Design of the Metal Precursors Molecular Structures in Impregnating Solutions for Preparation of Efficient Ni Mo/Al_2O_3 Hydrodesulfurization Catalysts  

作　　者：Li Huifeng Li Mingfeng Chu Yang Liu Feng Nie Hong 

机构地区：[1]SINOPEC Research Institute of Petroleum Processing

出　　处：《China Petroleum Processing & Petrochemical Technology》2015年第4期37-45,共9页中国炼油与石油化工（英文版）

基　　金：supported by the National Key Basic Research Program of China(973 Program,2012CB224802);the SINOPEC project(No.114013)

摘　　要：The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization（HDS） catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4（citrate）2O11]^4--like, [P2Mo18O62]^6--like and [P2Mo5O23]^6--like species in the solutions were confirmed by laser Raman spectroscopy（LRS）. The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of（Ni）Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^6--like species used as precursors exhibited worse dispersion of（Ni）Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4（citrate）2O11]^4--like species. Promisingly, the catalyst prepared with co-existing [Mo4（citrate）2O11]^4--like, [P2Mo18O62]^6--like and [P2Mo5O23]^6--like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.

关 键 词：molecular structures of metal precursors impregnating solution citric acid phosphorous hydrodesulfurization 

分 类 号：O643.36[理学—物理化学]