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XPS Characterization of Carbon Nanotube Supported CoMo Hydrodesulfurization Catalysts
作者姓名:商红岩  刘晨光  赵瑞玉  吴明铂  魏飞
作者单位:[1]KeyLaboratoryofCatalysis,ChineseNationalPetroleumCorporation(CNPC),UniversityofPetroleum,Dongying,Shandong257061,China [2]StateKeyLaboratoryofHeavyOilProcessing,UniversityofPetroleum,Dongying,Shandong257061,China [3]DepartmentofChemicalEngineering,TsinghuaUniversity,Beijing100084,China
基金项目:Project supported by the Foundation of Chinese National Petroleum Corporation for a Basic Research (No. 03A5050101).
摘    要:In this paper, the effect of catalytic support and sulfiding method on the chemical state of supported Co-Mo catalysts is studied by XPS. After sulfidation with in-situ method, the majority of molybdenum in CNT supported CoMo catalyst is transferred to a species with a formal chemical state Mo(Ⅳ) in MoS2 phase, and the rest to Mo(Ⅴ) which consists of Mo coordinated both to O and S, such as MoO2S2^2- and MoO3S^2-. In case of CoMo/γ-Al2O3 catalyst sulfided with in-situ method, a fraction of molybdenum is transferred to formal state Mo(Ⅳ) in the form of MoS2, but there is still a mount of unreduced Mo(VI) phase which is difficult to be sulfided. In CoMo/CNT catalyric system sulfided with ex-situ method, Mo(IV) in the form of MoS2 is detected along with a portion of unreduced Mo(VI) phase, suggesting that not all the Mo phases are reduced and sulfided by ex-situ method. As for CoMo/γ-Al2O3, a portion of molybdenum is sulfided to intermediate reduced state Mo(V) which consists of Mo coordinated both to O and S, such as MoO2S2^2- and MoO3S^2-, in addition, there is still a fraction of unreduced Mo(Ⅵ)phase. XPS analyses results suggest that CNT support facilitates the reduction and sulfidation of active species to a large extent, and that alumina support strongly interacts with active species, hereby producing a fraction of phase which resists complete sulfiding. Catalytic measurements of catalysts in the HDS of dibenzothiophene (DBT) show that CoMo/CNT catalysts are of higher HDS activity and selectivity than CoMo/γ-Al2O3 catalyst, which is in good relation with the sulfiding behavior of the corresponding catalyst.

关 键 词:碳纳米管  加氢脱硫  钴-钼催化剂  X射线光电子光谱

XPS Characterization of Carbon Nanotube Supported CoMo Hydrodesulfurization Catalysts
SHANG,Hong-Yan,a LIU,Chen-Guanga ZHAO,Rui-Yua WU,Ming-Bob WEI,Feic a Key Laboratory of Catalysis,Chinese National Petroleum Corporation.XPS Characterization of Carbon Nanotube Supported CoMo Hydrodesulfurization Catalysts[J].Chinese Journal of Chemistry,2004,22(11):1250-1256.
Authors:SHANG  Hong-Yan  a LIU  Chen-Guanga ZHAO  Rui-Yua WU  Ming-Bob WEI  Feic a Key Laboratory of Catalysis  Chinese National Petroleum Corporation
Abstract:In this paper, the effect of catalytic support and sulfiding method on the chemical state of supported Co-Mo catalysts is studied by XPS. After sulfidation with in-situ method, the majority of molybdenum in CNT supported CoMo catalyst is transferred to a species with a formal chemical state Mo(IV) in MoS2 phase, and the rest to Mo(V) which consists of Mo coordinated both to O and S, such as MoO2S2-2 and MoO3S2-. In case of CoMo/-Al2O3 catalyst sulfided with in-situ method, a fraction of molybdenum is transferred to formal state Mo(IV) in the form of MoS2, but there is still a mount of unreduced Mo(VI) phase which is difficult to be sulfided. In CoMo/CNT cata-lytic system sulfided with ex-situ method, Mo(IV) in the form of MoS2 is detected along with a portion of unre-duced Mo(VI) phase, suggesting that not all the Mo phases are reduced and sulfided by ex-situ method. As for CoMo/-Al2O3, a portion of molybdenum is sulfided to intermediate reduced state Mo(V) which consists of Mo co-ordinated both to O and S, such as MoO2S2-2 and MoO3S2-, in addition, there is still a fraction of unreduced Mo(VI) phase. XPS analyses results suggest that CNT support facilitates the reduction and sulfidation of active species to a large extent, and that alumina support strongly interacts with active species, hereby producing a fraction of phase which resists complete sulfiding. Catalytic measurements of catalysts in the HDS of dibenzothiophene (DBT) show that CoMo/CNT catalysts are of higher HDS activity and selectivity than CoMo/-Al2O3 catalyst, which is in good relation with the sulfiding behavior of the corresponding catalyst.
Keywords:carbon nanotube  XPS  HDS  molybdenum  Co-Mo catalyst
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