Methanol Synthesis from Synthesis Gas utilziing an Innovated Ruthenium-Catalyzed Method Veronica Ibe, Duncan Wass, Richard Wingad, Jason Lee, and Terence Nile UNCG and University of Bristol Abstract Phosphorus NMRs of Ruthenium Catalyst (B) Methanol can be synthesized from Syngas using ruthenium catalysts. We report on the novel use of 3 new bidendate phosphinoamine ligands, to probe the 2 steps believed to be involved with these catalysis. The first step involves the formation of methyl formate from methanol using a base and carbon monoxide. In the second step this methyl formate is hydrogenated to give 2 moles of methanol. Reactions were done in a single cell autoclave and products were analyzed via GC chromatography. Conclusions of our studies will be reported as well as their relevance to the catalytic reaction. Results Conclusions Table 1: Concentration of MeOH and Formate of each catalytic run of Hydrogenation of Methyl Formate with H2 Ligand MeOH (mmol) Formate (mmol) 21.1 2.8 20.4 2.7 25.2 3.3 Reaction Process • Dimethyl: ~56.07 ppm • Non-methyl: ~62.65 ppm Table 2: Ratios of MeOH and Formate of each catalytic run of Hydrogenation of Methyl Formate with H2 Ligand MeOH % • 3 Ruthenium Catalysts were made • First part of the reaction (1 mole of MeOH to 1 mole of Formate) was successfully conducted. • Second part of the reaction (1 mole of Formate to 2 moles of Methyl Formate) proved less successful. • All 3 catalysts proved equally effective in the formation of methyl formate. • Catalyst (A) made the most MeOH in the formatin of MeOH from Syngas reaction. • Results are more qualitative due to the difficulties of measuring newly made MeOH in contra to starting MeOH. Formate % Future 79.00% • (1) 1 mole of Methanol is converted to methyl formate using Carbon moxide and base NaOMe. 21.00% 79.00% 21.00% 79.40% 20.60% • Attempt alternative experimental conditions: - longer reflux time - increase amount of catalyst used - differing bases - differing pressure • (2) 1 mole of Methyl Formate is converted to 2 moles of Methanol using hydrogen and Ruthenium Catalyst. The extra mole of Methanol can be reused to restart the process. Table 3: Concentration of MeOH and Formate of each catalytic run of Syngas to MeOH References • (3) Exemplifies the combined reaction of reaction (1) and (2) Hydrogenation of Methyl Formate Ruthenium Catalysts • • • • Ru Catalyst (0.01 mmol) NaOMe (1 mmol) = 0.054 g THF = 10 mL Methyl Formate (20 mmol) = 1.23 mL Ligand MeOH (mmol) Formate (mmol) 14.5 6.7 7.3 11.7 12.8 6.7 • S. Carobene, R.L. Wingad, D.F. Wass. Thesis. Cloning Methanol: A Novel Ruthenium-Catalyzed Method for Methanol Synthesis from Syngas via Methyl Formate. 2010 • E.S. Lee, K. Aika. Journal of Molecular Catalysis. 141. 241-248. 1999. • L. Fan, Y. Sakaiya, K. Fujimoto. Applied Catalysis. 180. L11-L13. 1999 • S.P. Tanner, D.L. Trimm, M.S. Wainwright. Journal of Molecular Catalysis. 18. 215-222. 1999 Duration: 1 hour Temperature: 100° C H2 50 bar Syngas to Methanol (A) (B) • • • • Ru Catalyst (0.01 mmol) NaOMe (1 mmol) = 0.054g THF = 10 mL MeOH (20 mmol) = 0.81 mL Duration: 24 hours Temperature: 100° C H2/CO 50 bar (C) RESEARCH POSTER PRESENTATION DESIGN © 2012 www.PosterPresentations.com Acknowledgements Thanks to Dr. Duncan Wass, Richard L. Wingad, Jason Lee, and Terrence A. Nile. Thanks to University of Bristol. Special thanks to the financial support from the National Science Foundation (grant 0964420) is gratefully acknowledged.