Methanol to Olefins Reaction Route Based on Methylcyclopentadienes as Critical Intermediates

doi:10.1021/acscatal.9b02487

	Methanol to Olefins Reaction Route Based on Methylcyclopentadienes as Critical Intermediates
	Zhang, Wenna 1,2; Zhi, Yuchun 2; Huang, Jindou 2; Wu, Xinqiang 2; Zeng, Shu 1,2; Xu, Shutao 2; Zheng, Anmin3,4 ; Wei, Yingxu 2; Liu, Zhongmin 2
刊名	ACS CATALYSIS
	2019-08-01
卷号	9 期号:8 页码:7373-7379
关键词	methanol-to-olefins H-SAPO-34 indirect mechanism methylcyclopentadiene cyclopentadienes-based cycle
ISSN号	2155-5435
DOI	10.1021/acscatal.9b02487
英文摘要	Starting from C1 raw material, methanol conversion to hydrocarbons has been realized via a rather complicated pathway. In this contribution, we proposed an alternative methanol reaction route and provided a general understanding of such complex indirect mechanism. The methylcyclopentenyl cations and their deprotonated counterparts (methylcyclopentadienes) were validated to appear on the working H-SAPO-34 catalyst by in situ C-13 MAS NMR spectroscopy and the GC-MS technique, and their catalytic reactivity was revealed by the C-12/C-13-CH3OH isotopic switch experiment. In this context, a cyclopentadienes-based cycle was established, in which light olefins were formed with methylcyclopentadienes as critical intermediates. The feasibility of this alternative route was confirmed by density functional theory calculations. Notably, the cyclopentadienes-based cycle runs in parallel with the traditional alkenes-based and aromatics-based cycles; these three mechanistic cycles are interrelated through interconversion of the involved intermediates, including alkene, cyclopentadiene, and aromatic species. All these three cycles work together for the C-C bond assembly in the methanol-to-olefins reaction system. These findings help to build a more complete methanol conversion network and advance the in-depth understanding of indirect mechanism of methanol conversion.
资助项目	National Natural Science Foundation of China[91745109] ; National Natural Science Foundation of China[21703239] ; National Natural Science Foundation of China[91545104] ; National Natural Science Foundation of China[21473182] ; Youth Innovation Promotion Association of the Chinese Academy of Sciences[2014165] ; LiaoNing Revitalization Talents Program[XLYC1807227] ; Key Research Program of Frontier Sciences, CAS[QYZDY-SSW-JSC024]
WOS关键词	HYDROCARBON-POOL ; REACTION-MECHANISM ; ZEOLITE H-ZSM-5 ; CO-REACTION ; CONVERSION ; INSIGHTS ; HSAPO-34 ; ETHENE ; CYCLE ; IONS
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000480503700080
资助机构	National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; LiaoNing Revitalization Talents Program ; LiaoNing Revitalization Talents Program ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; LiaoNing Revitalization Talents Program ; LiaoNing Revitalization Talents Program ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; LiaoNing Revitalization Talents Program ; LiaoNing Revitalization Talents Program ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; LiaoNing Revitalization Talents Program ; LiaoNing Revitalization Talents Program ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS
内容类型	期刊论文
源URL	[http://ir.wipm.ac.cn/handle/112942/14765]
专题	中国科学院武汉物理与数学研究所
通讯作者	Zheng, Anmin; Wei, Yingxu; Liu, Zhongmin
作者单位	1.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 2.Chinese Acad Sci, Natl Engn Lab Methanol Olefins, iChEM Collaborat Innovat Ctr Chem Energy Mat, Dalian Inst Chem Phys,Dalian Natl Lab Clean Energ, Dalian 116023, Peoples R China 3.Chinese Acad Sci, Inst Phys & Math, Natl Ctr Magnet Resonance Wuhan, State Key Lab Magnet Resonance & Atom Mol Phys, Wuhan 430071, Hubei, Peoples R China 4.Zhengzhou Univ, Sch Mat Sci & Engn, Zhengzhou 450052, Henan, Peoples R China
推荐引用方式 GB/T 7714	Zhang, Wenna,Zhi, Yuchun,Huang, Jindou,et al. Methanol to Olefins Reaction Route Based on Methylcyclopentadienes as Critical Intermediates[J]. ACS CATALYSIS,2019,9(8):7373-7379.
APA	Zhang, Wenna.,Zhi, Yuchun.,Huang, Jindou.,Wu, Xinqiang.,Zeng, Shu.,...&Liu, Zhongmin.(2019).Methanol to Olefins Reaction Route Based on Methylcyclopentadienes as Critical Intermediates.ACS CATALYSIS,9(8),7373-7379.
MLA	Zhang, Wenna,et al."Methanol to Olefins Reaction Route Based on Methylcyclopentadienes as Critical Intermediates".ACS CATALYSIS 9.8(2019):7373-7379.