OXIDATIVE STEAM REFORMING OF METHANE IN MICROCHANNEL REACTORS

Mustafa Karakaya, Eyup Simsek, Ahmet K. Avci, Z. Ilsen Onsan Department of Chemical Engineering, Bogazici University, Bebek 34342, Istanbul, Turkey

Summary Oxidative Steam Reforming (OSR) of methane to synthesis gas over -Al2O3 supported bimetallic 0.2wt%Pt-2wt%Rh catalyst was investigated in coated and packed microchannel reactors. Methane conversion and CO selectivity in product were investigated in terms of reaction temperature, molar steam-to-carbon (S:C) and oxygen-to-carbon (O2:C) ratios, and contact time over two catalyst geometries. It was found that the coated microchannel reactor, which gives higher CO selectivity is more preferable than the packed microchannel reactor. Keywords Microchannel reactor, oxidative steam reforming, methane, bimetallic Pt-Rh

Introduction
Syngas (CO+H2) is an important feedstock in industrial chemicals production processes such as Fischer-Tropsch and methanol syntheses. Oxidative steam reforming (OSR), which is a combination of endothermic steam reforming and exothermic total oxidation, is a major route for producing syngas from hydrocarbon-based fuels. While combustion of part of the fuel facilitates steam reforming, it might also lead to hot-spot formation in industrial reactors, which, in turn, causes deactivation of the Ni-based catalyst generally used. Hot spots during OSR can be eliminated by using Rh- or Pt-based catalysts [1]. Emerging microchannel technology can be another option for the solution of the problem described above. With their characteristic channel dimensions between 10 and 1000 m, microchannels provide enhanced heat transfer rates that are a few orders of magnitude greater than those possible with conventional reactors [2]; therefore, heat generated locally can rapidly be spread over the entire domain, and nearly isothermal operating conditions can be guaranteed. Moreover, due to reduced mass transfer limitations owing to micrometer channel dimensions, the reactions can be carried out in the kinetic regime. The aim of this work is to assess the methane OSR performances of two typical microchannel reactor

configurations wall-coated and packed that are operated under identical conditions in a wide range of parameter values including residence time, reaction temperature, inlet steam-to-carbon (S:C) and oxygen-to-carbon (O2:C) molar ratios.

Experimental
Oxidative steam reforming runs on the bimetallic 0.2wt%Pt-2wt%Rh dispersed on a suitable porous -Al2O3 support. Powdered catalyst is prepared by incipient-to-wetness impregnation and then mixed with water to form slurry which is coated on two heat-treated FeCrAlY plates to give a catalyst amount of 0.0107 g. The coated plates are then inserted into an engineered steel housing such that the space between the catalytic faces of the plates forms a microchannel. In the packed configuration (Fig. 1), the particulate catalyst is also prepared by incipient-to-wetness impregnation, and then filled into the microchannel having the same flow-by (void space+catalytic coating) volume. In this case, two uncoated plates are inserted into the central part of the housing and supported with a ceramic wool plug. The resulting space forms a microchannel, having dimensions of 0.75 mm x 4 mm x 20 mm (height x width x depth). This microchannel is filled with a total amount of 0.0107 g of the particulate catalyst. The reactor is placed inside a long quartz tube whose temperature is kept constant by an electric furnace.

The effects of reaction temperature, contact time, oxygen-to-carbon (O2:C), steam-to-carbon (S:C) molar ratios are studied. The temperature is varied at 50C increments between 500 and 650C. The O2:C ratio with the specific values of 0.47, 0.54 and 0.63 is kept below the stoichiometric value of 2. The S:C ratio is varied between 0.5 and 3. Using N2 as balance, total flow rate and CH4 mole fraction are kept constant at 210 cm3/min and 0.14, respectively, except in testing the effect of contact time (Wcat/FCH4,0) where contact times of 0.35, 0.41, 0.50 and 0.71 mg.min/cm3 are used in both reactor configurations.

Fig. 3. Effect of temperature on CO selectivity in coated and packed microchannels (S:C=3.0, O2:C=0.47) Full oxygen conversion is achieved in all runs, indicating that total oxidation is much faster than steam reforming and that increasing temperature only enhances the reforming conversion. Higher temperatures lead to higher CO selectivity (moles CO/(moles CO+moles CO2)) values (Fig. 3). Comparing two catalyst geometries, lower CO selectivity is obtained in packed microchannel because water gas shift activity seems to suppress the partial oxidation of methane. As for the effect of O2:C ratio, total oxidation conversion increases with increasing oxygen partial pressure, and the amount of extra water produced increases steam reforming conversion, which, however, also decreases the CO selectivity (Fig. 3).

Fig. 1. Top (left) and cross-sectional (right) views of the packed microchannel configuration (1: Engineered metal housing; 2: FeCrAlY plates; 3: Packed catalyst; 4: Ceramic wool plug) SEM-EDX characterization of the reduced catalyst showed uniform distribution of metals across the plate and no coke formation in both geometries.

Results and Discussion

Although increase in reaction temperature increases CH4 conversion in both reactor configurations, coated microchannel gives higher CH4 conversions up to 600-625C, after which performances of coated and packed reactor configurations are similar (Fig. 2).

Acknowledgement
Financial support provided by Bogazici University projects BAP-09HA506D and BAP 6349, and TUBA-GEBIP support to Ahmet K. Avci are acknowledged.

References
[1] K. Tomishige, S. Kanazawa, K. Suzuki, M. Asadullah, M. Sato, K. Ikushima, K. Kunimori, Effective heat supply from combustion to reforming in methane reforming with CO2 and O2: comparison between Ni and Pt catalysts, Appl. Catal. A Gen. 233 (2002) 35- 44. Fig. 2. Effect of temperature on CH4 conversion in coated and packed microchannels (S:C=3.0, O2:C=0.47) [2] L. Kiwi-Minsker, A Renken, Microstructured reactors for catalytic reactions, Catal. Today, 110 (2005) 2-14.