Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium

被引：75

作者：

Yarulina, Irina ^{[1
]}

Bailleul, Simon ^{[2
]}

Pustovarenko, Alexey ^{[1
]}

Martinez, Javier Ruiz ^{[3
]}

De Wispelaere, Kristof ^{[2
]}

Hajek, Julianna ^{[2
]}

Weckhuysen, Bert M. ^{[3
]}

Houben, Klaartje ^{[4
]}

Baldus, Marc ^{[4
]}

Van Speybroeck, Veronique ^{[2
]}

Kapteijn, Freek ^{[1
]}

Gascon, Jorge ^{[1
]}

机构：

[1] Delft Univ Technol, Catalysis Engn Grp, Dept Chem Engn, Fac Sci Appl, Julianalaan 136, NL-2628 BL Delft, Netherlands

[2] Univ Ghent, Ctr Mol Modeling, Technol Pk 903, B-9052 Zwijnaarde, Belgium

[3] Univ Utrecht, Inorgan Chem & Catalysis Grp, Debye Inst Nanomat Sci, Univ Weg 99, NL-3584 CG Utrecht, Netherlands

[4] Univ Utrecht, NMR Res Grp, Debye Inst Nanomat Sci, Univ Weg 99, NL-3584 CG Utrecht, Netherlands

来源：

CHEMCATCHEM | 2016年 / 8卷 / 19期

关键词：

acidity; alkenes; calcium; density functional calculations; zeolites; SOLID-STATE NMR; DENSITY-FUNCTIONAL THEORY; HIGH-SILICA HZSM-5; CATALYTIC PERFORMANCE; SELECTIVE OXIDATION; SHAPE SELECTIVITY; ZEOLITE H-ZSM-5; ACID PROPERTIES; DIMETHYL ETHER; ACTIVE-SITES;

D O I：

10.1002/cctc.201600650

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Incorporation of Ca in ZSM-5 results in a twofold increase of propylene selectivity (53%), a total light-olefin selectivity of 90%, and a nine times longer catalyst lifetime (throughput 792 g(MeOH)g(catalyst)(-1)) in the methanol-to-olefins (MTO) reaction. Analysis of the product distribution and theoretical calculations reveal that post-synthetic modification with Ca2+ leads to the formation of CaOCaOH+ that strongly weaken the acid strength of the zeolite. As a result, the rate of hydride transfer and oligomerization reactions on these sites is greatly reduced, resulting in the suppression of the aromatic cycle. Our results further highlight the importance of acid strength on product selectivity and zeolite lifetime in MTO chemistry.

引用

页码：3057 / 3063

页数：7

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