One-step conversion of syngas to light olefins over bifunctional metal-zeolite catalyst

doi:10.1016/j.cjche.2020.09.004

中国化学工程学报 ›› 2021, Vol. 36 ›› Issue (8): 101-110.DOI: 10.1016/j.cjche.2020.09.004

• Catalysis, Kinetics and Reaction Engineering • 上一篇下一篇

One-step conversion of syngas to light olefins over bifunctional metal-zeolite catalyst

Ce Du^1,2, Linet Gapu Chizema¹, Emmerson Hondo¹, Mingliang Tong¹, Qingxiang Ma³, Xinhua Gao³, Ruiqin Yang¹, Peng Lu¹, Noritatsu Tsubaki²

1 Zhejiang Provincial Key Lab for Chem. & Bio. Processing Technology of Farm Product, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, China;
2 Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan;
3 State Key Laboratory Cultivation Base of Natural Gas Conversion, Ningxia University, Yinchuan 750021, China

收稿日期:2020-04-28 修回日期:2020-08-11 出版日期:2021-08-28 发布日期:2021-09-30
通讯作者: Peng Lu, Noritatsu Tsubaki
基金资助:
This research is financially supported by Youth Foundation of ZUST, China (2019QN23) and Foundation of State Key Laboratory of Highefficiency Utilization of Coal and Green Chemical Engineering (2019-KF-21).

One-step conversion of syngas to light olefins over bifunctional metal-zeolite catalyst

Ce Du^1,2, Linet Gapu Chizema¹, Emmerson Hondo¹, Mingliang Tong¹, Qingxiang Ma³, Xinhua Gao³, Ruiqin Yang¹, Peng Lu¹, Noritatsu Tsubaki²

1 Zhejiang Provincial Key Lab for Chem. & Bio. Processing Technology of Farm Product, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, China;
2 Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan;
3 State Key Laboratory Cultivation Base of Natural Gas Conversion, Ningxia University, Yinchuan 750021, China

Received:2020-04-28 Revised:2020-08-11 Online:2021-08-28 Published:2021-09-30
Contact: Peng Lu, Noritatsu Tsubaki
Supported by:
This research is financially supported by Youth Foundation of ZUST, China (2019QN23) and Foundation of State Key Laboratory of Highefficiency Utilization of Coal and Green Chemical Engineering (2019-KF-21).

摘要/Abstract

摘要： Light olefins (C₂-C₄) are fundamental building blocks for the manufacture of polymers, chemical intermediates, and solvents. In this work, we realized a composite catalyst, comprising Mn_xZr_y oxides and SAPO-34 zeolite, which can convert syngas (CO + H₂) into light olefins. Mn_xZr_y oxide catalysts with different Mn/Zr molar ratios were facilely prepared using the coprecipitation method prior to physical mixing with SAPO-34 zeolite. The redox properties, surface morphology, electronic state, crystal structure, and chemical elemental composition of the catalysts were examined using H₂-TPR, SEM, XPS, XRD, and EDS techniques, respectively. Tandem reactions involved activation of CO and subsequent hydrogenation over the metal oxide catalyst, producing methanol and dimethyl ether as the main reaction intermediates, which then migrated onto SAPO-34 zeolite for light olefins synthesis. Effects of temperature, pressure and reactant gas flow rate on CO conversion and light olefins selectivity were investigated in detail. The Mn₁Zr₂/SAPO-34 catalyst (Mn/Zr ratio of 1:2) attained a CO conversion of 10.8% and light olefins selectivity of 60.7%, at an optimized temperature, pressure and GHSV of 380 ℃, 3 MPa and 3000 h^-1 respectively. These findings open avenues to exploit other metal oxides with CO activation capabilities for a more efficient syngas conversion and product selectivity.

关键词: Catalyst, C—C coupling, CO activation, Hydrogenation, Light olefins, Syngas

Abstract: Light olefins (C₂-C₄) are fundamental building blocks for the manufacture of polymers, chemical intermediates, and solvents. In this work, we realized a composite catalyst, comprising Mn_xZr_y oxides and SAPO-34 zeolite, which can convert syngas (CO + H₂) into light olefins. Mn_xZr_y oxide catalysts with different Mn/Zr molar ratios were facilely prepared using the coprecipitation method prior to physical mixing with SAPO-34 zeolite. The redox properties, surface morphology, electronic state, crystal structure, and chemical elemental composition of the catalysts were examined using H₂-TPR, SEM, XPS, XRD, and EDS techniques, respectively. Tandem reactions involved activation of CO and subsequent hydrogenation over the metal oxide catalyst, producing methanol and dimethyl ether as the main reaction intermediates, which then migrated onto SAPO-34 zeolite for light olefins synthesis. Effects of temperature, pressure and reactant gas flow rate on CO conversion and light olefins selectivity were investigated in detail. The Mn₁Zr₂/SAPO-34 catalyst (Mn/Zr ratio of 1:2) attained a CO conversion of 10.8% and light olefins selectivity of 60.7%, at an optimized temperature, pressure and GHSV of 380 ℃, 3 MPa and 3000 h^-1 respectively. These findings open avenues to exploit other metal oxides with CO activation capabilities for a more efficient syngas conversion and product selectivity.

Key words: Catalyst, C—C coupling, CO activation, Hydrogenation, Light olefins, Syngas

Ce Du, Linet Gapu Chizema, Emmerson Hondo, Mingliang Tong, Qingxiang Ma, Xinhua Gao, Ruiqin Yang, Peng Lu, Noritatsu Tsubaki. One-step conversion of syngas to light olefins over bifunctional metal-zeolite catalyst[J]. 中国化学工程学报, 2021, 36(8): 101-110.

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One-step conversion of syngas to light olefins over bifunctional metal-zeolite catalyst

One-step conversion of syngas to light olefins over bifunctional metal-zeolite catalyst

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