SCI和EI收录∣中国化工学会会刊

中国化学工程学报 ›› 2024, Vol. 67 ›› Issue (3): 166-173.DOI: 10.1016/j.cjche.2023.11.023

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In situ modification of heavy oil catalyzed by nanosized metal-organic framework at mild temperature and its mechanism

Li Wang1, Ji-Xiang Guo1, Rui-Ying Xiong1, Chen-Hao Gao1, Xiao-Jun Zhang1, Dan Luo2   

  1. 1 The Unconventional Oil and Gas Institute, China University of Petroleum-Beijing, Beijing 102200, China;
    2 Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences, Beijing 101400, China
  • 收稿日期:2023-05-26 修回日期:2023-11-24 出版日期:2024-03-28 发布日期:2024-06-01
  • 通讯作者: Ji-Xiang Guo,E-mail address:guojx002@163.com.
  • 基金资助:
    This study was financially supported by the National Natural Science Foundation of China (52174047) and Sinopec Project (P21063-3).

In situ modification of heavy oil catalyzed by nanosized metal-organic framework at mild temperature and its mechanism

Li Wang1, Ji-Xiang Guo1, Rui-Ying Xiong1, Chen-Hao Gao1, Xiao-Jun Zhang1, Dan Luo2   

  1. 1 The Unconventional Oil and Gas Institute, China University of Petroleum-Beijing, Beijing 102200, China;
    2 Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences, Beijing 101400, China
  • Received:2023-05-26 Revised:2023-11-24 Online:2024-03-28 Published:2024-06-01
  • Contact: Ji-Xiang Guo,E-mail address:guojx002@163.com.
  • Supported by:
    This study was financially supported by the National Natural Science Foundation of China (52174047) and Sinopec Project (P21063-3).

摘要: Two catalysts, nano-sized cobalt-metal-organic framework (Co-MOF) and nickel (Ni)-MOF, were successfully prepared by the modification method. Tetralin (C10H12) was used as the hydrogen donor for the catalytic cracking and hydrogenation modification study of the dehydrated crude oil from the Shengli Oilfield. The optimal reaction conditions were determined through orthogonal experiments, and the components of the crude oil and modified oil samples were analyzed. The results revealed that the nanoMOF catalysts were successfully prepared and exhibited high catalytic activity. They could catalyze the cracking of large molecules in heavy oil at mild temperatures (<300 ℃), leading to the decomposition of the hydrogen donor. When the mass fraction of the catalyst was≥0.2%, the mass fraction of the hydrogen donor was 1%, and the reaction temperature was 280 ℃, the Ni-MOF showed the best catalytic viscosity reduction effect. It could reduce the viscosity of heavy oil at 50 ℃ from 15761.9 mPa·s to 1266.2 mPa·s, with a viscosity reduction rate of 91.97%. The modification effect of Co-MOF was the next best, which could reduce the viscosity of heavy oil to 2500.1 mPa·s with a viscosity reduction rate of 84.14%. Molecular dynamics simulations revealed a strong interaction force between the MOF surface and asphaltene molecules. In the process of heavy-oil catalytic hydrogenation, the nano-MOF catalyst exhibited high catalytic activity. On the one hand, the empty d orbitals outside the metal atoms in the catalyst could polarize the carbon atoms in the organic matter, accelerating the breaking of long chains. On the other hand, the metal atoms in the catalyst could bond with the carbon σ bonds, breaking the carbon ecarbon bonds. This disrupted the structure of the recombined components in the crude oil, irreversibly reducing the viscosity of the heavy oil and improving its fluidity.

关键词: Nano-sized MOF, Petroleum, Viscosity reduction, Catalyst, Nanomaterials

Abstract: Two catalysts, nano-sized cobalt-metal-organic framework (Co-MOF) and nickel (Ni)-MOF, were successfully prepared by the modification method. Tetralin (C10H12) was used as the hydrogen donor for the catalytic cracking and hydrogenation modification study of the dehydrated crude oil from the Shengli Oilfield. The optimal reaction conditions were determined through orthogonal experiments, and the components of the crude oil and modified oil samples were analyzed. The results revealed that the nanoMOF catalysts were successfully prepared and exhibited high catalytic activity. They could catalyze the cracking of large molecules in heavy oil at mild temperatures (<300 ℃), leading to the decomposition of the hydrogen donor. When the mass fraction of the catalyst was≥0.2%, the mass fraction of the hydrogen donor was 1%, and the reaction temperature was 280 ℃, the Ni-MOF showed the best catalytic viscosity reduction effect. It could reduce the viscosity of heavy oil at 50 ℃ from 15761.9 mPa·s to 1266.2 mPa·s, with a viscosity reduction rate of 91.97%. The modification effect of Co-MOF was the next best, which could reduce the viscosity of heavy oil to 2500.1 mPa·s with a viscosity reduction rate of 84.14%. Molecular dynamics simulations revealed a strong interaction force between the MOF surface and asphaltene molecules. In the process of heavy-oil catalytic hydrogenation, the nano-MOF catalyst exhibited high catalytic activity. On the one hand, the empty d orbitals outside the metal atoms in the catalyst could polarize the carbon atoms in the organic matter, accelerating the breaking of long chains. On the other hand, the metal atoms in the catalyst could bond with the carbon σ bonds, breaking the carbon ecarbon bonds. This disrupted the structure of the recombined components in the crude oil, irreversibly reducing the viscosity of the heavy oil and improving its fluidity.

Key words: Nano-sized MOF, Petroleum, Viscosity reduction, Catalyst, Nanomaterials