Fuel 95 (2012) 599–605

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Total methanation of syngas to synthetic natural gas over Ni catalyst in a

micro-channel reactor
Zhihong Liu, Bozhao Chu, Xuli Zhai, Yong Jin, Yi Cheng ⇑
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Methanation reaction from syngas to synthetic natural gas (SNG) has been successfully implemented over
Received 13 October 2011 Ni catalyst in a micro-channel reactor with high conversion and selectivity in milliseconds contact time. A
Received in revised form 22 December 2011 new method called improved thermal spray to manufacture the metal-ceramics complex substrate as cat-
Accepted 23 December 2011
alyst support was presented. The substrate demonstrated dual functions, i.e., the superior heat conduction
Available online 2 January 2012
as metal and stable catalyst coating on it as ceramics (e.g., Al2O3). The experiments verified that the fall-off
proportion of the catalyst can be neglected after the plates experienced methanation reaction and strong
Keywords:
vibration in ultrasonic cleaner. Meanwhile, the catalyst coatings on the walls of micro-channel reactor
Methanation
Synthetic natural gas (SNG)
showed high activity and stability, having the excellent catalytic performance for methanation reaction
Micro-channel reactor in micro-channel reactors and the reliability in long-term use as well. At the temperature of 550 °C and
Nickel catalyst the pressure of 30 atm, CO conversion and CH4 selectivity can remain above 98% and 92%, respectively,
Millisecond reaction at a high GHSV of 71,000 h1, where the corresponding residence time is only about 50 ms. Extensive char-
acterizations of these Ni catalyst plates were also made to get a better understanding of the catalytic per-
formance. The results of XRD, SEM, TEM and TPR characterizations demonstrated that Ni catalysts
prepared in this work did not show any sign of deactivation after being used in the micro-channel system.
It is expected that the methanation reactor technique based on the metal-ceramics complex substrate as
the catalyst support in (micro-)channel reactors would open opportunities for the reliable engineering
applications of either distributed or mass production of SNG from syngas.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction gas pipelines from the west to the east are already available, and
extra pipelines are being constructed for the energy supply (i.e.,
For the limited reserves and increased price of oil, coal utiliza- natural gas) to the developed areas in the east of China. Therefore,
tion becomes more and more significant nowadays. Among the dif- coal to SNG project becomes particularly important and feasible in
ferent routes of coal conversion, coal to SNG (synthetic or China.
substitute natural gas) [1] has attracted much attention in recent Kopyscinski et al. [1] made a thorough review on the technolo-
years in parallel to the processes of coal to liquid fuels and coal gies for the production of SNG from coal and dry biomass from
to light olefins [2–4]. It is well-known that SNG is a versatile en- 1950 to 2009. So far, there is only one commercialized industrial
ergy carrier, which can be readily produced from coal or biomass, technology to implement the coal to SNG process in the world, that
and is inter-changeable with Natural Gas (>95% methane, high is, the Great Plains Synfuels Plant (GPSP) in Beulah, North Dakota
HHV (i.e., higher heating value)) [5]. The advantages of SNG are (USA), producing approximately 15 TWh/year of SNG from lignite
the high conversion efficiency from either coal or biomass, the al- coal. For the mature development of gasification, water–gas–shift
ready existing gas distribution infrastructure such as pipelines and (WGS) and gas cleaning techniques, we only focus our attention
the well-established and efficient end use technologies. As an on the methanation process in this work.
example in China, natural gas resources are very much short of Methanation (CO + 3H2 = CH4 + H2O) is an important process in
supply but coal is rather abundant. In the remote, western areas the chemical industry, including removal of trace amounts of CO
of China, Xinjiang Province possesses 40% of the coal reserves in from H2-rich feed gas, purification of the reformate gas for fuel cell,
China, but the long distance transportation of solid coals are not al- and processes in relation to Fischer–Tropsch synthesis [6–9]. From
lowed from the viewpoint of economics. Alternatively, the natural the thermodynamic point of view, it can be concluded that the
methanation is favored at low temperature and high pressure.
Operating at high pressure produces a large amount of heat per
⇑ Corresponding author. Tel.: +86 010 6279 4468; fax: +86 010 6277 2051. volume compared to a low-pressure process. In the context, total
E-mail address: [email protected] (Y. Cheng). methanation is referred to the methanation reaction with pure

0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.12.045
600 Z. Liu et al. / Fuel 95 (2012) 599–605

syngas (i.e., CO and H2) as the feedstock, where the mole ratio of H2 – Plug flow pattern in the channels helps to obtain the ideal reac-
to CO is about 3.0. As a comparison, the partial methanation indi- tor performance (i.e., high conversion and selectivity) for
cates the conversion of little amount of CO in the feedstock, which methanation reaction.
is generally used to increase the heat-value of city gas. A distinct – Catalysts are coated on the channel walls so that there is little
difference in these two processes is the amount of heat released pressure drop across the empty channel.
from the reaction. In the former case (i.e., the total methanation), – Reactor scale-up is easy by the so-called ‘‘number-up’’ method-
the reactor design and the catalyst activity meet more challenges ology. Subsequently, the reactor technique can be suited for dis-
due to the much higher exothermicity than the partial methana- tributed and/or mass production of SNG from different syngas
tion, especially under the high pressure conditions (e.g., 3– resources (e.g., from coal or biomass gasification, or from coke
5 MPa). Except for the total methanation reaction in the SNG pro- oven gas).
duction process, the WGS reaction (CO + H2O = CO2 + H2) must be
suppressed as a side reaction, which reduces the selectivity of The key issues to implement the methanation process in above-
methane. In the industrial SNG production, the mole ratio of H2/ mentioned micro-reactor technique lie in the two aspects at the
CO in the feed gas is 3.0–3.1, slightly higher than the lab-scale research. The first is the stable catalyst coating on metal
stoichiometry. surface considering the potential risk of the catalyst layer falling off
Since the 1970s a number of methanation processes have been due to the difference of thermal expansion coefficients between
developed, comprising both fixed bed and fluidized bed methana- the metallic substrate and the catalyst layer. The second is the cat-
tion [1]. As mentioned above, the heat removal of total-methana- alyst activity and stability. Our earlier work [23,24] has demon-
tion reaction for the production of SNG is a major concern for strated that using the metal-ceramic complex substrate can
reactor design, which can be solved by a series of fixed bed metha- successfully overwhelm the bottleneck of catalyst layer stability.
nation reactors with intermediate gas cooling or recycle of product Ni catalyst was adopted to catalyze the SRM reaction in millisec-
gas considering the thermodynamics, reactions mechanism and onds. In particular, a 500-h on stream experiment was successfully
kinetics of total methanation [1,10,11]. As a comparison, fluidized carried out under the temperature of 900 °C, showing wonderful
bed is inherently suitable for the highly exothermic reaction sys- catalyst stability with high activity. In this work, we will inherit
tems due to the excellent heat transfer and removal capabilities. the above experience to further investigate the methanation reac-
Meanwhile, fluidized bed technique particularly fits the mass pro- tion in the micro-channel reactor. Since the methanation reaction
duction of chemicals in industry. However, a challenging problem is one of the representative exothermic reactions, this work should
is inevitably encountered for the methanation process that high be able to suit for many other applications that need well-con-
conversion and selectivity of the reactor performance is difficult trolled temperature conditions.
to be implemented in a fluidized bed, in which gas and solids back-
mixing plays a negative role in the overall reactor performance. Up
2. Experimental
to now, fluidized bed methanation reactor is still under-develop-
ment in a lab or a pilot-plant scale [12–14].
2.1. Catalyst plate preparation
Different from the conventional reactor techniques, we aim to
develop (micro-)channel reactors (or in other words, structured
As mentioned above, we have developed a type of metal-ceram-
reactors) to facilitate the highly exothermic methanation reaction
ics complex substrate as the support plate to load catalyst in order
under high pressure operation. It has been acknowledged that mi-
to implement stable and active catalyst coatings for methanation
cro-channel reactors have unique features of process intensifica-
reaction in micro-channels [24]. The specific approach is briefly de-
tion, for example, the excellent temperature control and
scribed as below.
improved mass transfer especially in the applications of highly
exothermic and endothermic reactions [15,16]. A metallic struc-
tured support, with its inherent high thermal conductivity, can 2.1.1. Manufacture of metal-ceramics complex substrate
be used as the substrate of catalysts and integrated for micro-chan- First of all, a layer of nano-particles, c-Al2O3, is thermally
nel reactor applications. Researchers from Velocys and Pacific sprayed on a metallic substrate, usually FeCrAlloy, to manufacture
Northwest National Laboratory (PNNL) reported the development the metal-ceramics complex substrate. But different from the tra-
of a millisecond micro-reactor concept for steam reforming of ditional thermal spraying, the metallic substrate is preheated to
methane (SRM) process (i.e., the reverse reaction of total methana- an appropriate temperature (e.g., 1200 °C) before deposition. Then
tion) with highly efficient integration of an exothermic combustion the binding force between the two different substances can be
channel and an endothermic reforming channel with high thermal greatly enhanced because the ceramic particles would embed into
efficiency through the channel (metal) wall [17–20]. This concept the bulk phase of metal very firmly.
can be alternatively applied for a highly exothermic reaction, such
as the methanation reaction, F–T synthesis [21,22] and so on. It can 2.1.2. Deposition of AlOOH sol
be expected that it would be much easier to remove the heat from According to the method indicated in the Ref. [25], the AlOOH
the exothermic reaction through the metal wall by either liquid sol was prepared in the following procedure: a commercial alumi-
media or steam in micro-channel reactor than to supply the heat num hydroxide powder was dispersed in water (e.g., 15–20 wt%)
to a high-temperature endothermic reaction in a short time. In with continuous agitation, then a 5 mol/L HNO3 aqueous solution
addition to the advantage of heat management, (micro-)channel was used to adjust its pH value from 7 to 2. The solution was stir-
reactors would also offer the following features to favor the metha- red for 5 h at 85 °C and a stable sol was obtained as a result. After-
nation reaction: wards, the metal-ceramics complex substrate is immersed into this
boehmite sol for 3 min, and then withdrawn at a constant speed of
– The small sized reactor space with highly conductive metal wall 3 cm/min to ensure the uniform coating, dried at room tempera-
can guarantee the uniform temperature profile in the catalyst ture for 30 min, then calcined at 600 °C for 6 h. As a result, a layer
coating layers in the reactor, which provides excellent condi- of c-Al2O3 with a higher specific surface area is obtained. The
tions to maintain the catalyst stability and reach the desired above procedures can be repeated until the thickness of the coating
thermodynamic equilibrium under a constant operating layer is up to the desired value [26]. In this work, the thickness of
condition. boehmite sol after immersing is about 200 lm, and the thickness
 Z. Liu et al. / Fuel 95 (2012) 599–605 601

of c-Al2O3 after drying and calcination is about 12 lm and 8 lm, the BET specific surface area is determined by nitrogen adsorption
respectively. method (Autosorb-1-C, Quantachrome Co. Ltd.). X-ray diffraction
(XRD) patterns of catalyst bulks are recorded on a Bruker D8 Ad-
2.1.3. Impregnation of active component vance equipment with Cu Ka radiation in the 2h range of 0  90°.
The modified metal-ceramics complex substrate is further Phase identification of the catalysts is carried out by comparing
impregnated into the prepared solution of Ni(NO3)2 (28 wt%) for the collected spectra with the spectra in the database.
6 h at 80 °C. Then it is dried and aged at 120 °C for 6 h, calcined The morphology of catalyst bulks is characterized using a
at 600 °C for 6 h, and at last the catalyst plate with stable catalyst scanning electron microscopy (SEM, JEOL, JSM-7401F), coupled
coatings is obtained. The specific surface area measured by nitro- with an X-ray energy dispersive spectroscopy (EDS) system to ana-
gen adsorption method is 174 m2/g. The catalyst loading is defined lyze the element composition of selected areas. A JEOL JEM2010
as the catalyst weight loaded on the plate divided by the area of the high-resolution transmission electron microscopy (HR-TEM) is
plate acting as the micro-channel wall. It can be adjusted by vary- used to characterize the diameter of the nickel particles. The
ing the concentration of Ni(NO3)2 solution and the times of TEM samples are prepared as follows: the catalyst powder is
impregnation. The catalyst loading in this work is about 6.8 g/m2. scraped from bulks and dispersed in ethanol by ultrasonic agita-
tion, and then the suspension is dropped on a carbon-coated cop-
2.2. Catalyst characterization per grid and finally dried in air.

Temperature programmed reduction with hydrogen (H2-TPR) is 2.3. Catalyst test

performed on a self-made device. The powder-type sample (ca.
500 mg) for the TPR analysis is prepared by scraping off catalyst First of all, the catalyst plate is cut into the size of
layers from the plate-type catalyst. After loading the powder sam- 2 cm  5.5 cm. Then two sheets of the catalyst plates are inserted
ple into a quartz tube, the sample cell is purged with 50 mL/min of into the slits of micro-channel reactor separately, and the space be-
Ar for 1 h at 500 °C to remove adsorbed H2O and other gases on the tween the two plates forms a channel, with the size of
sample, and then cooled to ambient temperature. Next, the inlet 1.8 cm  5.5 cm  0.08 cm, as shown in Fig. 1. The catalyst plates
gas flow is switched to 50 mL/min of the 20% H2/Ar gas. When can be easily assembled in the micro-reactor.
the system is stable, the sample is heated from room temperature The experimental setup consists of: (a) a gas supply unit (con-
to 1000 °C with a heating rate of 5 °C/min, while the hydrogen con- taining CO, H2 and H2/Ar cylinders and mass flow controllers), (b)
centration in the gas stream leaving the reactor is continuously a micro-channel reactor, and (c) a gas chromatograph (GC). Before
monitored by a thermal conductivity detector (TCD). In addition, the catalyst evaluation, the catalysts are reduced in situ under a

Fig. 1. Schematic diagrams of (a) metal-ceramics complex substrate with catalyst coating and (b) micro-channel reactor.
602 Z. Liu et al. / Fuel 95 (2012) 599–605

flow stream of dilute hydrogen (10%H2/Ar) with the total flow rate micro-channel reactor with coated catalyst walls. Influences of
of 30 NmL/min at 900 °C for 30 min. After reduction, H2/CO mix- the operation parameters such as (oven) temperature, pressure
ture with a fixed H2/CO of 3.1 and determined gas hourly space and GHSV on the catalytic performance for methanation reaction
velocity (GHSV) (varying from 1.0  104  7.1  104 h1) is intro- were investigated comprehensively.
duced into the system. The outlet gases are analyzed after water
condensation with an on-line GC equipped with a TCD. GHSV is de- 3.1.1. Influence of temperature
fined as the total volumetric flow rate at the inlet condition divided Fig. 3 shows the influence of temperature (measured at the
by the volume of micro-channel, and the residence time is the re- oven wall) on the reaction performance under different system
ciprocal of it. pressures. The GHSV of 3.1  104 h1 is maintained the same for
The CO conversion and CH4 selectivity for the reaction are de- this series of experiments. As illustrated, CO conversion increases
fined as follows: sharply with increasing temperature from 350 °C to 450 °C, and
fCO then changes slowly in the temperature range of 450  550 °C.
C CO ¼ 1  ð1Þ The temperature of 500  550 °C seems to be the optimal range
fCO þ fCH4 þ fCO2
in the specified reaction system. CH4 selectivity stays at a high
level when the temperature is lower than 450 °C (almost 100% at
fCH4
SCH4 ¼ ð2Þ T < 400 °C), while the corresponding CO conversion stays at a low
fCH4 þ fCO2
level. This information indicates that the catalyst prepared in this
where C is the conversion, S is the selectivity to a certain product work is not active at low temperatures so that the carbon conver-
and f is the molar fraction in the effluent gas. sions at these temperatures are all directed to the formation of
As pointed out above, a potential risk using such micro-reactors CH4. The GC–MS (Shimadzu QP2010S) gas analysis shows ne-
is the fall-off of the catalyst layer from the metallic substrate. To glected amount of other hydrocarbons. With increasing tempera-
evaluate the fall-off proportion, Ni catalyst plates are withdrawn ture, CH4 selectivity shows little change. While increasing the
from the micro-channel reactors after the catalyst test. The plates system pressure favors CH4 selectivity. At the pressure of 30 atm,
are immersed in an ultrasonic cleaner with frequency of 45 kHz CH4 selectivity can be above 95% in the temperature range of
and power of 200 W. They are then brought out, drought, and 500  600 °C.
weighted after a certain period. The proportions of fall-off are cal-
culated according to the original catalyst loading. As can be seen in 3.1.2. Influence of pressure
Fig. 2, the fall-off proportion of the catalyst plates tends to be un- Fig. 4 shows the influence of pressure on the catalytic perfor-
changed after vibrating for 60 min. In addition, the final fall-off mance of Ni for methanation reaction at different temperatures
proportion is less than 0.8%, which is much smaller than the pre- (with the same GHSV of 3.1  104 h1). It can be seen that with
ceding reports [27,28]. It can be concluded from our experiments the increase of pressure, both CO conversion and CH4 selectivity in-
that the manufactured metal-ceramics complex substrate can be crease. The reason can be directly attributed to the thermodynam-
successfully applied to obtain the stable and active catalyst coat- ics of total-methanation: low-temperature and high pressure are
ings on the plate surface. beneficial. At the same time, taking both CO conversion and CH4
selectivity into consideration, 550 °C shows an optimal tempera-
3. Results and discussion ture for this experimental system. While in general, the methana-
tion reaction would be operated at 350  450 °C for better reaction
3.1. Ni catalytic performance for methanation reaction in micro- performance using particle catalyst of Ni, where the unavoidable
channel reactors temperature rise in a conventional reactor like a fixed bed can be
reasonably allowed. For the excellent heat management in the mi-
According to the procedures described above, two Ni catalyst cro-reactor using the metal-ceramics plates as the wall, the rela-
plates with catalyst loading of 6.8 g/m2 were firstly prepared. Then, tively higher operation temperature (e.g., 550 °C) in the reaction
they were inserted into the slits in the reactor, forming the channels is actually beneficial to the energy utilization. In other

Fig. 2. Fall-off proportion of Ni catalyst plates after reaction evaluated by vibrating Fig. 3. Influence of temperature on methanation performance over Ni catalyst plate
in an ultrasonic cleaner. (GHSV = 31,000 h1).
 Z. Liu et al. / Fuel 95 (2012) 599–605 603

Fig. 6. H2-TPR profile of Ni catalyst plate.

Fig. 4. Influence of pressure on methanation performance over Ni catalyst plate

(GHSV = 31,000 h1).

Fig. 7. XRD patterns of Ni catalyst plates (a) fresh catalysts and (b) used catalysts.

from the reduction of Ni2+ in the NiO phase, and the high temper-
Fig. 5. Influence of GHSV on methanation performance over Ni catalyst plate ature peak most likely corresponds to the reduction of Ni2+ in the
(pressure = 30 atm). NiAl2O4 phase. The TPR curve indicates that the active components
in the catalyst have stronger interaction with supports and are
words, the cooling efficiency in the adjacent channels becomes more difficult to be reduced compared to other Ni catalysts.
high, especially that high-grade steam can be obtained from the
heat exchange. 3.2.2. Crystalline phase identification by XRD
The XRD patterns are shown in Fig. 7. Besides NiO, NiAl2O4 also
3.1.3. Influence of GHSV exists in the oxidized catalyst, which is difficult to be reduced and
Fig. 5 shows the influence of GHSV on the catalytic performance results in the high temperature reduction peak at 760 °C. In the
of Ni for methanation reaction at the system pressure of 30 atm. used catalyst, both Ni and NiO appear. It indicates that a small part
With the increase of GHSV, both CO conversion and CH4 selectivity of Ni may be oxidized to NiO in the methanation process since
decrease to different extent. At 550 °C, CO conversion still remains steam is produced at high temperature.
above 98% at a high GHSV of 71,000 h1, and the corresponding
residence time is 50 ms. It can be concluded that the Ni catalyst 3.2.3. Particle size of active components
layers prepared in this work show adequate activity to catalyze the The size of Ni particles can be obtained by measuring and aver-
methanation reaction in the micro-channel reactors. aging over a number of particles from TEM images. It is 17.8 nm for
fresh catalysts and 21.5 nm for used catalysts. Therefore, Ni parti-
3.2. Catalyst characterization cles in the used catalysts aggregate a little bit compared to that in
the fresh catalysts, but not too much. It should be noticed that the
3.2.1. TPR analysis Ni particles show uniform dispersion for all catalysts from the SEM
Fig. 6 shows the TPR profile of the Ni catalyst prepared in this images. As a whole, the active components of the catalysts have
work. It can be identified that there are two reduction peaks at been well dispersed on the substrate plate, showing little differ-
432 °C and 760 °C individually. The low temperature peak results ence before and after reactions.
604 Z. Liu et al. / Fuel 95 (2012) 599–605

Fig. 8. TEM and SEM images of Ni catalyst plates (a) fresh catalysts and (b) used catalysts.

3.3. Catalyst deactivation 4. Conclusions

Generally speaking, the main reasons for catalyst deactivation This work presented a comprehensive study on the catalytic
in the methanation reaction are sintering and coking. The uniform performance of Ni as the catalyst to implement methanation reac-
dispersion of active components of Ni catalyst is regarded as the tion in micro-channel reactors. Firstly, we developed a new meth-
crucial factor to obtain the excellent catalytic performance. Here, od to manufacture the metal-ceramics complex substrate as the
we try to analyze these two possible reasons for catalyst deactiva- catalyst support, on which Ni catalyst was impregnated, forming
tion for a better understanding of the process. stable and active catalyst coatings. Such catalyst coated plates
showed reliability in long-term use and excellent catalytic perfor-
3.3.1. Sintering of active phase mance for methanation reaction in micro-channel reactors. At
As mentioned above, the size of active components is 17.8 nm 550 °C, CO conversion can still remain above 98% at a high GHSV
for fresh catalysts and 21.5 nm for used catalysts. Thus it does of 71,000 h1. Extensive characterizations of these Ni catalyst
not become bigger obviously after the methanation reactions. plates were also carried out to get a better understanding of the
Moreover, the dispersion of active components is still uniform after catalytic performance. The results of XRD, SEM, TEM and TPR char-
reaction, as seen in SEM images in Fig. 8. This indicates that the ac- acterizations demonstrated that Ni catalysts prepared in this work
tive phase does not sinter visibly and the dispersion state is almost did not show any sign of deactivation after being used in the
unchanged. One reason is that the interaction between active com- micro-channel system.
ponent and substrate plate could be much stronger than that in In conclusion, it would be more promising and practical to ex-
powder form, which may lead to the un-complete reduction of plore the application of Ni catalyst in micro-channel reactors to
the catalyst. Another reason could be attributed to the existence realize methanation reaction. While, the metal-ceramics complex
of NiO, which may have a positive effect to inhibit sintering of Ni. substrate and the according catalyst coating technique might open
more opportunities for the reliable engineering applications of (mi-
3.3.2. Coke formation cro-)channel reactors.
In XRD patterns of used catalysts, no visible peak of coke can be
detected, as shown in Fig. 7. Furthermore, the peak of coke would
Acknowledgments
also appear in SEM–EDS images if coking occurred. Likewise, no
coke can be detected when sampled at several points using EDS.
Financial supports from National Natural Science Foundation of
It demonstrated that no coke be formed in such a reaction system.
China (No. 20990223), Program for New Century Excellent Talents
The high resistance to carbon formation of the catalysts here may
in University and PetroChina are acknowledged.
be attributed to the fine dispersion of active components. On the
other hand, due to the excellent efficiency of heat transfer in mi-
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