Heteropolyacids As Effective Catalysts to Obtain Zero Sulfur Diesel*
Pure Appl. Chem., Vol. 79, No. 11, pp. 1887–1894, 2007. doi:10.1351/pac200779111887 © 2007 IUPAC Heteropolyacids as effective catalysts to obtain zero sulfur diesel* Alberto de Angelis1,‡, Paolo Pollesel1, Daniele Molinari1, Wallace O’Neal Parker Jr.1, Alessandra Frattini2, Fabrizio Cavani2, Susie Martins3, and Carlo Perego1 1Eni, Refining and Marketing Division, via F. Maritano 26, San Donato Milanese, Italy; 2University of Bologna, viale Risorgimento 4, Bologna, Italy; 3UOP, 25 East Algonquin Road, Des Plaines, IL 60017, USA Abstract: This paper deals with the catalytic properties of different supported heteropolyacids (HPAs), both molybdenum- and tungsten-based, in the oxidative desulfurization process of diesel. We are jointly developing a new oxidative desulfurization process, aimed at reducing the sulfur content in diesel to less than 10 ppm (parts per million) using in situ produced per- oxides. In this new process, high-molecular-weight organosulfur compounds, such as 4,6-di- methyl-dibenzothiophene (DMDBT), difficult to be eliminated by conventional hydro- desulfurization, are oxidized to the corresponding sulfones and subsequently removed by adsorption. Molybdenum-based HPAs, with Keggin structure, proved to be the most active and selective catalysts for oxidizing DMDBT with on-stream lifetimes exceeding 1500 h time on stream (t.o.s.). Keywords: heteropolyacids; desulfurization; diesel; air pollution; molybdenum. INTRODUCTION The sulfur content in fuels is required, by regulations, to be progressively lowered. In diesel, it will have to be reduced to a value lower than 15 ppm (parts per million) in the United States, and to a value lower than 10 ppm in the European Union within the year 2009.
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