Energy Conversion and Management 47 (2006) 459469

www.elsevier.com/locate/enconman

Comparative study between uidized bed and xed bed

reactors in methane reforming with CO2 and O2 to produce
syngas
Qiangshan Jing

a,b

, Hui Lou b, Liuye Mo b, Xiaoming Zheng

b,*

Department of Chemistry, Xinyang Normal University, Xinyang 464000, PR China

Institute of Catalysis, Department of Chemistry, Zhejiang University, Hangzhou 310028, PR China
Received 15 March 2004; received in revised form 2 November 2004; accepted 18 May 2005
Available online 14 July 2005

Abstract
Reforming of methane with carbon dioxide and oxygen was investigated over Ni/MgOSiO2 catalysts
using xed bed and uidized bed reactors. The conversions of CH4 and CO2 in a uidized bed reactor were
close to thermodynamic equilibrium. The activity and stability of the catalyst in the xed bed reactor were
lower than that in the uidized bed reactor due to carbon deposition and nickel sintering. TGA and TEM
techniques were used to characterize the spent catalysts. The results showed that a lot of whisker carbon
was found on the catalyst in the rear of the xed bed reactor, and no deposited carbon was observed on
the catalysts in the uidized bed reactor after reaction. It is suggested that this phenomenon is related to
a permanent circulation of catalyst particles between the oxygen rich and oxygen free zones. That is, uidization of the catalysts in the uidized bed reactor favors inhibiting deposited carbon and thermal uniformity in the reactor.
2005 Elsevier Ltd. All rights reserved.
Keywords: Methane reforming; Fixed bed; Fluidized bed; Syngas

Corresponding author. Tel.: +86 571 88273272; fax: +86 571 88273283.
E-mail address: zhengxm@zju.edu.cn (X. Zheng).

0196-8904/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2005.05.006

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1. Introduction
Synthesis gas is a versatile feedstock for methanol, FischerTropsch syntheses and dimethyl
ether (DME). Recently, major research eorts have been concentrated on CO2 reforming [13]
and partial oxidation [46]. The problem of dry reforming of methane with CO2 is carbon
deposition, and it is highly endothermic. However, partial oxidation of methane is an exothermic
reaction, as has been reported [7], consisting of methane combustion and successive reforming
with the produced CO2 and H2O. Therefore, a serious temperature gradient is caused in the catalyst bed, which often leads to hot spots.
Recent literatures have shown that combined CO2 reforming and partial oxidation of methane
can eectively minimize the external energy requirements [810]. Reforming of methane with CO2
and O2 involves a coupling of methane oxidation with CO2 reforming of methane in the same
reactor. The uidized bed reactor provides a close idealization in gassolid contactors for high
heat transfer rates, which is needed to ensure isothermal operation in a reactor [11]. The use of
solid catalysts as internal heat carriers will provide a more homogeneous temperature distribution
in the uidized bed reactor. In addition, deactivation of the catalyst for carbon deposition is also
minimized in a uidized bed reactor. This can be attributed to the permanent circulation of catalyst particles, which favors burning the deposited carbon on the catalyst in the oxygen rich zone
of the catalyst bed.
A catalyst requires a number of special characteristics in order to t the combined process using
a uidized bed reactor [12,13]. The catalyst should be stable at high temperatures and high stream
partial pressure, be mechanically strong, be resistant to coke and have suitable support/metal
interaction and activity. In addition, a catalyst suitable for this combined process will need to
be uidizable and stable when exposed to continuous redox cycles.
Previous works [14,15] in our laboratory have shown that the Ni/SiO2 modied by alkaline metal oxides has excellent activity and stability for this combined reaction using a uidized bed reactor. In this paper, the combined reaction to produce syngas with a suitable H2/CO ratio over
magnesium oxide modied Ni/SiO2 catalysts was investigated. Especially, this study focused on
the comparison between uidized bed and xed bed reactors.

2. Experimental
2.1. Catalyst preparation
Ni/MgOSiO2 catalysts were prepared by successive impregnation. The precursors of Ni and
MgO were Ni(NO3)2 6H2O and Mg(NO3)2 6H2O. Silica gel (supplied from Qingdao Oceanic
Chemical Co, B = 0.180.30 mm, SBET = 363 m2/g) was used as the support material for its excellent abrasive resistance, and it was rstly modied with the MgO. Supported Ni catalysts were
prepared by impregnation of the support (MgOSiO2) with an aqueous solution of Ni(NO3)2
6H2O. After drying at 383 K for 24 h, the samples were calcined in air at 973 K for 4 h. The prepared catalysts were denoted by xM1/yMgOSiO2, in which x or y means wt.% of metal content in
the reduced catalysts.

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2.2. Catalytic reaction

Reforming of methane with CO2 and O2 was performed in a uidized bed and a xed bed reactor at atmospheric pressure. The illustration of the experimental setup is presented in Fig. 1. Both
the reactors, a 12 mm (ID) quartz tube tted with a stainless mesh distributor were placed in a
well insulated temperature programmable electric furnace. A telescopic thermocouple (TC1), inserted axially within the bed, permitted temperature measurements at dierent positions along the
reactor length. The reaction temperature was monitored inside (TC1) and outside the reactor
(TC2). The reaction temperature was usually controlled by TC1 as described in Fig. 1 (temperature deviation in a uidized bed reactor: 5 K at 973 K). In the xed bed reactor, quartz wool was
put on the catalyst so as to prevent the catalyst particles from moving. Feed gas (CH4(99.9%),
CO2(99.9%) and O2(99.9%)) and euent were metered by electric mass ow controllers (Brooks,
5850E, 1%.FS). The pretreatment of 2 ml catalysts was H2 reduction at 923 K for 1 h at atmospheric pressure. The euent gas of the reaction was cooled in an ice water bath and analyzed
with an online gas chromatograph (GC) equipped with a TCD (column packing: TDX-01).
The conversion and selectivity of products were calculated by an area normalization method,
which is presented as follows:
X CH4 % F CH4 ;in  F CH4 ;out =F CH4 ;in  100%
X CO2 % F CO2 ;in;  F CO2 ;out; =F CO2 ;in  100%

1
2

S H2 F H2 ;out =2F CH4 ;in  F CH4 ;out  100%

S CO F CO;out =F CH4 ;in  F out;CH4 F CO2 ;in  F CO2 ;out   100%

F i F total C i
where X, S, F and Ci is conversion, selectivity, gas ow rate and molar fraction of i in the feed
gas or the euent gas, respectively. The calculation of conversion and selectivity is based on C,

Fig. 1. Schematic representation of experimental setup.

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H balances in the reactants and the product. The systematic deviation of the calculated conversion
and selectivity is not more than 2%. The methane conversion of 15% is due to combustion in the
case of CH4/CO2/O2 = 1/0.4/0.3. The methane conversion beyond this 15% can be assigned to
reforming. In our reaction conditions, when the formation of CO2 due to methane combustion
is larger than the consumption of CO2 due to methane reforming, the CO2 conversion shows negative. In all reaction tests, the detected oxygen conversion was 100%.
2.3. Characterization
Transmission electron microscope (TEM) images were taken on the JEM-2020F(JEOL) operated at 200 kV. The samples were dispersed in tetrachloromethane by supersonic waves and put
on Cu grids for the TEM observation in air.
Thermogravimetric analysis (TGA) for estimation of the carbon amount was performed with a
PerkinElmer TAC T/DX. After the catalytic reaction, a part of the catalyst (ca. 10 mg) was removed from the catalyst bed. The TGA prole was measured under oxygen (99.99%, 20 ml/min)
at a programmed temperature velocity of 20 K/min.
2.4. Fluidization characterization study
According to Baeyens formula [16], the dependency of the minimum uidization velocity (xmf)
on temperature and particle density can be described as
d p1.82 rs  rg 0.94
m=s
xmf 0.00923
lg0.88 rg0.06
where rs is the particle density, rg is the gas density, lg is the gas viscosity and the dp is the average
particle diameter.
Using this formula as a basis, the calculated xmf in the case of Ni/MgOSiO2 and the feedstock
with CH4/CO2/O2 = 1/0.4/0.3 (volume ratio) at 293 K is 3.23 cm/s. Its corresponding ow rate is
218 ml/min. The ow rate used in our experiment is set as 300 ml/min. Thus, the uidized bed was
between the bubbling and turbulent regime over the range of ow rates used. The bubbles were
seen visually at lower ow rates. No channeling was observed except when the catalysts agglomerated at high temperature. At high ow rates closer to the turbulent regime, there was more
entrainment of nes. The turbulent regime is characterized by breakup of the bubbles and more
uniformity in the bed. Since the uidized bed was close to the turbulent mode, these results should
simulate the behavior of a large scale reactor operating in the turbulent regime fairly closely, making scale up relatively straightforward.

3. Results and discussion

3.1. Catalyst performance
Fig. 2 shows the eect of space velocity on the methane and CO2 conversions in reforming
methane with CO2 and O2 using uidized bed and xed bed reactors. The space velocity was

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463

Fig. 2. Methane and CO2 conversion in reforming of methane with CO2 and O2 using uidized bed and xed bed
reactors as a function of space velocity. (Reaction conditions: CH4/CO2/O2 = 176/71/53; temperature, 973 K).

varied via diluting the catalyst with SiO2 support. The activity was measured for 1.5 h at each
space velocity. At the low space velocity (6000 h1), the conversions of CH4 and CO2 in both
the uidized and xed beds were almost the same. This indicated that the catalyst particles
did not uidize under these ow conditions in the uidized bed reactor, and the state in the reactor
was similar to that in the xed bed reactor. However, a large dierence between the two reactors
in the methane and CO2 conversions was observed at high space velocity. In the xed bed reactor, the conversions decrease monotonously with increasing space velocity. At the space velocity
of 45,000 h1, the conversions of CH4 and CO2 in the xed bed reactor were reduced to 42%
and 16% compared to 52.1% and 38% in the uidized bed reactor, respectively. Methane combustion can proceed in a very short contact time, while reforming of methane with CO2 and/or H2O
cannot be complete at conditions of high space velocity. The uidized bed reactor also gives higher CH4 and CO2 conversions than the xed bed reactor. Furthermore, the dierence in CH4 and
CO2 conversion between the two reactors becomes larger with increasing space velocity. This suggests that the uidized bed reactor enhances the CH4 and CO2 conversions in this combined
reaction.
The conversions of CH4 and CO2 as a function of time on stream in reforming methane with
CO2 and O2 over 5Ni/MgOSiO2 catalyst at 973 K are shown in Fig. 3. The catalytic activity can
be maintained during 600 min in both reactors. The methane and CO2 conversions in the xed bed
reactor were slightly lower than those in the uidized bed reactor. Tomishige et al. [10] have reported that methane reforming reaction is practical only on Ni0 species. There are more reduced
nickel species in the uidized bed reactor than in the xed bed reactor due to the redox circulation.
Consequently, the reforming activity was dierent for each of the two reactors. The dierence in
methane conversion exists during the stability test.

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Fig. 3. Dependence of CH4 and CO2 conversion on time on stream in reforming of methane with CO2 and O2 over
5 wt.%Ni/MgOSiO2 using uidized bed and xed bed reactors. (Reaction temperature 973 K; space velocity:
9000 h1).

3.2. Characterization results and discussion

Fig. 4 shows the TEM images of fresh and spent 5Ni/MgOSiO2. On the catalysts in the upper
part of the xed bed reactor (Fig. 4d), a lot of whisker carbon was observed. In contrast, there
were some particles on which no whisker carbon was observed on the catalyst in the inlet of
the xed bed reactor (Fig. 4c). That is, two kinds of catalyst particles were existing in the xed
bed reactor. One is catalyst particles with carbon, and the other is catalyst particles without carbon. Probably, this is because the catalyst bed was divided into two parts. One part is in the reducing atmosphere, and the other is in the oxidizing atmosphere.
From Fig. 4(d), the diameters of whisker carbon observed in the TEM image of the used catalyst in the rear of the xed bed reactor were relatively uniform. Sakae et al. have reported that
the position and size of the Ni metal particles located at the tips of the whisker carbon observed
in the TEM images and the diameter of the Ni particles was almost the same as that of the whisker
carbon [17]. This whisker carbon did not decrease the reforming activity of the supported
nickel catalysts. However, with prolonged time on stream, this deposited whisker carbon
would transform into graphite carbon, which may cover the active sites and result in catalyst deactivation. The surface of a Ni metal particle present on the tip of a whisker carbon adsorbs
methane, and then the adsorbed methane decomposes into carbon and hydrogen atoms. A valuable advantage of the uidized bed reactor is its lower carbon deposition on catalysts when
compared to xed bed operation, especially in the case of the supported nickel catalyst [18].
This is a consequence of the permanent circulation of the solid particles, which are periodically

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465

Fig. 4. TEM images of 5 wt.%Ni/MgOSiO2 catalysts: (a) after H2 reduction at 923 K for 1 h; (b) after reaction in a
uidized bed reactor; (c) outlet catalyst after the reaction in a xed bed reactor and (d) inlet catalyst after the reaction in
a xed bed reactor).

transported to the oxygen rich entrance zone of the bed, and the gasication processes involving oxygen and steam (from the total oxidation of methane) help to control the level of coke
on the catalysts. Fig. 4(c) also shows that slight nickel aggregation was observed in both the catalysts in the xed bed and the uidized bed reactor after reaction relative to that on the fresh
catalyst.
The TGA results of 5Ni/MgOSiO2 catalyst after the reaction (Fig. 3) in the uidized and xed
bed reactors are shown in Fig. 5. The weight loss due to carbon combustion (773873 K) was
clearly observed on the catalyst in the upper part of the xed bed reactor. In contrast, no weight
loss was observed on the catalysts in the uidized bed reactor and the oxygen rich zone in the xed
bed reactor. The TGA results were in accord with that of the TEM, and the uidized bed reactor
was ecient in inhibiting carbon deposition on the catalyst.
The response for heating and cooling in methane reforming with CO2 and O2 in a uidized bed
reactor is shown in Fig. 6. On the Ni/MgOSiO2 catalyst without being pretreated by hydrogen,
methane combustion started at 723 K, while methane reforming started at 1023 K. In addition,
the conversion in the heating process was much lower than that in the cooling process. This is
due to the dierence in the reduction degree of the catalysts. When the Ni/MgOSiO2 catalysts
were pre-reduced with H2 at 923 K, it had a similar activity like that in the cooling process (see
Fig. 3). That is, the catalyst is reduced gradually with methane and/or produced syngas in the
heating process. The catalyst in the cooling process can have a higher reduction degree. The

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Fig. 5. Thermogravimetric analysis of 5Ni/MgOSiO2 after the reaction shown in Fig. 3 using uidized bed and xed
bed reactor: (a) catalyst in the upper part of xed bed reactor; (b) catalyst in uidized bed reactor and (c) catalyst in the
inlet part of xed bed reactor.

Fig. 6. The response for heating and cooling in methane reforming with CO2 and O2 in a uidized bed reactor.
CH4/CO2/O2 = 176/71/53; 2 ml catalyst; uidized bed reactor. Catalyst was used without the hydrogen pretreatment.

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467

Fig. 7. Models of uidized bed and xed bed reactors in methane reforming with CO2 and O2.

dierence in the conversion of methane between the heating and cooling processes indicates that
the degree of reducibility of Ni/MgOSiO2 is not so high.
The results reported by Dissanake et al. showed that the catalyst bed was divided into three
parts in partial oxidation of methane using a xed bed reactor [19]. Methane combustion happened in the anterior two zones in a xed bed reactor. In the rear zone, in contact with an oxygen
free atmosphere, H2 and CO were formed at near equilibrium concentrations via the endothermic
reforming reactions. Models of uidized bed and xed bed reactors are depicted in Fig. 7. In the
uidized bed reactor, there also exists a zone, near the distributor plate, in which the catalyst sees
a highly oxidant mixture and a second zone, which is located further into the bed, in which the
oxygen has been consumed and metallic centers are reproduced on the solid. The main dierence
is that the catalyst is in a permanent circulation between the oxygen rich and oxygen free zones.
Thus, the catalyst that is oxidized by oxygen in the front region can transfer to the rear part where
it is re-reduced and exhibits reforming activity. This decreases the amount of oxidized catalyst and
increases the amount of reduced catalyst [9]. Enhancement of the methane reforming activity by
using the uidized bed reactor can be explained by the model described above. The uidized bed
reactor is a very useful tool for laboratory studies in this system because temperature uniformity is
achieved. Since the uidized bed reactor was close to the turbulent mode, these results should simulate the behavior of a large scale reactor operating in the turbulent regime fairly closely, making
scale up relatively straightforward. The high conversions and autothermal operation suggest that
the uidized bed oers a viable energy ecient alternative reactor conguration for synthesis gas
generation by the catalytic combined CO2 reforming and partial oxidation of methane.

4. Conclusions
The following conclusions can be derived from the results of the present study.
The reforming of methane with CO2 and oxygen can be operated at very short contact times
and nearly uniform temperatures in the catalyst bed. The performance of the Ni/MgOSiO2 catalyst depends strongly on the oxidation state of the active component. Oxidized nickel sites
showed a very low reforming activity compared to the reduced metallic ones. Conversions of

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CH4 and CO2 near thermodynamic equilibrium were obtained if a reduced catalyst was used, but
the fresh unreduced catalyst exhibited lower reforming activity when the temperature is under
1023 K.
A lot of whisker carbon was observed on the used catalyst in the rear of the xed bed reactor.
Therefore, the CH4 and CO2 conversions catalyzed by in situ reduced catalyst are lower than predicted by thermodynamic equilibrium. Enhancement of the conversion is caused by uidization of
the catalyst in the uidized bed. Fluidization has a favorable eect on inhibition of carbon deposition. Probably, this is because the catalyst particles are circulated between the oxidizing and the
reducing zone and the carbon gasication proceeds in the oxidizing zone.

Acknowledgement
This research project is supported by the National Natural Science Foundation (Project:
20343002) and the Ministry of Education Foundation (Project: 20030335068).

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