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Kinetic studies of CO2 reforming of methane over a highly active Ni/La/R-Al2O3 catalyst were
performed in an atmospheric microcatalytic fixed-bed reactor. The reaction temperature was
varied between 700 and 900 °C, while partial pressures of CO2 and CH4 ranged from 16 to 40
kPa. From these measurements kinetic parameters were determined; the activation energy
amounted to 90 kJ/mol. The rate of CO2 reforming was described by applying a Langmuir-
Hinshelwood rate equation. The developed kinetics was interpreted with a two-phase model of
a fluidized bed. The predictions for a bubbling-bed reactor operated with an undiluted feed
(CH4:CO2 ) 1:1) at 800 °C showed that, on an industrial scale, significantly longer contact times
(Hmf ) 7.8 m, mcat/VSTP ) 31.8 g‚s‚mL-1) are necessary for achieving thermodynamic equilibrium
(XCH4 ) 88.2%, XCO2 ) 93.6%). The performance of the reactor was strongly influenced by the
interphase gas exchange: the highest space time yields were obtained for small particles (dp )
80 µm).
( )
0.045-0.090 mm).
kpCH4pCO2 pCO2pH22 3.2. Model Validation and Catalyst Deactivation
1- in a Fluidized Bed. Model Validation. The CH4
(1 + K1pCH4 + K2pCO)(1 + K3pCO2) KeqpCH4 pCO2 conversion profiles measured after 1000 min on stream
in a laboratory-scale fluidized-bed reactor are presented
(7) in Figure 4. The gas velocity applied corresponds to a
The water-gas shift reaction was also included in the u/umf ratio of 8.5. The kinetic parameters applied in
model reaction scheme, assuming first-order reaction in the simulations were recalculated from the initial
each reactant and the same rate constant as the CO2- activity by applying the deactivation constant deter-
reforming reaction. It was further assumed that the mined in the fluidized bed. The steep increase of
influence of pH2 and pCO does not change at low reactant- conversions in the distributor zone and the fact that
to-product ratios. thermodynamic equilibrium is already achieved on a
Kinetic Parameters. The data were fit to the model height of 2 cm above the distributor confirm the high
by using a least-squares fitting procedure. The best fit activity of the applied Ni/La/Al2O3 catalyst. The high
was obtained with the constants presented in Table 2. catalytic activity is also confirmed by the different
5184 Ind. Eng. Chem. Res., Vol. 36, No. 12, 1997
Mleczko, L.; Malcus, S.; Wurzel, T. Catalytic Reformer- Teuner, S. A new process to oxo-feed. Hydrocarbon Process. 1987,
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Mleczko, L.; Malcus, S.; Wurzel, T. Reaction engineering investi- combustion chemistry. Part 1. Methane and related compounds.
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Osaki, T.; Masuda, H.; Mori, T. Intermediate hydrocarbon species of methane to produce synthesis gas over metal-supported
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Santos, A.; Menéndez, M.; Santamaria, J. Partial oxidation of
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Ross, J. R. H. Carbon dioxide reforming of methane in the
presence of nickel and platinum catalysts supported on ZrO2. Received for review March 27, 1997
Stud. Surf. Sci. Catal. 1994, 81, 285. Revised manuscript received August 4, 1997
Slagtern, A° .; Olsbye, U.; Dahl, I. M.; Blom, R.; Fjellvåg, H. Accepted August 12, 1997X
Characterisation of Ni on La modified Al2O3 during CO2
reforming of methane. Appl. Catal. A 1997, in press. IE970246L
Swaan, H. M.; Kroll, V. C. H.; Martin, G. A.; Mirodatos, C.
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X Abstract published in Advance ACS Abstracts, October 15,
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