Hierarchical ZSM-11 with intergrowth structures:Synthesis,characterization and catalytic properties  

作　　者：Qingjun Yu Chaoyue Cui Qiang Zhang Jing Chen Yang Li Jinpeng Sun Chunyi Li Qiukai Cui Chaohe Yang Honghong Shan 

机构地区：[1]State Key Laboratory of Heavy Oil Processing, Department of Chemical Engineering, China University of Petroleum (East China) [2]Dagang Petrochemical Company, PetroChina Corporation

出　　处：《Journal of Energy Chemistry》2013年第5期761-768,共8页能源化学（英文版）

基　　金：supported by the National Program on Key Basic Research Project(973 Program)(Grant No.2012CB215000);the financial support from Fundamental Research Funds for the Central Universities

摘　　要：Hierarchical ZSM-11 microspheres with intercrystalline mesoporous properties and rod-like crystals intergrowth morphology have been synthesized using a spot of tetrabutylammonium as a single template.XRD,FTIR,SEM,TEM and N2 adsorption analysis revealed that each individual particle was composed of nanosized rod crystals inserting each other and the intercrystalline voids existing among rods gave a significant mesopore size distribution.Steam treatment result demonstrated the excellent hydrothermal stability of samples.Various crystallization modes including constant temperature crystallization (one-stage crystallization) and two-stage temperature-varying crystallization with different 1st stage durations were investigated.The results suggested that the crystallization modes were mainly responsible for the adjustable particle size and textural properties of samples while the small amount of tetrabutylammonium bromide was mainly used to direct the formation of both ZSM-11 framework and its intergrowth morphology.Furthermore,the performance of optimal ZSM-11 as an active component for the catalytic pyrolysis of heavy oil was also investigated.Compared with the commercial pyrolysis catalyst,the hierarchical ZSM-11 catalyst exhibited a high selectivity to desired products(LPG+gasoline+diesel),as well as a much lower dry gas and coke yield,plus a high selectivity and yield of light olefins(C=3 C=4)and very poor selectivity to benzene.Therefore,fully open micropore-mesopore connectivity would make such hierarchically porous ZSM-11 zeolites very attractive for applications in clean petrochemical catalysis field.Hierarchical ZSM-11 microspheres with intercrystalline mesoporous properties and rod-like crystals intergrowth morphology have been synthesized using a spot of tetrabutylammonium as a single template.XRD,FTIR,SEM,TEM and N2 adsorption analysis revealed that each individual particle was composed of nanosized rod crystals inserting each other and the intercrystalline voids existing among rods gave a significant mesopore size distribution.Steam treatment result demonstrated the excellent hydrothermal stability of samples.Various crystallization modes including constant temperature crystallization (one-stage crystallization) and two-stage temperature-varying crystallization with different 1st stage durations were investigated.The results suggested that the crystallization modes were mainly responsible for the adjustable particle size and textural properties of samples while the small amount of tetrabutylammonium bromide was mainly used to direct the formation of both ZSM-11 framework and its intergrowth morphology.Furthermore,the performance of optimal ZSM-11 as an active component for the catalytic pyrolysis of heavy oil was also investigated.Compared with the commercial pyrolysis catalyst,the hierarchical ZSM-11 catalyst exhibited a high selectivity to desired products(LPG+gasoline+diesel),as well as a much lower dry gas and coke yield,plus a high selectivity and yield of light olefins(C=3 C=4)and very poor selectivity to benzene.Therefore,fully open micropore-mesopore connectivity would make such hierarchically porous ZSM-11 zeolites very attractive for applications in clean petrochemical catalysis field.

关 键 词：intercrystalline mesopore rod-like crystal single template crystallization modes ACCESSIBILITY hydrothermal stability catalytic pyrolysis 

分 类 号：O643.36[理学—物理化学]