1. Optimization of Oxidative Desulfurization: Using a film-shear reactor to achieve ultra-low sulfur levels in diesel fuel Helen B. Dauer*, Brandy R. Fox #, and David R. Tyler #. Department of Chemistry, (*)The University of the South, Sewanee, TN, (#) University of Oregon, Eugene, OR Rotation Speed → 854-6941 rpm Gap Width → 25-150 μm Residence Time → 4-48 s Temperature → 30-70 ºC Possible reactor parameters thiophene in decane aqueous oxidizing agents Reactor Products: Two-layered solution Organic layer: contains unoxidized thiophene Aqueous layer: contains oxidized thiophene Conclusions/ Future Work: Thiophene contaminants found in diesel and jet fuel are oxidized by the reactor in less than a minute. Quantitative gas chromatography analysis with a sulfur chemiluminescence detector is needed to determine the amounts of each thiophene oxidized by the reactor. The reactor conditions need to be optimized. Oxidation of benzothiophene has been performed in the reactor with varying parameters, but quantitative analysis of each of these samples is needed. Future work will also attempt to determine the reaction pathway for the oxidative desulfurization reaction in the reactor. Acknowledgments: NSF-REU Geri Richmond, Jeanne Basom University of Oregon Materials Science Institute Introduction: Sulfur contaminants in diesel fuel include thiophenes, benzothiophenes, dibenzothiophenes, and their alkylated derivatives. These contaminants cause sulfur emissions which contribute to acid rain. Sulfur contaminants in fuel also poison catalysts which control hydrocarbon and carbon monoxide emissions. 1,2 Although jet fuel could be used in fuel cells, any sulfur contaminants in jet fuel will deactivate the fuel cell. 1 Sterically hindered compounds such as 4,6 dimethyldibenzothiophene are particularly difficult to remove. Problems with this oxidation method: Elevated temperatures Long reaction times (6+ hours) Aqueous oxidizing agent is separate from organic fuel Performing this reaction in a film-shear spinning disc reactor will potentially improve reaction conditions so that oxidation can be achieved at lower temperatures and in shorter time periods. 4 Standard oxidation reaction: 3 Known diesel fuel thiophene contaminants were run through the reactor and the reactor products were analyzed by TLC : Known jet-fuel thiophene contaminants were synthesized and run through the reactor, and the reactor products were analyzed by TLC: 5 Parameters: Rotation Speed → 6941 rpm Gap Width → 100 μm Residence Time → 32 s Temperature → 30 ºC Oxidation of thiophenes by the reactor: References: 1)Lee, I., Ubanyionwu, H. Fuel, 2008, 87, 312-318. 2) Song, C., Ma, X. Applied Catalysis B: Environmental, 2003, 41, 207-208. 3) Otsuki, S., Nonaka, T., Takashima, N., Qian, W., Ishihara, A., Imai, T., Kabe, T. Energy and Fuels, 2000, 14, 1232-1239. 4) Holl, R. A. PI with Sheared Film Reactors – A Comparison. Presentation at the Dutch Process Intensification Network (PIN-NL) Symposium, April 6, 2005. 5) Werner, E. Recueil des Travaux Chimiques des Pays-Bas, 1949, 68, 509-519. 2-methylbenzothiophene starting material 30% H 2 O 2 / formic acid sulfone standard reactor product sulfone standard 4,6-dimethyldibenzothiophene starting material sulfoxide standard 30% H 2 O 2 / formic acid 2.3.7-trimethylbenzothiophene starting material oxidized standard 2.3.-dimethylbenzothiophene starting material oxidized standard One possible method of sulfur removal involves oxidizing the sulfur compound and extracting the oxidized sulfone species.