Novel Catalytic Methods for Heteroatom Removal in Coal Liquids Upgrading. Final Report, September 1983-December 1985

摘要

The goal of this project is to optimize the reaction conditions for upgrading coal liquids through the development of novel hydrotreating catalysts. Results for this quarter are summarized by tasks. Task 1: The objectives in this task were to compare the relative effects of the added nucleophiles H sub 2 S, LiHS, NH sub 4 HS, NH sub 3 , and H sub 2 O on the hydrodenitrogenation of an SRC-II coal liquid with a commercial sulfided CoMo catalyst. We found that only H sub 2 S enhances the HDN activity of the catalyst, whereas NH sub 3 retards the process. However, under our conditions, H sub 2 S had a negligible effect when a NiMo catalyst was substituted for CoMo. In a complementary study we studied the interaction of H sub 2 S with potential coal model compounds and with coal. From the work on coal models we found that H sub 2 S catalyzes hydrogen transfer from tetralin to the models or to coal. Task 2: We used organometallic precursors to synthesize several surface confined NiMo and CoMo catalysts on alumina and tested them for quinoline HDN activity. These catalysts were found to have a higher activity than conventional catalysts. However, the selectivities for aromatic and aliphatic hydrocarbon products were similar to those of conventional catalysts. We also found that bulk ruthenium is an exceptionally efficient HDN catalyst. Furthermore, when a commercial CoMo catalyst was doped with ruthenium, a dramatic increase was seen in both the HDN activity of the catalyst and the selectivity to aromatic products. Task 3: We found that addition of acids to SRC-II liquid aids in removing the nitrogen, without concurrent polymerization. Also, in model systems, the addition of acids aids in the hydrogenation of quinoline to tetrahydroquinoline. 14 refs. (ERA citation 11:015510)