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A Thermochemical Ladder to Biosynthetic Fuels: From Quantum Chemistry Downstairs to the Liquid-Phase Energetics of Eugenol Hydrodeoxygenation as a Model for Lignin Upgrading Научная публикация

Журнал Chemical Engineering Journal
ISSN: 1385-8947 , E-ISSN: 1873-3212
Вых. Данные Год: 2025, Том: 521, Номер статьи : 166609, Страниц : 19 DOI: 10.1016/j.cej.2025.166609
Ключевые слова Lignin; Hydrodeoxygenation; Enthalpies of phase transitions; Halloysite; Enthalpy of formation; Quantum-chemical calculations; Vapor pressure
Авторы Verevkin Sergey P. 1,2 , Zasypalov Gleb O. 3 , Klimovsky Vladimir A. 3 , Pimerzin Aleksey A. 3,4 , Vutolkina Anna V. 5 , Samarov Artemiy A. 6 , Vostrikov Sergey V. 2 , Metalnikova Vera M. 7 , Siewert Riko 1 , Müller Karsten 1 , Glotov Aleksandr P. 3
Организации
1 Institute of Technical Thermodynamics, University of Rostock, 18059 Rostock, Germany
2 Engineering and Technology Department, Samara State Technical University, 443100 Samara, Russian Federation
3 Gubkin Russian State University of Oil and Gas, 119991, Moscow 65, Russian Federation
4 Gazpromneft Industrial Innovations LLC, 197350 Saint Petersburg, Russian Federation
5 Lomonosov Moscow State University, 119991 Moscow, Russian Federation
6 Saint Petersburg State University, 198504 Saint Petersburg, Russian Federation
7 Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk, Russian Federation

Реферат: The valorisation of lignin is one of the current challenges for science and industry. Studies on eugenol as a model compound for hydrodeoxygenation considerably facilitate the understanding of the general trends in this complex reaction cascade. The thermochemical properties of the starting material eugenol, the end products (alkylcyclopentanes and alkylcyclohexanes) and the intermediate products of the network, which comprises 18 possible reactions, were evaluated. According to the quantitative thermodynamic analysis, none of the 18 reactions are subject to significant thermodynamic limitations. However, the final distribution of reaction products is determined by acidity, textural properties and active phase valence state at constant experimental conditions. Nevertheless, a quantitative understanding of thermodynamics is indispensable to evaluate the magnitude of the equilibrium constant at a particular temperature and to adjust the type and amount of catalyst, time and temperature and to obtain sufficient yields of biosynthetic fuel compounds. The thermodynamic investigation findings were corroborated through the empirical data. The highest selectivity to 2-methoxy-4-propylphenol (side chain hydrogenation) of 79 % over Ru/HNT with low acidity was observed. In contrast, for the Ru/HNT-t catalyst with enhanced Brønsted and Lewis acidity the major products were propylcyclohexane (42 %, complete hydrodeoxygenation) and 4-propylcyclohexanol (20 %, demethoxylation‑hydrogenation) at 180 °C. An increase in the temperature to 210 °C leads to the quantitative conversion of eugenol and an increase in propylcyclohexane selectivity for both catalysts (Ru/HNT – 38.2 %, Ru/HNT-t – 77.9 %). Other parallel routes are consistent with thermodynamic analysis performed in this work.
Библиографическая ссылка: Verevkin S.P. , Zasypalov G.O. , Klimovsky V.A. , Pimerzin A.A. , Vutolkina A.V. , Samarov A.A. , Vostrikov S.V. , Metalnikova V.M. , Siewert R. , Müller K. , Glotov A.P.
A Thermochemical Ladder to Biosynthetic Fuels: From Quantum Chemistry Downstairs to the Liquid-Phase Energetics of Eugenol Hydrodeoxygenation as a Model for Lignin Upgrading
Chemical Engineering Journal. 2025. V.521. 166609 :1-19. DOI: 10.1016/j.cej.2025.166609 WOS Scopus OpenAlex
Даты:
Поступила в редакцию: 31 мар. 2025 г.
Принята к публикации: 28 июл. 2025 г.
Опубликована online: 12 авг. 2025 г.
Опубликована в печати: 1 окт. 2025 г.
Идентификаторы БД:
Web of science: WOS:001550822100003
Scopus: 2-s2.0-105012819642
OpenAlex: W4413105583
Цитирование в БД: Пока нет цитирований
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