Thermodynamic analysis of the reactions of sulphur containing compounds in the process of diesel fractions hydrodesulphurization on the base of quantum-chemical calculations
| Parent link: | Petroleum and Coal Vol. 61, iss. 1.— 2019.— [P. 74-80] |
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| 其他作者: | , , , |
| 总结: | Title screen On the base of quantum-chemical calculations (DFT, B3LYP, 3-21G), thermodynamic parametersof the reactions of sulfur-containing compounds in the process of diesel fractions hydrodesulphurization were estimated. Based on the thermodynamic analysis, the probability of reactions occurrence was determined, the reaction scheme for hydrocarbon transformations was proposed, whichcan be used in mathematical modeling. It was shown that thermodynamic probability of the hydrogenolysis reactions increases in the series: dibenzothiophenes (?Gr=-33.27 kJ/mol), benzothiophenes(?Gr=-71.36 kJ/mol), thiophenes (?Gr=-137.20 kJ/mol) and sulfides (?Gr=-142.64 kJ/mol). It wasfound that hydrogenolysis of sulfides, thiophenes, and benzothiophenes proceeds irreversibly, andhydrogenolysis of dibenzothiophenes proceeds reversibly through the stage of aromatic hydrocarbons formation, followed by their hydrogenation to cycloparaffins. It was shown that in the seriesof thiophenes, benzothiophenes, and dibenzothiophenes, the thermodynamic probability of thehydrogenolysis reactions decreases with increasing molecular weight.The values of the enthalpies of the sulfur-containing compounds reactions are calculated, and allreactions were shown to be exothermic. The greatest thermal effect is is observed for reactions ofdibenzothiophenes hydrogenation to bicyclic paraffins (?Hr=-514.89 kJ/mol), reactions of benzothiophenes to cycloparaffins (?Hr=-398.71 kJ/mol), reactions of thiophenes to paraffins (?Hr=-317.85 kJ/mol. |
| 语言: | 英语 |
| 出版: |
2019
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| 主题: | |
| 在线阅读: | https://www.vurup.sk/wp-content/uploads/2019/01/PC_x_2018_Frantsina-129.pdf |
| 格式: | 电子 本书章节 |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=660496 |
| 总结: | Title screen On the base of quantum-chemical calculations (DFT, B3LYP, 3-21G), thermodynamic parametersof the reactions of sulfur-containing compounds in the process of diesel fractions hydrodesulphurization were estimated. Based on the thermodynamic analysis, the probability of reactions occurrence was determined, the reaction scheme for hydrocarbon transformations was proposed, whichcan be used in mathematical modeling. It was shown that thermodynamic probability of the hydrogenolysis reactions increases in the series: dibenzothiophenes (?Gr=-33.27 kJ/mol), benzothiophenes(?Gr=-71.36 kJ/mol), thiophenes (?Gr=-137.20 kJ/mol) and sulfides (?Gr=-142.64 kJ/mol). It wasfound that hydrogenolysis of sulfides, thiophenes, and benzothiophenes proceeds irreversibly, andhydrogenolysis of dibenzothiophenes proceeds reversibly through the stage of aromatic hydrocarbons formation, followed by their hydrogenation to cycloparaffins. It was shown that in the seriesof thiophenes, benzothiophenes, and dibenzothiophenes, the thermodynamic probability of thehydrogenolysis reactions decreases with increasing molecular weight.The values of the enthalpies of the sulfur-containing compounds reactions are calculated, and allreactions were shown to be exothermic. The greatest thermal effect is is observed for reactions ofdibenzothiophenes hydrogenation to bicyclic paraffins (?Hr=-514.89 kJ/mol), reactions of benzothiophenes to cycloparaffins (?Hr=-398.71 kJ/mol), reactions of thiophenes to paraffins (?Hr=-317.85 kJ/mol. |
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