### Abstract

On the base of quantum-chemical calculations (DFT, B3LYP, 3-21G), thermodynamic parameters of the reactions of sulfur-containing compounds in the process of diesel fractions hydrodesulphuri-zation were estimated. Based on the thermodynamic analysis, the probability of reactions occur-rence was determined, the reaction scheme for hydrocarbon transformations was proposed, which can be used in mathematical modeling. It was shown that thermodynamic probability of the hydro-genolysis reactions increases in the series: dibenzothiophenes (ΔGr=-33.27 kJ/mol), benzothiophenes (ΔGr=-71.36 kJ/mol), thiophenes (ΔGr=-137.20 kJ/mol) and sulfides (ΔGr=-142.64 kJ/mol). It was found that hydrogenolysis of sulfides, thiophenes, and benzothiophenes proceeds irreversibly, and hydrogenolysis of dibenzothiophenes proceeds reversibly through the stage of aromatic hydrocar-bons formation, followed by their hydrogenation to cycloparaffins. It was shown that in the series of thiophenes, benzothiophenes, and dibenzothiophenes, the thermodynamic probability of the hydrogenolysis reactions decreases with increasing molecular weight. The values of the enthalpies of the sulfur-containing compounds reactions are calculated, and all reactions were shown to be exothermic. The greatest thermal effect is is observed for reactions of dibenzothiophenes hydrogenation to bicyclic paraffins (ΔHr=-514.89 kJ/mol), reactions of ben-zothiophenes to cycloparaffins (ΔHr=-398.71 kJ/mol), reactions of thiophenes to paraffins (ΔHr=-317.85 kJ/mol.

Original language | English |
---|---|

Pages (from-to) | 74-80 |

Number of pages | 7 |

Journal | Petroleum and Coal |

Volume | 61 |

Issue number | 1 |

Publication status | Published - 1 Jan 2019 |

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### Keywords

- Diesel fractions
- Hydrodesulphurization
- Quantum-chemical calculations
- Sulphur-containing compounds
- Thermodynamic analysis

### ASJC Scopus subject areas

- Energy(all)

### Cite this

*Petroleum and Coal*,

*61*(1), 74-80.

**Thermodynamic analysis of the reactions of sulphur-containing compounds in the process of diesel fractions hydrodesulphurization on the base of quantum-chemical calculations.** / Frantsina, Evgeniya; Krivtsova, Nadezhda; Belinskaya, Nataliya; Kotkova, Elena.

Research output: Contribution to journal › Article

*Petroleum and Coal*, vol. 61, no. 1, pp. 74-80.

}

TY - JOUR

T1 - Thermodynamic analysis of the reactions of sulphur-containing compounds in the process of diesel fractions hydrodesulphurization on the base of quantum-chemical calculations

AU - Frantsina, Evgeniya

AU - Krivtsova, Nadezhda

AU - Belinskaya, Nataliya

AU - Kotkova, Elena

PY - 2019/1/1

Y1 - 2019/1/1

N2 - On the base of quantum-chemical calculations (DFT, B3LYP, 3-21G), thermodynamic parameters of the reactions of sulfur-containing compounds in the process of diesel fractions hydrodesulphuri-zation were estimated. Based on the thermodynamic analysis, the probability of reactions occur-rence was determined, the reaction scheme for hydrocarbon transformations was proposed, which can be used in mathematical modeling. It was shown that thermodynamic probability of the hydro-genolysis reactions increases in the series: dibenzothiophenes (ΔGr=-33.27 kJ/mol), benzothiophenes (ΔGr=-71.36 kJ/mol), thiophenes (ΔGr=-137.20 kJ/mol) and sulfides (ΔGr=-142.64 kJ/mol). It was found that hydrogenolysis of sulfides, thiophenes, and benzothiophenes proceeds irreversibly, and hydrogenolysis of dibenzothiophenes proceeds reversibly through the stage of aromatic hydrocar-bons formation, followed by their hydrogenation to cycloparaffins. It was shown that in the series of thiophenes, benzothiophenes, and dibenzothiophenes, the thermodynamic probability of the hydrogenolysis reactions decreases with increasing molecular weight. The values of the enthalpies of the sulfur-containing compounds reactions are calculated, and all reactions were shown to be exothermic. The greatest thermal effect is is observed for reactions of dibenzothiophenes hydrogenation to bicyclic paraffins (ΔHr=-514.89 kJ/mol), reactions of ben-zothiophenes to cycloparaffins (ΔHr=-398.71 kJ/mol), reactions of thiophenes to paraffins (ΔHr=-317.85 kJ/mol.

AB - On the base of quantum-chemical calculations (DFT, B3LYP, 3-21G), thermodynamic parameters of the reactions of sulfur-containing compounds in the process of diesel fractions hydrodesulphuri-zation were estimated. Based on the thermodynamic analysis, the probability of reactions occur-rence was determined, the reaction scheme for hydrocarbon transformations was proposed, which can be used in mathematical modeling. It was shown that thermodynamic probability of the hydro-genolysis reactions increases in the series: dibenzothiophenes (ΔGr=-33.27 kJ/mol), benzothiophenes (ΔGr=-71.36 kJ/mol), thiophenes (ΔGr=-137.20 kJ/mol) and sulfides (ΔGr=-142.64 kJ/mol). It was found that hydrogenolysis of sulfides, thiophenes, and benzothiophenes proceeds irreversibly, and hydrogenolysis of dibenzothiophenes proceeds reversibly through the stage of aromatic hydrocar-bons formation, followed by their hydrogenation to cycloparaffins. It was shown that in the series of thiophenes, benzothiophenes, and dibenzothiophenes, the thermodynamic probability of the hydrogenolysis reactions decreases with increasing molecular weight. The values of the enthalpies of the sulfur-containing compounds reactions are calculated, and all reactions were shown to be exothermic. The greatest thermal effect is is observed for reactions of dibenzothiophenes hydrogenation to bicyclic paraffins (ΔHr=-514.89 kJ/mol), reactions of ben-zothiophenes to cycloparaffins (ΔHr=-398.71 kJ/mol), reactions of thiophenes to paraffins (ΔHr=-317.85 kJ/mol.

KW - Diesel fractions

KW - Hydrodesulphurization

KW - Quantum-chemical calculations

KW - Sulphur-containing compounds

KW - Thermodynamic analysis

UR - http://www.scopus.com/inward/record.url?scp=85063598631&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85063598631&partnerID=8YFLogxK

M3 - Article

VL - 61

SP - 74

EP - 80

JO - Petroleum and Coal

JF - Petroleum and Coal

SN - 1337-7027

IS - 1

ER -