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

能源化学(英文) ›› 2013, Vol. 22 ›› Issue (5): 761-768.

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

Qingjun Yu^a, Chaoyue Cui^a, Qiang Zhang^a, Jing Chen^a, Yang Li^a, Jinpeng Sun^a, Chunyi Li^a, Qiukai Cui^b, Chaohe Yang^a, Honghong Shan^a

a. State Key Laboratory of Heavy Oil Processing, Department of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China;
b. Dagang Petrochemical Company, PetroChina Corporation, Tianjin 300280, China

收稿日期:2012-12-06 修回日期:2013-01-10 出版日期:2013-09-20 发布日期:2013-09-30
通讯作者: Chunyi Li
基金资助:
This work was supported by the National Program on Key Basic Research Project (973 Program) (Grant No. 2012CB215000).

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

Qingjun Yu^a, Chaoyue Cui^a, Qiang Zhang^a, Jing Chen^a, Yang Li^a, Jinpeng Sun^a, Chunyi Li^a, Qiukai Cui^b, Chaohe Yang^a, Honghong Shan^a

a. State Key Laboratory of Heavy Oil Processing, Department of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China;
b. Dagang Petrochemical Company, PetroChina Corporation, Tianjin 300280, China

Received:2012-12-06 Revised:2013-01-10 Online:2013-09-20 Published:2013-09-30
Supported by:
This work was supported by the National Program on Key Basic Research Project (973 Program) (Grant No. 2012CB215000).

摘要/Abstract

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 (C₃⁼-C₄⁼) 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

Abstract: 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 (C₃⁼-C₄⁼) 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.

Key words: intercrystalline mesopore, rod-like crystal, single template, crystallization modes, accessibility, hydrothermal stability, catalytic pyrolysis

Qingjun Yu, Chaoyue Cui, Qiang Zhang, Jing Chen, Yang Li, Jinpeng Sun, Chunyi Li, Qiukai Cui, Chaohe Yang, Honghong Shan. Hierarchical ZSM-11 with intergrowth structures: Synthesis, characterization and catalytic properties[J]. 能源化学(英文), 2013, 22(5): 761-768.

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

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

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