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A potassium tert-butoxide and hydrosilane system for ultra-deep desulfurization of fuels

Toutov, Anton A. and Salata, Mike and Fedorov, Alexey and Yang, Yun-Fang and Liang, Yong and Cariou, Romain and Betz, Kerry N. and Couzijn, Erik P. A. and Shabaker, John W. and Houk, Kendall N. and Grubbs, Robert H. (2017) A potassium tert-butoxide and hydrosilane system for ultra-deep desulfurization of fuels. Nature Energy, 2 . Art. No. 17008. ISSN 2058-7546.

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Hydrodesulfurization (HDS) is the process by which sulfur-containing impurities are removed from petroleum streams, typically using a heterogeneous, sulfided transition metal catalyst under high H_2 pressures and temperatures. Although generally effective, a major obstacle that remains is the desulfurization of highly refractory sulfur-containing heterocycles, such as 4,6-dimethyldibenzothiophene (4,6-Me_2DBT), which are naturally occurring in fossil fuels. Homogeneous HDS strategies using well-defined molecular catalysts have been designed to target these recalcitrant S-heterocycles; however, the formation of stable transition metal sulfide complexes following C–S bond activation has largely prevented catalytic turnover. Here we show that a robust potassium (K) alkoxide (O)/hydrosilane (Si)-based (‘KOSi’) system efficiently desulfurizes refractory sulfur heterocycles. Subjecting sulfur-rich diesel (that is, [S] ∼ 10,000 ppm) to KOSi conditions results in a fuel with [S] ∼ 2 ppm, surpassing ambitious future governmental regulatory goals set for fuel sulfur content in all countries. Fossil fuels contain naturally occurring organosulfur impurities, with quantities varying depending on the type of feedstock. These sulfur-containing organic small molecules poison catalytic converters and generate polluting sulfur dioxides when combusted. Hydrodesulfurization (HDS) is the industrial process by which sulfur impurities are removed from petroleum fractions prior to their use as fuels. Currently, HDS is performed by treating petroleum with H_2 at high pressures and temperatures (that is, 150–2,250 psi and 400 °C) over heterogeneous catalysts such as cobalt-doped molybdenum sulfide supported on alumina (that is, CoMoS_x∕γ-Al_2O_3; Fig. 1a). However, certain organosulfur species, in particular dibenzothiophenes alkylated at positions 4 and 6, are not efficiently removed. Homogeneous strategies employing sophisticated, well-defined transition metal complexes—including those based on platinum, nickel, tungsten, molybdenum, palladium, ruthenium, rhodium, iron, cobalt, and others—have been extensively investigated. While these studies have provided valuable mechanistic insights, several fundamental issues, such as the formation of stable organometallic S–M species upon C–S bond activation by the metal centre (Fig. 1b), generally restrict industrial implementation of such methods. Rare examples of desulfurization of dibenzothiophenes alkylated at the 4 and 6 positions by homogeneous transition metal catalysis utilized either Ni compounds in combination with superstoichiometric alkyl Grignard reagents or Ni or Co phosphoranimide complexes in the presence of superstoichiometric KH. These issues pose a formidable challenge for the development of new HDS methods. Moreover, increasingly strict governmental regulations require limiting the sulfur content in diesel fuel and gasoline (in the US: typically <15 and <30 ppm, respectively) as well as other fuels, rendering the development of new powerful HDS methods a primary global concern. In 2013, Grubbs and co-workers reported the KO^tBu mediated cleavage of aryl C–O bonds in lignin models in the absence of transition metals using hydrosilanes. Careful inductively coupled plasma mass spectrometry (ICP-MS) analyses of the reagents and reaction mixtures ruled out catalysis with transition metals. We thus became interested in extending this method to sulfur heterocycles of relevance in oil and gas refining applications. Herein, we report that the robust KOtBu/silane-based (that is, KOSi) system is a powerful and effective homogeneous HDS method, which desulfurizes HDS-resistant dibenzothiophenes in good yield and reduces the sulfur content in diesel fuel to remarkably low levels (Fig. 1c).

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URLURL TypeDescription ReadCube access
Toutov, Anton A.0000-0002-6561-0462
Fedorov, Alexey0000-0001-9814-6726
Houk, Kendall N.0000-0002-8387-5261
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2017 Macmillan Publishers Limited. Received 30 July 2016; accepted 13 January 2017; published 17 February 2017. Support of this work by BP under the XC2 program is gratefully acknowledged. A.A.T. is additionally grateful to the Resnick Sustainability Institute at Caltech, Dow Chemical, and Bristol–Myers Squibb for predoctoral fellowships, and to NSERC for a PGS D fellowship. K.N.H. is grateful to the US National Science Foundation (CHE-1205646 and CHE-1361104) for financial support and to the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the US National Science Foundation (OCI-1053575). Y.L. thanks the ‘National Thousand Young Talents Program’ and ‘Jiangsu Specially-Appointed Professor Plan’ in China for financial support. E.P.A.C. thanks K. Lammertsma (Division of Organic Chemistry, Vrije Universiteit Amsterdam, The Netherlands) for access to, and SURFsara ( for their support in using the Lisa Computer Cluster. G. Huff, G. Sunley, D. Braden, P. Metelski, M. Pinderski, E. Doskocil, A. Lucy, C. Buda, A. Dinse, R. Taylor, J. Bercaw, J. Labinger, M. Howard, M. Desmond, J. Elks, D. Leitch and F. Bell are gratefully thanked for technical contributions and/or invaluable discussion. Author Contributions: A.A.T., A.F. and R.H.G. had the idea and designed experiments with M.S., J.W.S., R.C. and K.N.B. A.A.T., M.S., A.F. and K.N.B. performed experiments and analysed data. Y.-F.Y., Y.L., E.P.A.C. and K.N.H. designed, performed, analysed, and interpreted density functional theory calculations. A.A.T., A.F., M.S., K.N.B. and E.P.A.C. wrote the manuscript with contributions from all authors. All authors contributed to discussions. Data availability: Computational data are available in Supplementary Table 1 and Supplementary Data 1. Further data that support the plots within this paper and other findings of this study should be requested directly from the corresponding authors. Competing interests: A company commercializing the technology reported in this paper is being founded and one of the authors (A.A.T.) will be a co-founder. The other authors declare no competing interests.
Group:Resnick Sustainability Institute
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Resnick Sustainability InstituteUNSPECIFIED
Dow Chemical CompanyUNSPECIFIED
Bristol-Myers SquibbUNSPECIFIED
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
National Thousand Young Talents program of ChinaUNSPECIFIED
Jiangsu Specially-Appointed Professor PlanUNSPECIFIED
Record Number:CaltechAUTHORS:20161205-153231512
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Official Citation:Toutov, A A. et al. A potassium tert-butoxide and hydrosilane system for ultra-deep desulfurization of fuels. Nat. Energy 2, 17008 (2017).
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:72573
Deposited By: Katherine Johnson
Deposited On:21 Feb 2017 21:07
Last Modified:21 Feb 2017 21:26

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