KFU. Card publication. Theoretical Substantiation Based on DFT Calculations and Experimental Confirmation of Soft Conditions for Catalytic Aquathermolysis of Heavy Crude Oil

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THEORETICAL SUBSTANTIATION BASED ON DFT CALCULATIONS AND EXPERIMENTAL CONFIRMATION OF SOFT CONDITIONS FOR CATALYTIC AQUATHERMOLYSIS OF HEAVY CRUDE OIL

Form of presentation

Articles in international journals and collections

Year of publication

2025

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Authors, employees of KFU

Varfolomeev Mikhail Alekseevich, author

Kadkin Oleg Nikolaevich, author

Bibliographic description in the original language

Neklyudov V.V, Mikhailova A.N, Al-Muntaser A.A, Zhou Xiaodong, Varfolomeev M.A, Khafizov N.R, Kadkin O.N., and Jorge Ancheyta / Theoretical Substantiation Based on DFT Calculations and Experimental Confirmation of Soft Conditions for Catalytic Aquathermolysis of Heavy Crude Oil // Industrial and Engineering Chemistry Research. - 2025. - Vol. 64, Is.2 - 11879–11887 .

Annotation

Catalytic aquathermolysis of carbon−heteroatom bonds in maltene fractions of heavy crude oil is theoretically studied by using DFT calculation techniques with the use of model compounds that mimic carbon−heteroatom bonds. The calculations show that the hydrolysis of carbon−heteroatom bonds cannot be thermodynamically achieved in the temperature range of up to 700 K. The heterolytic cleavage of bonds with the formation of ionic intermediates is the most preferable route. The noticeably lower kinetic barriers of the ionic mechanism compared with the homolytic cleavage reactions with the formation of free radicals make it possible to use soft aquathermolysis conditions in the presence of catalysts, thereby limiting polymerization and oligomerization reactions. The theoretical calculation results agree with experimental data on the catalytic aquathermolysis of dibenzyl sulfide at 200, 300, and 350 ?C. The gas chromatography−mass spectrometry analysis shows that minimum coke formation can be achieved at 300 ?C. An increase in the temperature to 350 ?C leads to efficient sulfur removal in the form of gaseous H2S (7.139 wt %), although coke formation substantially increases (to 17.09 wt %). The combination of DFT calculations and experimental validation suggests that optimizing the catalyst composition and reaction temperature (≤300 ?C) can maximize the desulfurization rate while minimizing undesired side reactions.

Keywords

heavy oil, in situ upgrading, DFT, thermodynamics, kinetics, aquathermolysis

The name of the journal

Industrial and Engineering Chemistry Research

URL

https://www.scopus.com/inward/record.uri?eid=2-s2.0-105007607368&doi=10.1021%2facs.iecr.5c01182&partnerID=40&md5=918123db68e0207c8fe28433f5df6e45

Please use this ID to quote from or refer to the card

https://repository.kpfu.ru/eng/?p_id=315437&p_lang=2

Full metadata record

Field DC	Value	Language
dc.contributor.author	Varfolomeev Mikhail Alekseevich	ru_RU
dc.contributor.author	Kadkin Oleg Nikolaevich	ru_RU
dc.date.accessioned	2025-01-01T00:00:00Z	ru_RU
dc.date.available	2025-01-01T00:00:00Z	ru_RU
dc.date.issued	2025	ru_RU
dc.identifier.citation	Neklyudov V.V, Mikhailova A.N, Al-Muntaser A.A, Zhou Xiaodong, Varfolomeev M.A, Khafizov N.R, Kadkin O.N., and Jorge Ancheyta / Theoretical Substantiation Based on DFT Calculations and Experimental Confirmation of Soft Conditions for Catalytic Aquathermolysis of Heavy Crude Oil // Industrial and Engineering Chemistry Research. - 2025. - Vol. 64, Is.2 - 11879–11887 .	ru_RU
dc.identifier.uri	https://repository.kpfu.ru/eng/?p_id=315437&p_lang=2	ru_RU
dc.description.abstract	Industrial and Engineering Chemistry Research	ru_RU
dc.description.abstract	Catalytic aquathermolysis of carbon−heteroatom bonds in maltene fractions of heavy crude oil is theoretically studied by using DFT calculation techniques with the use of model compounds that mimic carbon−heteroatom bonds. The calculations show that the hydrolysis of carbon−heteroatom bonds cannot be thermodynamically achieved in the temperature range of up to 700 K. The heterolytic cleavage of bonds with the formation of ionic intermediates is the most preferable route. The noticeably lower kinetic barriers of the ionic mechanism compared with the homolytic cleavage reactions with the formation of free radicals make it possible to use soft aquathermolysis conditions in the presence of catalysts, thereby limiting polymerization and oligomerization reactions. The theoretical calculation results agree with experimental data on the catalytic aquathermolysis of dibenzyl sulfide at 200, 300, and 350 ?C. The gas chromatography−mass spectrometry analysis shows that minimum coke formation can be achieved at 300 ?C. An increase in the temperature to 350 ?C leads to efficient sulfur removal in the form of gaseous H2S (7.139 wt %), although coke formation substantially increases (to 17.09 wt %). The combination of DFT calculations and experimental validation suggests that optimizing the catalyst composition and reaction temperature (≤300 ?C) can maximize the desulfurization rate while minimizing undesired side reactions.	ru_RU
dc.language.iso	ru	ru_RU
dc.subject	heavy oil	ru_RU
dc.subject	in situ upgrading	ru_RU
dc.subject	DFT	ru_RU
dc.subject	thermodynamics	ru_RU
dc.subject	kinetics	ru_RU
dc.subject	aquathermolysis	ru_RU
dc.title	Theoretical Substantiation Based on DFT Calculations and Experimental Confirmation of Soft Conditions for Catalytic Aquathermolysis of Heavy Crude Oil	ru_RU
dc.type	Articles in international journals and collections	ru_RU