Aqueous High-Temperature Chemistry of Carbo- and Heterocycles. 21. Reactions of Sulfur-Containing Compounds in Supercritical Water at 460 .degree.C

Katritzky, Alan R.; Barcock, Richard A.; Balasubramanian, M.; Greenhill, John V.; Siskin, Michael; Olmstead, William N.

doi:10.1021/ef00044a031

Cited by 52 publications

(53 citation statements)

References 7 publications

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“…[11][12][13][14] Hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemethylation, hydrocracking, and hydrogenation have been reported during the aquathermolysis process. [15][16][17] In catalytic aquathermolysis, different types of catalysts, such as iron-based catalysts, have been widely reported. 11 Various type of iron-based catalysts, such as FeSO 4 , Fe-naphthenate, Fe(CH 3 COCHCOCH 3 ) 3 , iron (III) dodecylbenzene sulfonate, and iron-based ionic liquid, have been successfully used in aquathermolysis.…”

Section: Introductionmentioning

confidence: 99%

Hematite nanoparticles in aquathermolysis: A desulfurization study of thiophene

Khalil

Lee

Liu

2015

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The potential usage of hematite nanoparticles as heterogeneous catalysts in aquathermolysis was investigated in this work. The desulfurization of thiophene was studied to investigate the catalytic activity of hematite in the aquathermolysis of heavy oil. It was found that reaction conditions, e.g., reaction time and temperature, ratio between thiophene and water, hematite nanoparticle size, catalyst concentration, and the presence of hydrogen donors, influenced the ability of hematite nanoparticles to decompose thiophene. Experimental results showed that thiophene conversion was increased with reaction time, temperature and catalyst concentration but decreased with thiophene/water ratio and particle size. Further analysis showed that the activity of the hematite nanocatalyst was also reduced in the presence of hydrogen donors. This is because hydrogen donors occupy the catalyst surface and block the catalytic sites. Furthermore, FTIR and XRD analyses revealed that thiophene underwent oxidative

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Section: Introductionmentioning

confidence: 99%

Hematite nanoparticles in aquathermolysis: A desulfurization study of thiophene

Khalil

Lee

Liu

2015

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“…Their reactivity trend can be expressed in the following order: alkyl sulfides ≈ aromatic sulfides >> thiophenic compounds [144,148,149]. Free radical reactions are typically used to describe the formation of alkyl polysulfides [146][147][148], alkyl-tetrahydrothiophene [146,147], 1-alkene and alkyl thiol from n-alkyl sulfides through radical elimination reactions [146] or (n−1)-alkanes [146,150,151]. In a recent study combining both experimental work and theoretical calculations, the free radical mechanism of the decomposition of n-alkyl sulfide in supercritical water has been further investigated [151].…”

Section: Organosulfur Compoundsmentioning

confidence: 99%

“…The reaction of a C=S bond with water, most likely via pericyclic addition, and the formation of an intermediate geminal mercaptoalcohol leads to the formation of H 2 S and an aldehyde, the latter decomposing to CO and (n−1)-alkyl. All the sulfur-containing aromatic molecules typically found in petroleum, such as diphenylsulfide, naphthyl phenyl sulfides or benzothiophenes, are rather stable under hydrothermal conditions, with or without additives [150]. For instance, diphenylsulfide showed 0 and 9% conversion after 60 min at 460 • C in pure water and 15 wt.% Na 2 CO 3 water solution, while benzo[b]thiophene showed 0 and 1.6% conversion after 60 min at 460 • C in pure water and 15 wt.% HCO 2 Na water solution.…”

Section: Organosulfur Compoundsmentioning

confidence: 99%

Sub- and Supercritical Water Liquefaction of Kraft Lignin and Black Liquor Derived Lignin

et al. 2020

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To mitigate global warming, humankind has been forced to develop new efficient energy solutions based on renewable energy sources. Hydrothermal liquefaction (HTL) is a promising technology that can efficiently produce bio-oil from several biomass sources. The HTL process uses sub- or supercritical water for producing bio-oil, water-soluble organics, gaseous products and char. Black liquor mainly contains cooking chemicals (mainly alkali salts) lignin and the hemicellulose parts of the wood chips used for cellulose digestion. This review explores the effects of different process parameters, solvents and catalysts for the HTL of black liquor or black liquor-derived lignin. Using short residence times under near- or supercritical water conditions may improve both the quality and the quantity of the bio-oil yield. The quality and yield of bio-oil can be further improved by using solvents (e.g., phenol) and catalysts (e.g., alkali salts, zirconia). However, the solubility of alkali salts present in black liquor can lead to clogging problem in the HTL reactor and process tubes when approaching supercritical water conditions.

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“…Previous research suggests that the desulfurization and cracking of heavy oils in SCW has the potential to be a sustainable, commercial-scale process. [24][25][26][27][28][29][30] However, large-scale commercialization of processes using SCW has been impeded in part by a lack of mechanistic details and kinetic information of the upgrading and sulfur removal chemistry. As a step towards filling that gap, we undertook a study to elucidate the mechanisms and rates of hexyl sulfide decomposition with or without water present.…”

Section: Introductionmentioning

confidence: 99%