Volume 95 Issue 9 | p. 11 | Concentrates
Issue Date: February 27, 2017

New approach plucks more sulfur from diesel fuel

Noncatalytic method eliminates recalcitrant sulfur compounds in fuels, could supplement current refinery desulfurization processes
Department: Science & Technology
News Channels: Organic SCENE, Environmental SCENE
Keywords: process chemistry, desulfurization, diesel fuel, sulfur dioxide, acid rain, thiophene
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Current refinery desulfurization processes use a metal catalyst and hydrogen at high temperature and pressure to remove sulfur from fuels, but they are ineffective against some compounds, such as alkylated dibenzothiophenes. A new approach can strip out sulfur from those compounds, making it potentially useful as a supplemental process to further lower the sulfur content of fuels.
Two reactions schemes compare a catalytic and noncatalytic method to remove sulfur from fuels.
 
Current refinery desulfurization processes use a metal catalyst and hydrogen at high temperature and pressure to remove sulfur from fuels, but they are ineffective against some compounds, such as alkylated dibenzothiophenes. A new approach can strip out sulfur from those compounds, making it potentially useful as a supplemental process to further lower the sulfur content of fuels.

An international industry-academic research team has reported a new approach to removing sulfur from diesel fuel that could improve vehicle performance and reduce the environmental impact of using fossil fuels. Gasoline and diesel contain residual amounts of natural organosulfur compounds that can foul catalytic converters and generate polluting sulfur dioxide. Refineries employ heterogeneous catalysts such as cobalt-doped molybdenum sulfide that use hydrogen at high temperature and pressure to strip out as much sulfur as possible from the fuel. But the most recalcitrant compounds, in particular alkylated dibenzothiophenes, are mostly left untouched. Researchers led by BP’s John W. Shabaker, UCLA’s Kendall N. Houk, and Caltech’s Robert H. Grubbs have devised a noncatalytic solution-based process that employs potassium tert-butoxide and alkylsilanes under mild conditions to create silyl radicals that cleave the C–S bond of the heterocyclic compounds, with the silicon whisking away the sulfur. The researchers show that the method, which they call KOSi, can reduce sulfur in diesel fuel to about 2 ppm, well below the current target of 15 ppm (Nat. Energy 2017, DOI: 10.1038/nenergy.2017.8). The researchers note that their proof-of-concept process will need to be adapted to function as a continuous refinery process, but they envision it could become a “polishing treatment” to supplement current desulfurization processes.

 
Chemical & Engineering News
ISSN 0009-2347
Copyright © American Chemical Society
Comments
Robert Buntrock (Thu Mar 02 16:34:10 EST 2017)
It's been known for decades that heteroaromatic sulfur and nitrogen are the most difficult compounds to remove from both crudes and fuels. This reaction looks promising on the face but it's a non-catalytic reaction and to develop a viable process any such desulfurization would have to be catalytic, especially on the scales required.

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