Catalytic partial oxidation of methane. Novel approaches to the catalysts design and process study

The goal of the project is to develop novel approaches in design of advanced catalysts and study kinetic peculiarities of catalytic partial oxidation (CPO) of methane on monolithic catalysts. CPO is an alternative to steam reforming for production of synthesis gas. The exothermic nature of partial oxidation makes the process less energy and capital cost intensive than the conventional endothermic steam reforming, and the lower H2:CO ratio about 2 is more favourable with respect to down stream processes such as methanol synthesis, Fischer-Tropsch synthesis of higher hydrocarbons and using resulting gas mixture as fuel cells feedstock. But for realising a successful CPO of methane reformer there is need to develop catalysts which provide high selectivity and have high temperature durability. To accomplish this goal the following project plan is proposed: 1. Catalyst preparation and characterisation The monolithic supports on the base of alumina modified with Ba, Ca, La, Ce, TiO2, ZrO2-Y2O3, ZrO2-CeO2 will be synthesised. Crucial requirement to the catalytic supports is their high thermal stability (upto 900oC). The non-traditional structured supports on the base of different refractory materials manufactured via self-propagating high temperature synthesis will be elaborated. The active components on the base of combinations of Pt, Rh and transition metal oxides will be selected and methods of their deposition onto support will be developed. Prepared samples - both initial monoliths and catalysts will be characterized with variety of techniques (XRD, XPS, EXAFS, FTIR, ESDR, SEM, TEM). In situ NMR tomographic study of the process of drying of extruded monoliths and study of impregnation of both self-made and commercial monolithic supports will be conducted to elucidate optimal conditions of catalyst preparation. The variation of channel geometry and pitch size of monoliths is the point of special interest since the overall process is combination of heterogeneous reaction on the surface of the catalyst and homogeneous gas phase reactions, and the reaction selectivity toward synthesis gas depends strongly on the ratio of the surface of channel walls to the volume of the channel. 2. Kinetic study of CPO on monolithic catalysts. For testing the catalytic activity the existing laboratory set-up with on-line GC analysis will be adapted to the project purposes. The catalytic properties will be studied at variation of short contact time - around 10 msec. The temperature range is 600-900oC. The methane concentration range is 10-30% vol. The samples with various channel geometry and pitch size of monolith will be used in kinetic studies. Single monolith pieces with a diameter 10 mm and 20 mm and with a length of 10 - 50 mm or combination of several pieces of 10 mm length will be used. Thermal stability of selected monolithic catalysts during extended (1000 hours) experiments will be monitored. Data on catalytic performance and physico-chemical properties will be analysed and recommendation on the procedure of catalyst preparation as well as on optimal operation parameters.