Hydrogenation kinetic of alkenes and aromatics over NiMo hydrotreatment catalysts

doi:10.1016/j.cjche.2024.10.036

Chinese Journal of Chemical Engineering ›› 2025, Vol. 79 ›› Issue (3): 11-22.DOI: 10.1016/j.cjche.2024.10.036

Hydrogenation kinetic of alkenes and aromatics over NiMo hydrotreatment catalysts

Wenbo Li¹, Xinyao Fu¹, Weiming Zhai², Xingyang Huang¹, Wenbin Chen², Chen Zhang¹, Wei Zhang¹, Cuiqing Li¹, Yong Luo³, Feng Liu², Mingfeng Li²

1. Beijing Key Laboratory of Enze Biomass Fine Chemicals, School of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China;
2. SINOPEC Research Institute of Petroleum Processing Co., LTD, Beijing 100083, China;
3. State Key Laboratory of Organic-Inorganic Composites, Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029, China

Received:2024-05-26 Revised:2024-10-10 Accepted:2024-10-11 Online:2025-01-18 Published:2025-03-28
Supported by:
The authors would like to acknowledge funding support provided by the National Key Research & Development of China (2022YFA1504401), the Project of Cultivation for Young Top-notch Talents of Beijing Municipal Institutions (BPHR202203094) and Young Elite Scientists Sponsorship Program by the BAST (BYESS2023256).

Hydrogenation kinetic of alkenes and aromatics over NiMo hydrotreatment catalysts

Wenbo Li¹, Xinyao Fu¹, Weiming Zhai², Xingyang Huang¹, Wenbin Chen², Chen Zhang¹, Wei Zhang¹, Cuiqing Li¹, Yong Luo³, Feng Liu², Mingfeng Li²

1. Beijing Key Laboratory of Enze Biomass Fine Chemicals, School of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China;
2. SINOPEC Research Institute of Petroleum Processing Co., LTD, Beijing 100083, China;
3. State Key Laboratory of Organic-Inorganic Composites, Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029, China

通讯作者: Chen Zhang,E-mail:zhangc@bipt.edu.cn;Cuiqing Li,E-mail:licuiqing@bipt.edu.cn;Mingfeng Li,E-mail:limf.ripp@sinopec.com
基金资助:
The authors would like to acknowledge funding support provided by the National Key Research & Development of China (2022YFA1504401), the Project of Cultivation for Young Top-notch Talents of Beijing Municipal Institutions (BPHR202203094) and Young Elite Scientists Sponsorship Program by the BAST (BYESS2023256).

Abstract

Abstract: Hydrotreatment is a critical process in the petrochemical industry to produce gasoline or diesel. Proper kinetic models and accurate kinetic parameters of hydrotreatment reactions are important for the industrial reactor design and scale-up research. In this work, hydrogenation kinetics of alkene and aromatic model compounds were studied thoroughly to provide deep understanding on alkene and aromatic hydrogenation behaviors in gasoline and diesel hydrotreating. Commercial NiMo hydrotreatment catalysts were used to obtain experimental data of hydrogenation reactions. Cyclohexene, 1-octene, naphthalene and phenanthrene were used as model compounds of alkenes and aromatics. Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic models for hydrotreatment reactions were established. In addition, phase equilibrium calculations were combined with kinetic study, and it is discovered that using calculated liquid phase compositions as kinetic model input could greatly enhance the accuracy of kinetic models and the quality of kinetic parameters, leading to higher accordance with experimental results. Using kinetic models and phase equilibrium analysis, the effect of reaction conditions (temperature, pressure, and H₂/oil ratio) on reaction rates were also predicted and clarified. The importance of phase equilibrium in kinetic analysis for hydrotreating reactions was demonstrated in this study, which provides an effective approach for future hydrotreatment reactor design and catalyst optimization.

Key words: Kinetic, Hydrogenation, Phase equilibria, H₂/oil ratio

摘要： Hydrotreatment is a critical process in the petrochemical industry to produce gasoline or diesel. Proper kinetic models and accurate kinetic parameters of hydrotreatment reactions are important for the industrial reactor design and scale-up research. In this work, hydrogenation kinetics of alkene and aromatic model compounds were studied thoroughly to provide deep understanding on alkene and aromatic hydrogenation behaviors in gasoline and diesel hydrotreating. Commercial NiMo hydrotreatment catalysts were used to obtain experimental data of hydrogenation reactions. Cyclohexene, 1-octene, naphthalene and phenanthrene were used as model compounds of alkenes and aromatics. Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic models for hydrotreatment reactions were established. In addition, phase equilibrium calculations were combined with kinetic study, and it is discovered that using calculated liquid phase compositions as kinetic model input could greatly enhance the accuracy of kinetic models and the quality of kinetic parameters, leading to higher accordance with experimental results. Using kinetic models and phase equilibrium analysis, the effect of reaction conditions (temperature, pressure, and H₂/oil ratio) on reaction rates were also predicted and clarified. The importance of phase equilibrium in kinetic analysis for hydrotreating reactions was demonstrated in this study, which provides an effective approach for future hydrotreatment reactor design and catalyst optimization.

关键词: Kinetic, Hydrogenation, Phase equilibria, H₂/oil ratio

Wenbo Li, Xinyao Fu, Weiming Zhai, Xingyang Huang, Wenbin Chen, Chen Zhang, Wei Zhang, Cuiqing Li, Yong Luo, Feng Liu, Mingfeng Li. Hydrogenation kinetic of alkenes and aromatics over NiMo hydrotreatment catalysts[J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 11-22.

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Hydrogenation kinetic of alkenes and aromatics over NiMo hydrotreatment catalysts

Hydrogenation kinetic of alkenes and aromatics over NiMo hydrotreatment catalysts

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