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States of Carbon Nanotube Supported Mo-Based HDS Catalysts
作者姓名:Hongyan  Shang  Chenguang  Liu  Yongqiang  Xu  Jieshan  Qiu  Fei  Wei
作者单位:Hongyan Shang,Chenguang Liu,Yongqiang Xu,Jieshan Qiu,Fei Wei Key Laboratory of Catalysis,CNPC,College of Chemistry and Chemical Engineering,University of Petroleum,Dongying 257061,China; Carbon Research Laboratory,Center for Nano Materials and Science. Dalian University of Technology,Dalian 116012,China; Department of Chemical Engineering,Tsinghua University,Being 100084,China
基金项目:Acknowledgements The Nano-Materials Research Center of Tsinghua University is gratefully acknowledged for supplying the carbon nanotubes. The authors also gratefully acknowledge the Chinese National Petroleum Corporation (CNPC) for the financial support of this basic research (Foundation No. 03A5050101).
摘    要:The dispersion of the active phase and loading capacity of the Mo species on carbon nanotube (CNT) was studied by the XRD technique. The reducibility properties of Co-Mo catalysts in the oxide state over CNTs were investigated by TPR, while the sulfided Co-Mo/CNT catalysts were characterized by means of the XRD and LRS techniques. The activity and selectivity with respect to the hydrodesulfurization (HDS) performances on carbon nanotube supported Co-Mo catalysts were evaluated. It was found that the main active molybdenum species in the oxide state MoO3/CNT catalysts were MoO2, but not MoO3, as generally expected. The maximum loading before the formation of the bulk phase was lower than 6% (percent by mass, based on MoO3). TPR studies revealed that the active species in the oxide state Co-Mo/CNT catalysts were reduced more easily at relatively lower temperatures in comparison to those of the Co-Mo/γ-Al2O3 catalysts, indicating that the CNT support promoted or favored the reduction of the active species. The active species of a Co-Mo-0.7/CNT catalyst were more easily reduced than those of the Co-Mo/CNT catalysts with Co/Mo atomic ratios of 0.2, 0.35, and 0.5, respectively, suggesting that the Co/Mo atomic ratio has a great effect on the reducibility of the active species. It was found that the incorporation of cobalt improved the dispersion of the molybdenum species on the support, and a phenomenon of mobilization and re-dispersion had occurred during the sulfurization process, resulting in low valence state Mo3S4 and Co-MoS2.17 active phases. HDS measurements showed that the Co-Mo/CNT catalysts were more active than the Co-Mo/γ-Al2O3 ones for the desulfurization of DBT, and the hydrogenolysis/hydrogenation selectivity of the Co-Mo/CNT catalysts was also much higher than those of the Co-Mo/γ-Al2O3. The Co-Mo/CNT catalyst with a Co/Mo atomic ratio of 0.7 showed the highest activity, whereas the catalyst with a Co/Mo atomic ratio of 0.35 had the highest selectivity.

关 键 词:石油精炼  碳纳米棒  XRD  TPR  HDS  LRS  钼基催化剂  催化活性
收稿时间:07 7 2006 12:00AM
修稿时间:08 4 2006 12:00AM

States of Carbon Nanotube Supported Mo-based HDS Catalysts
Hongyan Shang Chenguang Liu Yongqiang Xu Jieshan Qiu Fei Wei.States of Carbon Nanotube Supported Mo-Based HDS Catalysts[J].Journal of Natural Gas Chemistry,2006,15(3):203-210.
Authors:Hongyan Shang  Chenguang Liu  Yongqiang Xu  Jieshan Qiu  Fei Wei
Institution:1. Key Laboratory of Catalysis, CNPC, College of Chemistry and Chemical Engineering, University of Petroleum,
Abstract:The dispersion of the active phase and loading capacity of the Mo species on carbon nanotube (CNT) was studied by the XRD technique. The reducibility properties of Co-Mo catalysts in the oxide state over CNTs were investigated by TPR, while the sulfided Co-Mo/CNT catalysts were characterized by means of the XRD and LRS techniques. The activity and selectivity with respect to the hydrodesulfurization (HDS) performances on carbon nanotube supported Co-Mo catalysts were evaluated. It was found that the main active molybdenum species in the oxide state MoO3/CNT catalysts were MoO2, but not MoO3, as generally expected. The maximum loading before the formation of the bulk phase was lower than 6% (percent by mass, based on MoO3). TPR studies revealed that the active species in the oxide state Co-Mo/CNT catalysts were reduced more easily at relatively lower temperatures in comparison to those of the Co-Mo/γ-Al2O3 catalysts, indicating that the CNT support promoted or favored the reduction of the active species. The active species of a Co-Mo-0.7/CNT catalyst were more easily reduced than those of the Co-Mo/CNT catalysts with Co/Mo atomic ratios of 0.2, 0.35, and 0.5, respectively, suggesting that the Co/Mo atomic ratio has a great effect on the reducibility of the active species. It was found that the incorporation of cobalt improved the dispersion of the molybdenum species on the support, and a phenomenon of mobilization and re-dispersion had occurred during the sulfurization process, resulting in low valence state Mo3S4 and Co-MoS2.17 active phases. HDS measurements showed that the Co-Mo/CNT catalysts were more active than the Co-Mo/γ-Al2O3 ones for the desulfurization of DBT, and the hydrogenolysis/hydrogenation selectivity of the Co-Mo/CNT catalysts was also much higher than those of the Co-Mo/γ-Al2O3. The Co-Mo/CNT catalyst with a Co/Mo atomic ratio of 0.7 showed the highest activity, whereas the catalyst with a Co/Mo atomic ratio of 0.35 had the highest selectivity.
Keywords:carbon nanotubes  XRD  TPR  HDS  LRS
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