Desulphurization of gasoline by metallic sodium

Reggel, Leslie; Blaustein, Bernard D.; Delledonne, C; Friedman, S.; Steffgen, Fred W.; Winslow, J.

doi:10.1016/0016-2361(76)90082-x

Cited by 7 publications

(14 citation statements)

References 2 publications

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“…We felt that it was likely that there would be negligible sulfur and phosphorus in the aqueous phase since SPBu 3 and PBu 3 are not very soluble in water. If these methods corroborated our 31 P NMR results, we would use this approach wherever appropriate, since it is more convenient. This 95208R10 methodology turns out to be unworkable for a variety of reasons, including retention of metal species in the organic phase as complexes ligated by PBu 3 .…”

Section: Speciation and Quantitation Of Spbu 3 And Pbu 3 In Reactionsupporting

confidence: 59%

“…Sonication instead of heating was also disappointing ( The desulfurization reaction in this work occurs as shown in eqn 1 in which the sulfur present in coal is predominantly converted to tributylphosphine sulfide. We observed in CPMAS 31 P NMR studies that the phosphorus species incorporated into the coal residue from this reaction can include Bu 3 P, Bu 3 P=S, Bu 3 P=O, Bu 3 PH + and a phosphate ester that can be written as (Coal-O) 3 P=O. After the desulfurization coal residue was washed with ethyl ether and/or methylene chloride eight times for all entries in Table 1, only Bu 3 P=O could be detected in the filtrate by GC analysis.…”

Section: Speciation and Quantitation Of Spbu 3 And Pbu 3 In Reactionmentioning

confidence: 71%

“…Earlier we showed that HPBu 3 + (observed by 31 P NMR spectroscopy in Illinois No. 6 treated with Bu 3 P) can be formed from phenolic (or carboxylic acid) protons present in the coals.…”

Section: R10mentioning

confidence: 93%

“…31 P NMR analysis by integration of SPBu 3 and PBu 3 peaks indicated that up to 90% of the sulfur was removed in some reactions. Elemental analysis of the coal residues gave variable and often conflicting results owing to the fact that some of PBu 3 and SPBu 3 remains in the coal matrix, and also, a small amount of the coal is dissolved in the SPBu 3 /PBu 3 product mixture.…”

Section: Speciation and Quantitation Of Spbu 3 And Pbu 3 In Reactionmentioning

confidence: 99%

“…Elemental analysis of the coal residues gave variable and often conflicting results owing to the fact that some of PBu 3 and SPBu 3 remains in the coal matrix, and also, a small amount of the coal is dissolved in the SPBu 3 /PBu 3 product mixture. Further complicating the 31 P NMR integrations are the paramagnetic mineral materials extracted from the coal that broaden the peaks and interfere with quantitation of the peak areas. The analytical problem here is a non-trivial one because part of the coal dissolves in the SPBu 3 /PBu 3 reagent mixture and part of this mixture is embedded in the coal residue.…”

Section: Speciation and Quantitation Of Spbu 3 And Pbu 3 In Reactionmentioning

confidence: 99%

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A Novel Approach to Catalytic Desulfurization of Coal

Verkade¹

2001

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Column chromatographic separation of the S=PBu 3 /PBu 3 product mixture followed by weighing the S=PBu 3 , and by vacuum distillation of S=PBu 3 /PBu 3 mixture followed by gas chromatographic analysis are described. Effects of coal mesh size, pre-treatment with methanol Coal (S) + excess PR 3 Coal + S=PR 3 /PBu 3 and sonication on sulfur removal by PBu 3 revealed that particle size was not observed to affect desulfurization efficiency in a consistent manner. Coal pretreatment with methanol to induce swelling or the addition of a filter aid such as Celite reduced desulfurization efficiency of the PBu 3 and sonication was no more effective than heating. A rationale is put forth for the lack of efficacy of methanol pretreatment of the coal in desulfurization runs with PBu 3 . Coal desulfurization with PBu 3 was not improved in the presence of miniscule beads of molten lithium or sodium as a desulfurizing reagent for SPBu 3 in a strategy aimed at regenerating PBu 3 inside coal pores. Although desulfurization of coals did occur in sodium solutions in liquid ammonia, substantial loss of coal mass was also observed.Of particular concern is the mass balance in the above reaction, a problem which is described in some detail. In an effort to solve this difficulty, a specially designed apparatus is described which we believe can solve this problem reasonably effectively.Elemental sodium was found to remove sulfur quantitatively from a variety of polycyclic organosulfur compounds including dibenzothiophene and benzothiophene under relatively mild conditions (150 0 C) in a hydrocarbon solvent without requiring the addition of a hydrogen donor. Lithium facilitates the same reaction at a higher temperature (254 0 C). Mechanistic pathways are proposed for these transformations. Curiously, dibenzothiophene and its corresponding sulfone was virtually quantitatively desulfurized in sodium solutions in liquid ammonia at -33 0 C, although the yield of biphenyl was only about 20 to 30%. On the other hand, benzothiophene gave a high yield of 2-ethylthiophenol under these conditions. Although our superbase P(MeNCH 2 CH 2 ) 3 N, which is now commercially available, is a more effective desulfurizing agent for a variety of organophosphorus compounds than PPh 3 or its acyclic analogue P(NMe) 3 , it does not desulfurize benzothiophene or dibenzothiophene.ii 95208R10

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Section: Speciation and Quantitation Of Spbu 3 And Pbu 3 In Reactionsupporting

confidence: 59%

Section: Speciation and Quantitation Of Spbu 3 And Pbu 3 In Reactionmentioning

confidence: 71%

“…Earlier we showed that HPBu 3 + (observed by 31 P NMR spectroscopy in Illinois No. 6 treated with Bu 3 P) can be formed from phenolic (or carboxylic acid) protons present in the coals.…”

Section: R10mentioning

confidence: 93%

Section: Speciation and Quantitation Of Spbu 3 And Pbu 3 In Reactionmentioning

confidence: 99%

Section: Speciation and Quantitation Of Spbu 3 And Pbu 3 In Reactionmentioning

confidence: 99%

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A Novel Approach to Catalytic Desulfurization of Coal

Verkade¹

2001

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Carbon‐Supported Potassium Hydride for Efficient Low‐Temperature Desulfurization

Chang

Fedorov

2022

Chemistry A European J

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The industrial removal of organosulfur impurities from fossil fuels relies on transition‐metal‐based catalysts in harsh conditions (ca. 400 °C, up to 100 bar H2), yet desulfurization (DS) of refractory alkyl dibenzothiophenes (DBTs) remains challenging. Here, we report that carbon‐supported potassium hydride (KH/C) enables efficient DS of DBTs in mild conditions, viz. >97 % conversion of DBTs is achieved at 165 °C in 3–6 h while the yields of respective biphenyls are 84–95 % by using only 15 % excess of KH per a C−S bond. In addition, KH/C allows to lower the concentration of 4,6‐Me2DBT in the mesitylene solution from 1000 ppm to <3 ppm (165 °C, 20 h) and provides deoxygenation, denitrogenation and catalytic aromatic hydrogenation reactions. DS of various sulfur heterocycles by using KH/C, a transition‐metal‐free material based on earth abundant elements, is viable at low temperature and has prospects for the further development towards decentralized removal of organosulfur species from fossil fuels.

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