sols (alumina, zirconia and mixed sol of alumina and zirconia) as a binder for the catalyst were applied to
compare the stability and performance. Among the dierent sols, mixed sol of alumina and zirconia comparatively produced better sta-
bility and performance.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Catalyst coating; Methanol; Fuel processor

1. Introduction amount of CO formed in the process. Steam reforming of

Methanol steam reforming refers to the chemical reac-
tion between methanol and water vapor for the production
of hydrogen gas. This process is typically carried out in the
presence of metal oxide catalysts at temperatures ranging
from 200 to 300 C. The chemical reactions taking place
during the reforming process are outlined as follows:
CH3 OH H2 O CO2 3H2 DH 0f 49:4 KJ=mol
CH3 OH CO 2H2 DH 0f 90:5 KJ=mol
Reaction (1) is the main reforming reaction which gives the
stoichiometric conversion of methanol to hydrogen. It can
be regarded as the overall eect of methanol decomposition
reactions to CO and H2O and the watergas shift reaction.
The amount of carbon monoxide (CO) as intermediate
product formed in the process is determined from the rela-
tive kinetics of these two reactions. Appropriate feed ratio
of methanol to water, proper control of temperature and
pressure in the reformer are required to minimize the
*
Corresponding author. Present address: Electro-materials and Device
Laboratory (eMD Lab), Corporate R&D Center, Samsung Electro-
Mechanics, Maetan3-Dong, Suwon, Republic of Korea.
E-mail address: arunabhakundu@gmail.com (A. Kundu).
methanol is an endothermic reaction. Therefore the tem-
perature is dicult to control inside the reactor which
aects the performance.
Conventionally xed bed reaction system has often been
used for methanol steam reforming. It has disadvantages in
terms of size and weight which aect on the compactness of
fuel processor. Generally low gas velocity is maintained in
the reformer in order to achieve high conversion. The low
1 velocity lowers the eective thermal conductivity of the cat-
2 alyst bed. Furthermore, the low ratio of reactor to catalyst
particle diameter and the low gas velocity tend to introduce
a large heat transfer resistance between the wall and the
catalyst particle. The void fraction at the wall is larger than
that in the center of the bed and there are only limited
number of contact points between the catalyst particles
and the reactor wall. Hence the major heat transfer resis-
tance between the wall and catalyst particles is due to the
gas lm. Under these conditions, increasing thermal con-
ductivity of the solid material has only a modest impact
in improving overall heat transfer. For an endothermic
reaction such as methanol steam reforming, temperature
gradient in the packed bed leads to lowered catalyst activity
and falsied kinetics. In addition, hot and cold spots are
commonly encountered in the catalyst bed that results poor
performance. This type of reactor has also poor response to

0016-2361/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.08.003
1332 A. Kundu et al. / Fuel 86 (2007) 13311336
transients. Similarly, they require a prolonged time to reach
working temperature from cold start-up. The catalyst in
packed bed form also exhibits high pressure drop and
possible channeling of gases.
2. Literature review on micro-channel reactor for steam
reforming of methanol
Micro-channel reactor with catalyst coating in steam
reforming of methanol is a promising candidate for porta-
ble electronics in order to get the compactness in the struc-
ture of fuel processor, the advantages with respect to
transient behavior, hydrodynamics and heat and mass
transfer characteristics.
The main feature of micro-structured reactors is the
high surface-area-to-volume ratio in comparison to con-
ventional chemical reactors. Heat-transfer coecient in
this micro-channel reactor is also signicantly higher than
that for traditional heat exchangers. The high heat-
exchanging eciency allows to carry out reactions under
isothermal conditions. In addition to heat transport, mass
transport is also improved considerably in micro-struc-
tured reactors. The ows in the micro-channels are mostly
laminar, directed, and highly symmetric. Process parame-
ters such as pressure, temperature, residence time, and ow
rate are more easily controlled in this reactor. Micro-struc-
tured reactors also give opportunities for new production
concepts. Depending on demand, more micro-structured
reactors or such subunits could be connected in parallel
so that the required intermediate products and end-prod-
ucts can be produced.
The rst use of wall-coated reactor for steam reforming
of methanol was reported by de Wild and Verhaak [1].
They used the washcoated plate-n type heat exchanger
for the reaction. The washcoated heat exchanger showed
better performance as compared to packed beds. The prob-
lem in micro-channel reactors lies on low durability of the
catalyst. There is limited literature concerning the durabil-
ity of the catalyst where catalyst deactivation at faster rate
has been reported [1,2]. More catalyst loading and increase
in porosity inside the coating are required in order to
increase the durability of the catalyst. There are four types
of catalyst for steam reforming of methanol in the litera-
ture under this category of the reactor: CuO/ZnO/Al2O3,
CuO/Cr2O3/Al2O3, Cu/CeO2/Al2O3 and Pd/ZnO. In the
micro-channel reactor, CuO/ZnO/Al2O3 catalyst coating
was used by Bravo et al. [3], Park et al. [4], Lim et al. [5]
and Kawamura et al. [6]. Zapf et al. [7], Men et al. [8,9]
and Pfeifer et al. [10,11] studied CuO/Cr2O3/Al2O3, Cu/
CeO2/Al2O3 and Pd/ZnO catalyst respectively. For CuO/
ZnO/Al2O3 catalyst, all the groups except Kawamura
et al. [6] utilized commercial catalyst and the coating was
made with the slurry of catalyst powder and alumina/zirco-
nia sol. Before coating of the catalyst, the micro-channel
sheet was undercoated with the alumina/zirconia sol in
order to enhance the adhesion between catalyst powders
and the substrate structure. For CuO/Cr2O3/Al2O3 and
Cu/CeO2/Al2O3 catalyst, Zapf et al. [7], Men et al. [8,9]
used the alumina binder prepared by mixing of c-alumina
powder, water, PVA (binder) and acetic acid. Nitric acid
acted as a catalyst in all the above procedure for the
alumina/zirconia sol according to standard recipe. This
method produced non-continuous surface layer on the
thermally treated micro-structured metal foils [12]. The
likely reason for the bad adhesion of these coatings is high
condensation rate in the sol, leading to a granular ne
structure of the gel lm. Therefore, there is a need of
change of preparation of sol which gives continuous and
stable coating at high temperature.
With a view to the current status of this type of reactor,
there is an uncertainty of forming stable and continuous
coating on micro-channels and durability of catalyst for
steam reforming of methanol. As the fabrication of these
micro-channels is relatively costly, the frequent change of
these reactors questions on the applicability in electronic
purposes. The main aim of the present paper is to study
for the compact methanol steam reformer with high perfor-
mance and better durability of the system. Dierent sols
(alumina, zirconia and mixed sol of alumina and zirconia)
were applied to get more stable and durable coating in the
micro-channels.
3. Experimental set-up
Fig. 1 shows the experimental set-up. It mainly consists
of liquid feed pump (KdScientic), compact reactor unit
comprising vaporizer plate followed by reactor plate, PID
temperature controller and facilities for hydrogen ow.
The feed rate was varied from 0.005 ml/min to 0.05 ml/
min. The water and methanol ratio in the feed was 2:1 as
it is generally recommended for getting low concentration
of CO. The reactor was heated through electrical heater.
Micro-channeled plate made of stainless steel was used as
a reactor considering its high resistivity against corrosion.
The dimension of the plate has been given in Fig. 1(b)
[dimensions are in mm]. The plate was 62 mm in length
and 40 mm in width and each channel was 37 mm in length
and total width of 40 channels and 38 ns was 23 mm. The
channels were created by wet etching method. The dimen-
sion of each channel and n are given in Fig. 1(c). The
width of each channel and each n was 300 lm and the
depth of the channel was 200 lm. The coating procedure
is explained in Fig. 2. The etched channel was pretreated
with conc. HNO3 for removal of chloride ion followed by
heat treatment at 500 C for 1 h and undercoating with
the prepared sol. The undercoating was provided to
increase the adhesive strength between the catalyst and
the micro-channel wall. The dierent sols [alumina, zirco-
nia and mixed (alumina and zirconia in 1:1 molar ratio)
sol] were prepared for that purpose. The undercoating
was made by dipping into 20 wt% of the prepared sol. After
that, it was kept for drying at room temperature followed
by in an oven at 80 C for 5 h. Finally it was calcined at
500 C for 2 h in order to decompose carbon species
 A. Kundu et al. / Fuel 86 (2007) 13311336 1333

Fig. 1. Experimental set-up; (a) schematic diagram with the photo of reactor unit, (b) dimension of micro-channeled plate, (c) dimension of the micro-
channels, (d) catalyst coated micro-channels, and (e) SEM imaging of catalyst particles after bid-milling.

present in the sol and achieve high surface area [12]. The
dierent prepared sols were also used for the coating of
the commercial catalyst on the micro-channel plate. Cata-
lyst was layered on the under-coated micro-channels using
dip-coating method. Before that, the catalyst powder was
bid-milled to make very small size of catalyst particles fol-
lowed by making slurry with the prepared sol. Fig. 1(d)
shows the view of one catalyst coated micro-channeled
plate. Initially hydrogen was passed at low ow rate
(10 ml/min) for 1 h at 200 C to get the actual conversion.
The reactor was heated with two heating plates heated by
four cartridge heaters. The temperature of the reactor
was regulated by PID controller connected with the car-
tridge heaters. Three thermocouples of type K positioned
at the inside of the heating plate, the outlet of the micro-
channeled reactor plate and the inlet of reactant were xed
in order to monitor the temperature at dierent parts of the
system. The mean temperature of the inlet and outlet
1334 A. Kundu et al. / Fuel 86 (2007) 13311336
Pretreatment of the micro-
channeled stainless steel
Under coating
Preparation of catalyst slurry
Coating of catalyst on the
undercoated micro-channels
Performance test
Fig. 2. Dierent steps of coating on micro-channeled plate.
position was the reaction temperature. The produced gas
stream was directed through a cold trap to remove liquid
components and then passed to an on-line gas chromato-
graph for analysis of H2, CO and CO2 or to bubble ow
meter for measuring ow. The gas chromatograph (Acme
6000 M) was equipped with a Carbosphere column and a
TCD detector using helium as the carrier gas.
4. Preparation of sols
The precursors for alumina and zirconia were alumin-
ium secondary butoxide (Fluka) and zirconium(IV) prop-
oxide (Aldrich), respectively for the preparation of
alumina, zirconia and mixture of alumina and zirconia
(molar ratio=1:1) sols. The procedure of Haas-Santo
et al. [12] and Zeng [13] was followed for the method of
preparation of the sol. During the preparation of the sol,
the hydrolysis of the alkoxides, which is very fast leading
to ne particles in the sol, was protected by the addition
of acetylacetone as stabilizer. The acetylacetone was added
in the molar ratio of unity with alkoxide. Ethyl alcohol was
used as the solvent. The water added was in the molar ratio
Fig. 3. (a) SEM imaging of catalyst coated micro-channels. (b) Thickness of the catalyst coated layer.
Chemical treatment (Dipping in conc. HNO3
solution for 45 minutes followed by washing with
DM water for several times)
Alumina, zirconia, or mixed oxide from sol-
gel techniques
1.Bid milling the catalyst powder to make fine
catalyst powder
2.Making slurry with sol
Dip coating and drying followed by
calcination
Check the loading of the catalyst, uniformity
of the coating and hardness test and other
characterization
of 2:1 with respect to alkoxide. The nal pH of the solution
was maintained at 4.5 by adding nitric acid. The nal con-
centration of the resulting sol was 20 wt% which resulted
uniform coating on the stainless steel plate. The viscosity
and density of the resulting sol was 3.5 mPa s and
900 kg/m3.
5. Results
Commercial catalyst (Cu/ZnO/Al2O3-MDC-3: Sud-
Chemie) was used to test the performance of the wall-
coated micro-channel reactor. Catalyst size is one of the
factors to get uniform coating in the micro-channels. Cat-
alyst was bid milled for 10 h at 3000 rpm to get very ne
size of particles. The dierent sizes (>50 lm and 30 lm)
of catalyst particles were separated by sieving. The residual
catalyst particles were further bid-milled in order to obtain
smaller catalyst particles. The particle size of 1 lm (deter-
mined by SEM; Fig. 1(e)) was suitable for uniform washco-
ating compared to larger particle size. Then catalyst slurry
was prepared by adding the ne catalyst powder to the pre-
pared sol in the weight ratio of 85:15 of catalyst and metal
 A. Kundu et al. / Fuel 86 (2007) 13311336 1335

1.0
100

CO composition, volume %
70 Hydrogen 0.9

Methanol Conversion (%)

CO2 0.8 90
60 0.7 270 C
0.6 280 C
Volume %

80
50 290 C
0.5
0.4 70
40
0.3
60
30 0.2
0.1
50
20 0.0
270 275 280 285 290
40
Temperature (C)
0.00 0.01 0.02 0.03 0.04 0.05
Fig. 4. Composition of reformate vs temperature (290 C) with 45 mg Feed rate (ml/min)
catalyst coating (methanol:water = 1:2) WHSV = 1.245 h1 with mixed
Fig. 5. Eect of feed rate on methanol conversion (1:2 molar ratio of
sol coating.
methanol and water and weight of the catalyst = 45 mg).

oxide (sol) respectively. Dip coating method was used for Table 1
catalyst coating on the micro-channels. A uniform and Catalyst durability test with dierent sols as binder in micro-channel
catalyst coated reactor (290 C, WHSV = 1.245 h1)
robust catalyst layer was obtained (Fig. 3(a)). The amount
of coated catalyst in one plate was 45 mg and the thickness Catalyst Loss of catalyst
loss (wt%) performance (%)
of the catalyst layer was 25 lm (Fig. 3(b)).
The catalyst coated micro-channeled plate was dried at Al2O3 sol (undercoating) and 25 10
catalyst slurry with Al2O3 sol
room temperature followed by drying at 80 C for 5 h. ZrO2 sol (undercoating) and 40 20
Then it was calcined at 300 C for 2 h. The calcined catalyst catalyst slurry with ZrO2 sol
coated micro-channeled sheet was housed with the heater ZrO2 + Al2O3 sol (undercoating) and 15 5
and end plate for the performance test (Fig. 1(a)). The catalyst slurry with ZrO2 + Al2O3 sol
developed micro reformer exhibited good performance
(Fig. 4). In the performance test, methanol conversion of
99.3% at 290 C was obtained (Fig. 4) at the liquid feed rate mixed sol (alumina + zirconia) as undercoating and cata-
of 0.01 ml/min with 0.7% CO in the resulting gas with lyst binder. The production rate of hydrogen was

700

600

500

400
cps

300

200 Zirconia

100 Alumina +Zirconia

Alumina
0
0 10 20 30 40 50 60 70 80 90
2

Fig. 6. XRD Pattern of dierent prepared sol (calcination temperature = 500 C).
1336 A. Kundu et al. / Fuel 86 (2007) 13311336
0.025 mole/hr for one micro-channeled plate. Based on
lower heating value of 241 103 J/mol, this hydrogen pro-
duction rate corresponds to 1.6 W of hydrogen power, in
which electrical power greater than 0.5 W is expected
assuming 45% of fuel cell eciency and 70% of hydrogen
utilization in a PEMFC [6].
Fig. 5 shows the eect of feed rate (mixture) on the con-
version of methanol at dierent temperature. The almost
complete conversion was achieved at 290 C at the desired
ow rate of 0.01 ml/min (which corresponds to 1.245 h1
as WHSV) of the mixture of methanol and water. Table
1 shows the comparison of the stability and durability of
the catalyst coating in continuously operated system for
six days with dierent sol as a binder with respect to under-
coating and making catalyst slurry. Alumina and zirconia
mixed sol comparatively produced stable coating as the
catalyst loss after 6 days operation was only 15 wt%.
Though the catalyst performance with dierent sols
(Al2O3, ZrO2 and Al2O3 + ZrO2) was almost same initially,
it decreased by 20% with ZrO2 sol as a catalyst binder. This
may be attributed from unstable coating which resulted of
40 wt% loss of catalyst after 6 days operation. The ease of
textural control and thermal stability of alumina, when it
was mixed with zirconia, may be the other reason for rela-
tively higher performance with alumina and zirconia sol
plus catalyst. The thermal stability with mixed sol of alu-
mina and zirconia can be explained by the occurrence of
ZrOAl phases by migration of zirconium ions to the sub-
surface layers of the support [14]. Highly dispersed catalyst
particles on the highly disordered or amorphous states of
Al2O3/ZrO2 sol exhibited better performance on long term
basis. The relatively unstable coating with zirconia sol can
be explained by the crystalline structure at 500 C (Fig. 6),
whereas the crystanillity of ZrO2 was completely lost by
mixing with alumina and zirconia (1:1 molar ratio). It
may help on the thermal stability of the catalyst, but the
unstable coating facilitated the catalyst moving out from
the reactor. This was the main reason for exhibiting low
performance in the case of catalyst coating with the zirco-
nia sol. It may be noted that the catalyst loss was higher
than the loss of catalyst performance in every cases of
Table 1. This conrmed that the initial amount of catalyst
loading was in excess amount for the designed ow rate of
the reactant. In addition, the loss of catalyst performance
was not only due to the loss of amount of catalyst but also
for the loss of the activity of the catalyst in the prolonged
operation.
6. Conclusions
A stable coating of catalyst was obtained on micro-
channeled stainless steel plate. Dierent types of sols were
employed for the purpose of coating of the catalyst. Mixed
sols (Al2O3 + ZrO2) produced relatively stable coating in
comparison to other sols (Al2O3 and ZrO2). The durability
of the catalyst coating was tested by continuous 6 days
operation. Though the performance with the three dierent
prepared sols plus catalyst was initially same, the perfor-
mance with ZrO2 sol plus catalyst decreased after 6 days
operation by 20%.
Acknowledgements
The authors acknowledge the nancial assistance from
Samsung-SDI and Korea Research Foundation. One of
the authors (AK) wishes to thank Dr. P.K. Mukhopadha-
yay, former chairman, Indian Oil Corporation Ltd., India
to encourage for this research.
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