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Pure Appl. Chem., 2007, Vol. 79, No. 11, pp. 1887-1894

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

1 Eni, Refining and Marketing Division, via F. Maritano 26, San Donato Milanese, Italy
2 University of Bologna, viale Risorgimento 4, Bologna, Italy
3 UOP, 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 peroxides. In this new process, high-molecular-weight organosulfur compounds, such as 4,6-dimethyl-dibenzothiophene (DMDBT), difficult to be eliminated by conventional hydrodesulfurization, 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.).