STUDIES IN MOLTEN CHLOROALUMINATES; A. FISCHER-TROPSCH SYNTHESIS USING METALLIC DISPERSIONS. B. INFRARED SPECTROELECTROCHEMISTRY USING ATTENUATED TOTAL REFLECTANCE

The Fischer-Tropsch activity of several metallic catalysts in molten chloroaluminates has been studied at relatively low pressures. Low conversions of CO to alkanes were observed for Co, Fe, Ni, Pd, Pt, Ir, Rh and Re. No reaction was observed for W, Ta and the pure chloroaluminate melt. Methane was the major product formed using any of these heterogeneous catalysts. The most favorable product distribution for these metals was observed for Ni catalysts, since less than half of the products was CH(,4).; The effect of aluminum on the Fischer-Tropsch activity of these metallic catalysts in molten chloroaluminates has also been studied. In all cases, the conversion of CO was enhanced by the presence of aluminum. The magnitude of enhancement depended on the catalyst. Large enhancements were observed for Co, Ni and Fe catalysts, while only slight enhancements were observed for Pd, Pt and Re. Aluminum behaved as a reagent, and not as a catalyst, since CO conversion varied with the amount of Al in the system. The effect of Al on product distribution was also largely dependent on the metal catalyst involved. Small amounts of Al increased the production of CH(,4) relative to the other products for Co, Fe and Ni catalysts, while no clear pattern emerged for these catalysts, when larger amounts of Al were present.; The Ir(,4)(CO)(,12) catalyst precursor was also studied in chloro-aluminate melts. In batch reactions at relatively long times, a slight excess of CH(,4) over C(,2)H(,6) was found. No CH(,3)Cl was detected. In a recycle-flow reactor, C(,2)H(,6) was produced in greater amounts than CH(,4). CH(,3)Cl was observed in the flow system. Enhancement by Al was found to be greater for small amounts of Al than for large amounts. The proportion of CH(,4) in the products was observed to increase with increasing Al content.; An infrared spectroelectrochemical cell, based on attenuated total reflectance using a silicon crystal, has been developed for use in molten chloroaluminates. Spectra of chloranil and its reduction products have been obtained.