The synthesis of ethane and ethylene from methane and oxygen will be carried out in novel hydrogen transport inorganic membranes and in cyclic reactors in order to prevent undesirable secondary reactions of C2 molecules to CO and CO2. Neither inorganic membrane reactors nor cyclic tubular reactors are presently used in commercial processes. Their application to catalytic reactions represents a novel application of engineering and solid-state chemistry concepts to catalytic reactions. Our approach combines high temperature membrane and cyclic experimental reactors, synthesis and characterization of thin membrane films and of high surface area catalysts, and detailed models of complex gas phase and surface reactions involved in oxidative coupling. We anticipate that this approach will lead to novel reactors for carrying our kinetic-controlled sequential reactions, such as the oxidative coupling of methane. Careful spectrographic and wet chemical analyses of fresh and silent catalysts have shown considerable differences which have permitted conclusions as to the source of deactivation. Our activities in the first quarter FYI 995 have focused on the synthesis, structural characterization, and catalytic evaluation of membrane films, disks, and reactors. We have also continued to exploit reaction-transport models to predict the performance of membrane, cyclic, and recycle reactors in the oxidative coupling of methane.

Work continued on the development of catalysts for the steam gasification of chars and for the oxidative coupling of methane. Testing of the catalysts Ni-Ca-K-oxides and Co-Ca-K-oxides are described for gasification research; results of the testing of a Co-Mg-oxide catalysts for methane conversion are also described.

Work will continue on the oxidative coupling reaction of methane over ternary oxide catalysts to produce C2, C3 and C4 hydrocarbons and particularly olefins with high selectivity. The work which has shown that close to 100% selectivity can be obtained has received wide attention and has resulted in collaborative efforts with industry (CRADA) towards the development of a commercial process. An immediate purpose of additional work is to increase the conversion without diminishing the extremely high selectivity of the reaction and also to permit operation at higher space velocity to reduce equipment size. The mechanism of this reaction is not understood and much additional work is needed to explain the role of carbon formation and of water as intermediates in the reaction and to investigate whether carbon oxides are intermediates. It has been found that oxides other than calcium-nickel-potassium oxides can be useful catalysts for this reaction in the presence of steam and at relatively low temperatures and long contact times. Better definition of the class of binary metal oxides is required and better catalyst characterization is needed to ensure reproducibility of catalyst preparation and operational results. Pretreatment of the catalyst should be shortened and higher space velocities must be obtained. Close collaboration with Orion ACT is required to advance the project toward the pilot plant stage. In the area of coal and char catalytic steam gasification, the large volume of data obtained at atmospheric pressure will be extended to operations at higher pressures.

Work on catalytic steam gasification with chars and coals will be extended from atmospheric to elevated pressures using the newly built pressure unit. The novel finding that coking of petroleum in the presence of small amounts of caustic greatly improves the gasification rates and characteristics of the coke will be extended to chars; in the oxidative coupling of methane over ternary catalysts, emphasis will be placed on low temperature coupling and on the oxidative production of syngas from methane at low temperature. Experimental work will continue on the synthesis of the mixed catalyst, and they will be characterized by a number of techniques, including elemental analyses, x-ray diffraction, and surface area determination.