Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds

This paper selects two typical compounds containing organic sulfur as model compounds. Then, by analyzing the chromatograms of gaseous low-temp oxidation products and GC/MS of the extractable matter of the oxidation residue, we summarizing the mechanism of low-temp sulfur model compound oxidation. T...

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Main Authors: Lanjun Zhang, Zenghua Li, Jinhu Li, Yinbo Zhou, Yongliang Yang, Yibo Tang
Format: Article
Language:English
Published: MDPI AG 2015-12-01
Series:Molecules
Subjects:
Online Access:http://www.mdpi.com/1420-3049/20/12/19843
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author Lanjun Zhang
Zenghua Li
Jinhu Li
Yinbo Zhou
Yongliang Yang
Yibo Tang
author_facet Lanjun Zhang
Zenghua Li
Jinhu Li
Yinbo Zhou
Yongliang Yang
Yibo Tang
author_sort Lanjun Zhang
collection DOAJ
description This paper selects two typical compounds containing organic sulfur as model compounds. Then, by analyzing the chromatograms of gaseous low-temp oxidation products and GC/MS of the extractable matter of the oxidation residue, we summarizing the mechanism of low-temp sulfur model compound oxidation. The results show that between 30 °C to 80 °C, the interaction between diphenyl sulfide and oxygen is mainly one of physical adsorption. After 80 °C, chemical adsorption and chemical reactions begin. The main reaction mechanism in the low-temp oxidation of the model compound diphenyl sulfide is diphenyl sulfide generates diphenyl sulfoxide, and then this sulfoxide is further oxidized to diphenyl sulphone. A small amount of free radicals is generated in the process. The model compound cysteine behaves differently from diphenyl sulfide. The main reaction low-temp oxidation mechanism involves the thiol being oxidized into a disulphide and finally evolving to sulfonic acid, along with SO2 being released at 130 °C and also a small amount of free radicals. We also conducted an experiment on coal from Xingcheng using X-ray photoelectron spectroscopy (XPS). The results show that the major forms of organic sulfur in the original coal sample are thiophene and sulfone. Therefore, it can be inferred that there is none or little mercaptan and thiophenol in the original coal. After low-temp oxidation, the form of organic sulfur changes. The sulfide sulfur is oxidized to the sulfoxide, and then the sulfoxide is further oxidized to a sulfone, and these steps can be easily carried out under experimental conditions. What’s more, the results illustrate that oxidation promotes sulfur element enrichment on the surface of coal.
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spelling doaj.art-b4f004e3caf541d3be53793cb50cf4492022-12-22T02:32:50ZengMDPI AGMolecules1420-30492015-12-012012222412225610.3390/molecules201219843molecules201219843Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model CompoundsLanjun Zhang0Zenghua Li1Jinhu Li2Yinbo Zhou3Yongliang Yang4Yibo Tang5Key Laboratory of Coal Methane and Fire Control, Ministry of Education, China University of Mining and Technology, Xuzhou 221008, ChinaKey Laboratory of Coal Methane and Fire Control, Ministry of Education, China University of Mining and Technology, Xuzhou 221008, ChinaKey Laboratory of Coal Methane and Fire Control, Ministry of Education, China University of Mining and Technology, Xuzhou 221008, ChinaKey Laboratory of Coal Methane and Fire Control, Ministry of Education, China University of Mining and Technology, Xuzhou 221008, ChinaKey Laboratory of Coal Methane and Fire Control, Ministry of Education, China University of Mining and Technology, Xuzhou 221008, ChinaCollege of Mining Technology, Taiyuan University of Technology, Taiyuan 030024, ChinaThis paper selects two typical compounds containing organic sulfur as model compounds. Then, by analyzing the chromatograms of gaseous low-temp oxidation products and GC/MS of the extractable matter of the oxidation residue, we summarizing the mechanism of low-temp sulfur model compound oxidation. The results show that between 30 °C to 80 °C, the interaction between diphenyl sulfide and oxygen is mainly one of physical adsorption. After 80 °C, chemical adsorption and chemical reactions begin. The main reaction mechanism in the low-temp oxidation of the model compound diphenyl sulfide is diphenyl sulfide generates diphenyl sulfoxide, and then this sulfoxide is further oxidized to diphenyl sulphone. A small amount of free radicals is generated in the process. The model compound cysteine behaves differently from diphenyl sulfide. The main reaction low-temp oxidation mechanism involves the thiol being oxidized into a disulphide and finally evolving to sulfonic acid, along with SO2 being released at 130 °C and also a small amount of free radicals. We also conducted an experiment on coal from Xingcheng using X-ray photoelectron spectroscopy (XPS). The results show that the major forms of organic sulfur in the original coal sample are thiophene and sulfone. Therefore, it can be inferred that there is none or little mercaptan and thiophenol in the original coal. After low-temp oxidation, the form of organic sulfur changes. The sulfide sulfur is oxidized to the sulfoxide, and then the sulfoxide is further oxidized to a sulfone, and these steps can be easily carried out under experimental conditions. What’s more, the results illustrate that oxidation promotes sulfur element enrichment on the surface of coal.http://www.mdpi.com/1420-3049/20/12/19843coalorganic sulfurmodel compoundslow-temp oxidationXPS
spellingShingle Lanjun Zhang
Zenghua Li
Jinhu Li
Yinbo Zhou
Yongliang Yang
Yibo Tang
Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds
Molecules
coal
organic sulfur
model compounds
low-temp oxidation
XPS
title Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds
title_full Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds
title_fullStr Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds
title_full_unstemmed Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds
title_short Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds
title_sort studies on the low temp oxidation of coal containing organic sulfur and the corresponding model compounds
topic coal
organic sulfur
model compounds
low-temp oxidation
XPS
url http://www.mdpi.com/1420-3049/20/12/19843
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AT jinhuli studiesonthelowtempoxidationofcoalcontainingorganicsulfurandthecorrespondingmodelcompounds
AT yinbozhou studiesonthelowtempoxidationofcoalcontainingorganicsulfurandthecorrespondingmodelcompounds
AT yongliangyang studiesonthelowtempoxidationofcoalcontainingorganicsulfurandthecorrespondingmodelcompounds
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