i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Steam reforming of methane over Ni catalyst in micro-

channel reactor

Xuli Zhai a, Yinhong Cheng a, Zhongtao Zhang b, Yong Jin a, Yi Cheng a,*
a
Department of Chemical Engineering, Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Tsinghua University,
Beijing 100084, PR China
b
Daqing Chemical Engineering Research Institute of Petrochina, Daqing 163714, PR China

article info abstract

Article history: A comprehensive study on the catalytic performance of Ni catalyst to implement milli-
Received 25 January 2011 second steam reforming of methane (SRM) reaction in micro-channel reactors was con-
Received in revised form ducted in this work. A new method to manufacture the metaleceramics complex substrate
10 March 2011 as catalyst support was presented, that is, a layer of nano-particles, a-Al2O3, was thermally
Accepted 12 March 2011 sprayed on a metallic substrate, usually FeCrAlloy. Ni or Rh catalyst was then impregnated
Available online 7 April 2011 on the substrate, forming firm and active catalyst coatings. The fall-off rate of the catalyst
can be neglected after the plates experienced the high-temperature SRM reaction, showing
Keywords: the reliability in long-term use and the excellent catalytic performance for SRM reaction in
Hydrogen production micro-channel reactors. In comparison with the expensive Rh catalyst, Ni also showed
Steam reforming of methane wonderful performance to catalyze the SRM reaction in micro-reactors within millisec-
Micro-channel reactor onds. Using the appropriate reactor design, CH4 conversion reached above 90% when the
Nickel catalyst residence time was as short as 32 ms for catalyst loading of 6.8 g/m2. When the residence
Millisecond reaction time was longer than 100 ms, CH4 conversion was above 98%. Besides, catalyst deactivation
was not detected for 500 h on stream with S/C ratio of 3.0, and for 12 h with S/C of 1.0 as
well. Extensive characterizations on these Ni catalyst plates using XRD, SEM, TEM and XPS
demonstrated that Ni catalysts prepared in this work did not show any sign of deactivation
after being used in the micro-channel system under high-temperature operation.
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction important chemical feedstock, but also a clean energy carrier.

Hydrogen has been widely used in the petro-chemical processes
such as hydro-desulfurization, hydro-cracking, hydro-refining
and so on. Nowadays, hydrogen becomes more and more
involved as the feedstock in the synthesis of methanol/dimethyl
ether (DME), and particularly, in the FischereTropsch reactor to
make liquid fuels from coal or natural gas. Besides, hydrogen
serves as the ideal fuel for fuel cell, e.g., for proton exchange
membrane (PEM) fuel cell [1]. Therefore, hydrogen is not only an
The demand for low-cost hydrogen would be always predomi-
nant either for mass production or for distributed applications.
It is acknowledged that steam reforming of methane (SRM) is
the most economical method for hydrogen production among
the current commercial processes [2]. However, the large-scale
packed bed reactor with Ni catalyst supported on Al2O3 pellets
suffers from the poor heat transfer behavior, which inevitably
results in the large gradients in terms of temperature (and/or
pressure) in axial and radial directions. As a consequence, the

* Corresponding author. Tel.: 86 10 62794468; fax: 86 10 62772051.

E-mail address: yicheng@tsinghua.edu.cn (Y. Cheng).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.03.065
7106 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3
catalyst efficiency is reduced no matter how to improve the
catalyst performance, for example, by adding promoters, such
as Mo, P, CexZr1xO2 [3e6]; or by changing supports, such as
gadolinia doped ceria (GDC), ZrO2, yttria stabilized zirconia (YSZ)
[7e9]. A major challenge is that Ni catalysts have a high ther-
modynamic potential for coke formation during reforming
reactions, and several methods are discussed to synthesize coke
resistant Ni catalysts [10,11]. An alternative method is to use
structured catalyst supports such as foams and monoliths,
generally ceramic-based, for the beneficial effects of low-pres-
sure drop and high catalyst utilization efficiency in SRM reaction
[12,13]. Whereas, the low thermal conductivity still limits the
overall performance of the reactor.
In recent years, micro-channel reactors have received much
attention for the unique feature of process intensification, for
example, the excellent temperature control and improved mass
transfer especially in the applications of highly exothermic and
endothermic reactions [14,15]. A metallic structured support,
with its inherent high thermal conductivity, can be used as the
substrate of catalysts and integrated for micro-channel reactor
applications. Researchers from Velocys and Pacific Northwest
National Laboratory (PNNL) reported the development of
a millisecond micro-reactor concept for SRM process with the
highly efficient integration of an exothermic combustion
channel and an endothermic reforming channel with high
thermal efficiency through the channel (metal) wall [16e19].
However, all the reported results were mainly focused on the
expensive Rh catalyst, rarely on the relatively cheap Ni catalyst.
In the meantime, a potential risk existed due to the difference of
thermal expansion coefficients between the metallic substrate
and the catalyst layer, that is, the catalyst layer would fall off
during the reactions operated at high temperature. This would
hinder the practical applications of micro-channel reactor, and
has not been successfully solved yet [20,21].
In the present study, we demonstrated a new method to
implement firm and active Ni catalyst coatings on Fecralloy
plates for SRM reaction in milliseconds. These Ni catalyst
plates manifested excellent catalytic performance (i.e., activity
and stability) by the integration in micro-channel reactors.
2. Experimental
2.1. Catalyst plate preparation
Sol method is generally adopted to coat catalyst layer on
a metallic support in the microreactor at present. AlOOH sol,
as a primer sol or Al2O3 sol is deposited on metallic support
directly, but this is unlikely to stay firm under high-tempera-
ture operation, with ease to fall-off unexpectedly. Here, we
developed a type of metaleceramics complex substrate as the
support plate to load catalyst in order to implement firm and
active catalyst coatings for SRM reaction in microchannels.
The specific approach is described as below.
(i) manufacture of metaleceramics complex substrate
First of all, a layer of nano-particles, a-Al2O3, was thermally
sprayed on a metallic substrate, usually FeCrAlloy, to manu-
facture the metaleceramics complex substrate. But different
from the traditional thermal spraying, the metallic substrate is
preheated to an appropriate temperature (e.g., 1200  C) before
deposition. Then the binding force between the two different
substances can be greatly enhanced because the ceramic
particles would embed into the bulk phase of metal very firmly.
High-temperature spray gun was used to spray nano-particles
onto the metallic substrate. The thickness of a-Al2O3 is about
50 mm in this work, which can be adjusted according to the
specific requirement. Then the complex substrate was ultra-
sonically cleaned in acetone, then acidic solution, and then
thoroughly rinsed in de-ionized water to remove oil, primary
oxidation and superficial impurities.
(ii) deposition of AlOOH sol
The specific surface area of a-Al2O3 is too low to load active
component for SRM reaction. Therefore, a layer of g-Al2O3 with
a higher specific surface area is necessary to be added. The
AlOOH sol was prepared in the following procedure: a commer-
cial aluminium hydroxide powder (AlOOH) was dispersed in
water (e.g., 10 wt%) with continuous agitation. The pH value was
about 7 now, which should be further adjusted to 2 using HNO3
aqueous solution (5 mol/L). After that, the solution was stirred for
5 h at 85  C and then a stable sol was obtained. The AlOOH sol was
stable and suitable for our applications within 6 months after the
preparation, similar to the report using other methods [22].
Afterwards, the metaleceramics complex substrate was
immersed into this boehmite sol for 3 min, and then with-
drawn at a constant speed of 3 cm/min to ensure the uniform
coating, dried at room temperature for 30 min, then calcined
at 600  C for 6 h. As a result, a layer of g-Al2O3 with high
specific surface area was obtained. The specific surface area
was about 229 m2/g measured by BET test. The above proce-
dures can be repeated until the thickness of the coating layer
was up to the desired value. [23]
(iii) impregnation of active component
The modified metaleceramics complex substrate was
further impregnated into the prepared solution of Ni(NO3)2 or
RhCl3, with different concentrations, for 6 h at 80  C, which led
to different catalyst loadings. Then it was dried and aged at
120  C for 6 h, calcined at 600  C for 6 h, and at last the catalyst
plate with firm catalyst coatings was obtained.
2.2. Catalyst characterization
The morphology of catalyst bulks was characterized using
a scanning electron microscopy (SEM, JEOL, JSM-7401F),
coupled with an X-ray energy dispersive spectroscopy (EDS)
system to analyze the element composition of selected areas.
A JEOL JEM2010 high-resolution transmission electron
microscopy (HR-TEM) was used to characterize the diameter
of the nickel particles. The TEM samples were prepared as
follows: the catalyst powder was scraped from bulks and
dispersed in ethanol by ultrasonic agitation, and then the
suspension was dropped on a carbon-coated copper grid and
finally dried in air.
X-ray diffraction (XRD) patterns of catalyst bulks were
recorded on a Bruker D8 Advance equipment with Cu Ka
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3
radiation in the 2q range of 0e90 . Phase identification of the
catalysts was carried out by comparing the collected spectra
with the spectra in the database.
X-ray photoelectron spectra (XPS) was acquired using a PHI
Quantera SXM system, equipped with Al KaX-ray source.
Survey scans (0e1200 eV) and high-resolution Ni(2p), Al(2p),
C(1s) and O(1s) spectra were obtained. The uncertainty of the
peak positions was estimated to be 0.2 eV for all spectra. The
analysis of the measured high-resolution spectra was per-
formed using XPSPEAK3.1 software.
2.3. Catalyst test
In our experimental system, the catalyst plate was cut into
two sizes, 2 cm  3 cm and 2 cm  5.5 cm. The former one was
named as plate-I, inserted into the slit of reactor-I, where two
channels were formed as illustrated in Fig. 1-a. The size of
each channel was 1.8 cm  3cm  0.5 cm. The latter was
named as plate-II. Two sheets of plate-II were inserted into the
slits of reactor-II separately, and the space between the two
plates formed a channel, with size of 1.8 cm  5.5cm  0.4 cm,
as shown in Fig. 1-b.
The residence time in the context was defined as the
volume of microchannel(s) divided by the total volumetric
flow rate at the inlet condition (900  C and 101 kPa). Reactor-I
was used to study the difference of catalytic performance
between Rh and Ni catalysts, and reactor-II was employed to
study the catalytic behavior of Ni catalyst in details.
The catalyst plates can be easily assembled in the micro-
reactor. The experimental setup consisted of: (a) a gas supply
unit (containing CH4 and H2/Ar cylinders and mass flow
controllers), (b) a pump for feeding water, (c) a steam gener-
ator, (d) a micro-channel reactor, and (e) a gas chromatograph
(GC). Before the catalyst evaluation, the catalysts were
reduced in situ under a flow stream of dilute hydrogen (10%H2/
Ar) with the total flow rate of 30 NmL/min at 900  C for 30 min.
After reduction, CH4/H2O mixture with determined flow rate
(varying from 16 to 360 mL/min) and S/C (steam to methane,
varying from 1.0 to 3.0) ratio was introduced into the system.
The outlet gases were analyzed after water condensation with
an on-line GC (GC-7890II, Techcomp) equipped with a TCD.
Fig. 1 e Schematic diagram of micro-channel reactors (a) reactor-I, (b) reactor-II.
7107
The CH4 conversion and CO2 selectivity for the reaction are
defined as follows:
!
fCH4
XCH4 1  100% (1)
fCH4 fCO fCO2
fCO2
SCO2  100% (2)
fCO fCO2
where X is the methane conversion, S is the selectivity to
a certain product, and f is the molar fraction in the effluent gas.
3. Results and discussion
3.1. Comparison of catalytic performance between Rh
and Ni catalyst
As mentioned above, reactor-I (see Fig. 1-a) was used at the
beginning to compare the catalytic performance of Rh and Ni
in the micro-channel reactor. The same procedure was
applied to make catalyst plates for Rh and Ni.
It can be clearly seen from Fig. 2 that Rh shows much better
performance than Ni in the configuration of reactor-I. The CH4
conversion is above 90% using Rh catalyst when the residence
time is as short as 35 ms, and becomes unchanged when the
residence time is longer than 75 ms. While for Ni catalyst, the
CH4 conversion is only 56% even though the residence time is
450 ms, and it decreases sharply with the reduction of resi-
dence time. This comparison is fairly reasonable for the
inherent difference in terms of catalyst activity between Rh
and Ni, which would also be the reason why Ni is rarely
studied for millisecond SRM reaction. However, Rh is still too
expensive to be accepted as an industrial catalyst for SRM
reaction, though Rh has among the best catalyst performance.
Therefore, our focus is to investigate the most possibility to
have Ni catalyze the millisecond SRM reaction.
To be noted, the configuration of reactor-I is not the general
form of a micro-channel reactor, because half of the channel
wall is not covered by catalysts. Therefore, we improved the
reactor-I to the design of reactor-II, i.e., one channel with
coated catalyst on both walls and a larger dimension in the
7108 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3
Fig. 2 e Catalytic performance of Rh and Ni catalyst in
micro-reactors (T [ 900  C, S/C [ 3.0).
flow direction. Comprehensive experiments have been per-
formed to explore the catalytic performance based on Ni. Here
we quoted a group data of Ni catalysts of 6.8 g/m2 in reactor-II
to compare with the data in Fig. 2. It can be seen that Ni can
also show excellent performance by improving the design of
micro-channel reactor. The increased loading of Ni catalyst
and the better heat transfer to the catalyst layer would be the
reasons for such good performance of Ni, even better than Rh
in the reactor-I.
As we know, two main reactions, i.e., steam reforming of
methane (SRM) and water gas shift (WGS), take place in the
SRM process, as shown in Eqs. (3) and (4).
CH4 H2 O CO 3H2 DHq298 206 kJ=mol
CO H2 O CO2 H2 DHq298 41 kJ=mol
It can be seen that hydrogen is produced in both reactions. It
is deduced that the hydrogen yield can be calculated by the
following expression:
3 1
VH2 $GHSV$XCH4 $GHSV$XCH4 $SCO2
n1 n1
where, n d S/C, the ratio of steam to methane,
3
$GHSV$XCH4 dH2 obtained in SRM
n1
1
$GHSV$XCH4 $SCO2 dH2 obtained in WGS
n1
As illustrated in the above formula, the H2 yield depends on
both CH4 conversion and CO2 selectivity. So it is important to
know the relationship between the two parameters in such
a fast process without a separate WGS reactor following the
process.
It can be found from Fig. 2 that the CO2 selectivity shows an
opposite trend to CH4 conversion at a certain S/C ratio (i.e., 3.0
in Fig. 2). In other words, there is always a rise of CO2
selectivity with the decrease of CH4 conversion, and
a decrease of CO2 selectivity with the increase of CH4
conversion. The phenomenon also exists in other tests under
certain reaction conditions adopted in this work, such as at
high temperature (above 700  C) and low S/C ratio (in the range
of 1.0e3.0), as seen in Figs. 4 and 5. As indicated in Eqs. (3) and
(4), when the CH4 conversion rises, H2 produced in SRM
increases, leading to the increase of total amount of H2 in the
system. However, it goes against the WGS reaction to the
right, resulting in the decrease of CO2 selectivity, and vice
versa. Moreover, the reaction rate of WGS is slower than that
of SRM, and tens of milliseconds is not long enough to trans-
form CO into CO2 completely. Hence, in order to achieve the
highest H2 yield in the process, both the two factors should be
considered comprehensively.
As pointed out above, a potential risk using such micro-
reactors is the fall-off of the catalyst layer from the metallic
substrate. To evaluate the fall-off rate, Rh and Ni catalyst
plates were withdrawn from the micro-channel reactors after
the catalyst test. The plates were immersed in an ultrasonic
cleaner with frequency of 45 KHz and power of 20 W. They
were brought out, drought, and weighted after a certain
period, then the rates of fall-off were calculated according to
the original catalyst loading. As can be seen in Fig. 3, the fall-
off rates of the two different catalyst plates are similar and
they tend to be unchanged after vibrating for 60 min. In
addition, the final fall-off rate is less than 0.8%, which is much
smaller than the preceding reports [20,21]. It can be concluded
from our experiments that the manufactured metaleceramics
complex substrate can be successfully applied to obtain the
firm and active catalyst coatings on the plate surface, espe-
cially suitable for the applications under high-temperature
operation.
3.2. Catalytic performance of Ni catalyst
(3)
According to the procedures described above, Ni catalyst
(4) plates with three different catalyst loadings, i.e., 6.8 g/m2,
3.4 g/m2, 1.6 g/m2, were prepared. The catalyst loading is
(5)
Fig. 3 e Fall-off rate of Rh and Ni catalyst plates after
reaction evaluated by vibrating in an ultrasonic cleaner.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3 7109

defined as the catalyst weight loaded on the plate divided by

the area of the plate acting as the micro-channel wall. It can be
adjusted by varying the concentration of Ni(NO3)2 solution
and the times of impregnation. Next, each pair of catalyst
plates with the same catalyst loading was fixed in the reactor-
II, and the actual micro-channels were formed. The influences
of operation parameters such as the residence time, (oven)
temperature, the ratio of steam to carbon and the catalyst
loadings on the reactor performance based on Ni catalyst
plate, were studied in detail.

3.2.1. Influence of residence time

Fig. 4 shows the influence of residence time on CH4 conversion
and CO2 selectivity using the Ni catalyst plates. First of all, for
catalyst loading of 6.8 g/m2 and 3.4 g/m2, CH4 conversion is
above 90% when the residence time is as short as 32 ms; the
corresponding GHSV is 1.125  105 h1, which indicated that
Ni is also capable to catalyze the SRM reaction in micro-
channel reactors in milliseconds, though its activity is lower
than Rh. The catalyst loading has a dominant effect on the Fig. 5 e Influence of oven temperature on catalytic
reaction performance when the loading is relatively low. performance of Ni catalyst plate in reactor-II (residence
When the catalyst loading is just 1.6 g/m2, the performance of time [ 100 ms, S/C [ 3.0).
Ni catalyst plates is much poorer than others. In this case, the
amount of active sites is far from enough to satisfy the
demand of SRM reaction, especially at a short residence time.
time of 100 ms. As illustrated, CH4 conversion rises with the
However, the catalyst loadings of 6.8 g/m2 and 3.4 g/m2 show
increase of temperature for all the catalyst loadings. For the
little difference. In both cases, CH4 conversion reaches up to
catalyst loadings of 6.8 g/m2 and 3.4 g/m2, the difference
above 98% when the residence time is longer than 100 ms.
becomes less significant when the temperature ascends from
Compared to Fig. 2, the catalytic performance of Ni catalyst
700  C to 900  C, and CH4 conversions reach the same value of
plate is greatly enhanced ascribed to the improvement of the
98.8% at the temperature of 900  C.
micro-channel reactor design.

3.2.3. Influence of S/C ratio

3.2.2. Influence of temperature
Fig. 6 shows the influence of S/C ratio on the reactor perfor-
Since the SRM reaction is highly endothermic, increasing the
mance under the same residence time of 100 ms and the
temperature is beneficial to the thermodynamic equilibrium.
temperature of 900  C. When the S/C ratio changes from 1.0 to
Fig. 5 shows the influence of temperature (measured at the
3.0, CH4 conversion remains constant but CO2 selectivity
oven wall) on reaction performance under the same residence

Fig. 4 e Influence of residence time on catalytic Fig. 6 e Influence of S/C ratio on catalytic performance of Ni
performance of Ni catalyst plate in reactor-II (T [ 900  C, S/ catalyst plate in reactor-II(residence time [ 100 ms,
C [ 3.0). T [ 900  C).
7110 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3

increases steadily for the side reaction of WGS. Since the S/C
ratio would affect the stability of the catalyst, e.g., the deac-
tivation due to coking, experiments were carried out at S/
C 1.0 for 12 h with three catalyst loadings, as shown in Fig. 7.
CH4 conversion maintains constant for 12 h. It indicates that
there is no noticeable deactivation during the time although
the S/C ratio is as low as 1.0. It should be noted that the ability
to be operated stably at low S/C ratio (e.g., <3.0) can evidently
reduce the cost to produce hydrogen in a large scale.
Fig. 8 shows a 500 h test of Ni catalyst stability at S/C 3.0
and temperature of 900  C, which would be the typical oper-
ating condition for the SRM reaction in micro-reactors. It can be
seen that CH4 conversion maintains almost 100% for 500 h.
During the course of this experiment, the residence time was
changed from 600 ms to 300 ms, and then to 200 ms. The reason
to adjust the operating conditions during the test is to combine
the experiment of parameter influence for more valuable
results, together with the more severe test on the catalyst Fig. 8 e Stability of Ni catalyst at S/C ratio of 3.0 (catalyst
stability. After the above experiments, we have demonstrated loading [ 6.8 g/m2, T [ 900  C).
that the Ni catalyst plates prepared for the applications in
micro-channel reactors have excellent catalytic performance,
3.3.2. Particle size of active components
including the activity and the stability, to satisfy the demand of
The size of nickel particles can be obtained by measuring and
highly efficient SRM reaction in milliseconds.
averaging over a number of particles from TEM images. The
results are shown in Table 1. Catalysts with the loading of
3.3. Catalyst characterization 1.6 g/m2 own the smallest Ni particles. The sizes of Ni particles
are a little bigger for catalysts with the loadings of 3.4 g/m2 and
3.3.1. Crystalline phase identification by XRD 6.8 g/m2. As evidence, Ni particles in used catalysts did not
XRD patterns of both fresh and used catalysts for three aggregate obviously compared to that in fresh catalysts for
different loadings were carried out. As they showed similar each loading. Hence, only TEM and SEM images of used
patterns, the case with catalyst loading of 3.4 g/m2 was taken catalysts are shown in Fig. 10.
as an example. The XRD patterns were shown in Fig. 9. It can It can be also noticed that the Ni particles show uniform
be seen that NiO also exists in fresh catalysts, which indicates dispersion for all three used catalysts from the SEM images.
that not all NiO phase can be reduced even at a high The only difference is that the size of active components in
temperature of 900  C. But in general, NiO are almost totally catalysts with the loading of 1.6 g/m2 is smaller than that in
reduced to Ni at such a high temperature for powder catalyst the other two catalysts. As a whole, the active components of
[5,24]. This may indicate that the interaction between Ni the catalysts have been well dispersed on the substrate plate,
particle and substrate plate is much stronger than that in the showing little difference before and after reaction.
powder formed catalyst.

Fig. 7 e Stability of Ni catalyst at S/C ratio of 1.0 (residence Fig. 9 e XRD patterns of (a) fresh catalysts and (b) used
time [ 70 ms, T [ 900  C). catalysts (Ni catalyst loading [ 3.4 g/m2).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3 7111

Table 1 e Crystal sizes of active components in different

catalysts.
Crystal size, nm Catalyst loadings, g/m2

1.6 3.4 6.8

Fresh catalyst 11.9 17.8 17.5

Used catalyst 12.4 17.6 18.7

3.3.3. XPS analysis

Fig. 11 shows the XPS spectra of the Ni(2p3) for catalysts with
the loading of 3.4 g/m2 before and after SRM reaction. The
existence of two forms of Ni, located at w853.0 and w854.9 eV
was detected in all catalysts. The peak located at w853.0 eV can
be attributed to Ni, while the peak observed at w854.9 eV is
attributed to NiO. It also indicated that not all NiO phase was
reduced during the reduction process, as represented in XRD
patterns. Fig. 11 e XPS Ni(2p3) spectra of (a) fresh catalysts and (b)
used catalysts with catalyst loading of 3.4 g/m2.
3.4. Catalyst deactivation

Generally speaking, the main reasons for catalyst deactivation

in SRM reaction are sintering, coking, and oxidation. The
uniform dispersion of active components of Ni catalyst is
regarded as the crucial factor to obtain the excellent catalytic
performance [25,26]. Ni catalysts prepared in this work
showed excellent performance for SRM reaction: no notice-
able deactivation was detected in the experiments. Here we
tried to analyze the three possible reasons for catalyst deac-
tivation for a better understanding of the process.
3.4.1. Sintering of active phase
As listed in Table 1, the size of active components did not
become bigger obviously after SRM reactions. Besides, in XRD
profiles, the peak intensities of Ni in used catalysts did not
change clearly compared to that in fresh catalysts, as shown
in Fig. 9. Moreover, the dispersion of active components was
still uniform after reaction, as seen in Fig. 10. This indicated
that the active phase did not sinter visibly and the dispersion
state was almost unchanged. Nevertheless, sintering is a main
reason for deactivation of Ni catalysts in powder form, espe-
cially when the original dispersion is not well controlled [27].
One reason is that the interaction between active component
and substrate plate could be much stronger than that in
powder form, which may lead to the un-complete reduction of
the catalyst. Another reason could be attributed to the exis-
tence of NiO, which may have a positive effect to inhibit sin-
tering of Ni.

Fig. 10 e TEM and SEM images of Ni catalysts after reaction with different catalyst loadings (a) 1.6 g/m2, (b) 3.4 g/m2, (c) 6.8 g/
m2. The detailed scale bars are (a) top 10 nm, bottom 100 nm; (b) top 20 nm, bottom 100 nm; (c) top 20 nm, bottom 100 nm.
7112 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3
3.4.2. Coke formation
In XRD patterns of used catalysts, no visible peak of coke was
detected, as shown in Fig. 9. Furthermore, the peak of coke
would also appear in SEM-EDS images if coking occurred.
Likewise, no coke was detected when sampled at several
points using EDS. It demonstrated that no coke was formed in
such a reaction system, even at a rather low S/C ratio of 1.0.
Coking is generally considered as an important reason for
deactivation of Ni catalyst in powder form. The high resis-
tance to carbon formation of the catalysts here may be
attributed to the rather fine dispersion of active components.
On the other hand, due to the excellent efficiency of heat
transfer in micro-channel reactor, the temperature is highly
uniform across the catalyst coating layer, which inhibits the
existence of hot-spot temperature. Thus the coke formation
can be restrained effectively.
3.4.3. Oxidation of metal active phase
It is known that the relative amount of substance with
different valence can be obtained from XPS. In order to eval-
uate the oxidation tendency of Ni phase in SRM reaction, the
following calculation has been undertaken:
areaNi at 853:0 eV
X Excellent Talents in University are acknowledged. The
areaNiO at 854:9 eV
Fig. 11 shows the results corresponding to the catalyst
loading of 3.4 g/m2. For fresh catalyst, X equals 0.71, while it is
0.68 for used catalyst. The numbers of other four catalysts are
all around in the range. This illustrated that nearly no Ni
phase was oxidized to NiO in the SRM reaction. Additionally, it
can be seen from XRD patterns that the peak intensities of
both Ni phase and NiO phase do not change markedly after the
SRM reaction, which gave the same conclusion.
To sum up, no matter whether from the catalytic perfor-
mance of the catalysts, or from the analysis of catalyst char-
acterization, it can be concluded that Ni catalysts prepared in
this work did not show any sign of deactivation in the micro-
channel reactor system.
4. Conclusion
This work presented a comprehensive study on the catalytic
performance of Ni as the catalyst to implement millisecond
SRM reaction in micro-channel reactors. Firstly, we developed
a new method to manufacture the metaleceramics complex
substrate as catalyst support, on which Ni or Rh catalyst was
impregnated, formed firm and active catalyst coatings. The
fall-off rate of the catalyst can be neglected after the plates
experienced the high-temperature SRM reaction and strong
vibration in ultrasonic cleaner. Such catalyst coated plates can
be easily made, showing the reliability in long-term use and
the excellent catalytic performance for SRM reaction in micro-
channel reactors within milliseconds. Though less active than
Rh catalyst, Ni also showed wonderful performance to cata-
lyze the SRM reaction in micro-reactors. Using the appropriate
reactor design (i.e., reactor-II in this work), CH4 conversion
reached above 90% when the residence time was as short as
32 ms for catalyst loading of 6.8 g/m2. When the residence
time was longer than 100 ms, CH4 conversion was above 98%.
Besides, catalyst deactivation was not detected for a 500 h test
on stream with S/C ratio of 3.0, and for 12 h with S/C of 1.0 as
well. Extensive characterizations of these Ni catalyst plates
were also carried out to get a better understanding of the
catalytic performance. The results of XRD, SEM, TEM and XPS
characterizations demonstrated that Ni catalysts prepared in
this work did not show any sign of deactivation after being
used in the micro-channel system under high-temperature
operation. In conclusion, it would be more promising and
practical to explore the application of Ni catalyst in milli-
second micro-channel reactors to realize the SRM reaction for
hydrogen production than the expensive Rh catalyst. While,
the metaleceramics complex substrate might open more
opportunities for the reliable engineering applications of
(micro-)channel reactors.
Acknowledgements
Financial supports from National Natural Science Foundation
of China (No. 20990223) and the Program for New Century
authors would like to thank PetroChina for continuous
financial support.
references
[1] Rostrup-Nielsen JR. Fuels and energy for the future: the role
of catalysis. Catal Rev 2004;46:247e70.
[2] Mustafa B. Potential importance of hydrogen as a future
solution to environmental and transportation problems. Int J
Hydrogen Energy 2008;33:4013e29.
[3] Kepinski L, Stasinska B, Borowiecki T. Carbon deposition on
Ni/Al2O3 catalysts doped with small amounts of
molybdenum. Carbon 2000;38:1845e56.
[4] Xu J, Chen LW, Tan KF, Borgna A, Saeys M. Effect of boron on
the stability of Ni catalysts during steam methane reforming.
J Catal 2009;261:158e65.
[5] Wang K, Li XJ, Ji SF, Shi XJ, Tang JJ. Effect of Ce xZr1- xO2
Promoter on Ni-Based SBA-15 Catalyst for Steam Reforming
of Methane. Energy Fuels 2009;23:25e31.
[6] Oh YS, Roh HS, Jun KW, Baek YS. A highly active catalyst,
Ni/Ce-ZrO2/q-Al2O3, for on-site H2 generation by steam
methane reforming: pretreatment effect. Int J Hydrogen
Energy 2003;28:1387e92.
[7] Huang TJ, Huang MC. Effect of Ni content on hydrogen
production via steam reforming of methane over Ni/GDC
catalysts. Chem Eng J 2008;145:149e53.
[8] Nguyen LQ, Abella LC, Gallardo SM, Hinode H. Effect of nickel
loading on the activity of Ni/ZrO2 for methane steam
reforming at low temperature. React Kinet Catal Lett 2008;93:
227e32.
[9] Wang Y, Yoshiba F, Kawase M, Watanabe T. Performance
and effective kinetic models of methane steam reforming
over Ni/YSZ anode of planar SOFC. Int J Hydrogen Energy
2009;34:3885e93.
[10] Liu CJ, Ye JY, Jiang JJ, Pan YX. Progresses in the preparation of
coke resistant Ni-based catalyst for steam and CO2 reforming
of methane. ChemCatChem 2011;3:529e41.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 1 0 5 e7 1 1 3
[11] Liu CJ, Burghaus U, Besenbacher F, Wang ZL. Preparation and
characterization of nanomaterials for sustainable energy
production. ACS Nano 2010;4:5517e26.
[12] Makarshin LL, Andreev DV, Gribovskiy AG, Parmon VN.
Influence of the microchannel plates design on the efficiency
of the methanol steam reforming in microreactors. Int J
Hydrogen Energy 2007;32:3864e9.
[13] Villegas L, Masset F, Guilhaume N. Wet impregnation of
alumina-washcoated monoliths: effect of the drying
procedure on Ni distribution and on autothermal reforming
activity. Appl Catal A 2007;320:43e55.
[14] Lerou JJ, Ng KM. Chemical reaction engineering: A multiscale
approach to a multiobjective task. Chem Eng Sci 1996;51:
1595e614.
[15] Holladay JD, Wang Y, Jones E. Review of developments in
portable hydrogen production using microreactor
technology. Chem Rev 2004;104:4767e90.
[16] Tonkovich AY, Yang B, Perry S, Fitzgerald SP, Wang Y. From
seconds to milliseconds to microseconds through tailored
microchannel reactor design of a steam methane reformer.
Catal Today 2007;120:21e9.
[17] Tonkovich AY, Perry S, Wang Y, Qiu D, LaPlante T,
Rogers WA. Microchannel process technology for compact
methane steam reforming. Chem Eng Sci 2004;59:4819e24.
[18] Wang Y, Chin YH, Rozmiarek RT, Johnson BR, Gao Y,
Watson J, et al. Highly active and stable Rh/MgO-Al2O3
catalysts for methane steam reforming. Catal Today 2004;98:
575e81.
[19] Johnson BR, Canfield NL, Tran DN, Dagle RA, Li XS,
Holladay JD, et al. Engineered SMR catalysts based on
7113
hydrothermally stable, porous, ceramic supports for
microchannel reactors. Catal Today 2007;120:54e62.
[20] Wang F, Zhang DW, Zheng SW, Qi B. Characteristic of cold
sprayed catalytic coating for hydrogen production through
fuel reforming. Int J Hydrogen Energy 2010;35:8206e15.
[21] Wu XD, Weng D, Zhao S, Chen W. Influence of an aluminized
intermediate layer on the adhesion of a g-Al2O3 washcoat on
FeCrAl. Surf Coat Technol 2005;190:434e9.
[22] Valentini M, Groppi G, Cristiani C, Levi M, Tronconi E,
Forzatti P. The deposition ofg-Al2O3 layers on ceramic and
metallic supports for the preparation of structured catalysts.
Catal Today 2001;69:307e14.
[23] Wu XD, Weng D, Xu LH, Li HD. Structure and performance of
g-alumina washcoat deposited by plasma spraying. Surf Coat
Technol 2001;145:226e32.
[24] Christensen KO, Chen D, Lodeng R, Holmen A. Effect of
supports and Ni crystal size on carbon formation and
sintering during steam methane reforming. Appl Catal A
2006;314:9e22.
[25] Fonseca A, Assaf EM. Production of the hydrogen by methane
steam reforming over nickel catalysts prepared from
hydrotalcite precursors. J Power Sources 2005;142:154e9.
[26] Melo F, Morlanes N. Synthesis, characterization and catalytic
behaviour of NiMgAl mixed oxides as catalysts for hydrogen
production by naphtha steam reforming. Catal Today 2008;
133:383e93.
[27] Zhou L, Guo Y, Zhang Q, Yagi M, Hatakeyama J, Li HB, et al.
A novel catalyst with plate-type anodic alumina supports,
Ni/NiAl2O4/g-Al2O3/alloy, for steam reforming of methane.
Appl Catal A 2008;347:200e7.