Direct Synthesis of Dimethyl Carbonate from CO2 and CH3OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst*

Chin.J.Chem.Eng. ›› 2012, Vol. 20 ›› Issue (5): 906-913.

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Direct Synthesis of Dimethyl Carbonate from CO₂ and CH₃OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst^*

CHEN Huiling¹, WANG Shuanjin¹, XIAO Min¹, HAN Dongmei¹, LU Yixin², MENG Yuezhong¹

1. The Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province; State Key Laboratory of Optoelectronic Materials and Technologies, Sun Yat-sen University, Guangzhou 510275, China;
2. Department of Chemistry & Medicinal Chemistry Program, Office of Life Sciences, National University of Singapore, 3 Science Drive, Singapore 117543, Republic of Singapore

Received:2011-04-21 Revised:2012-02-25 Online:2012-11-06 Published:2012-10-28
Supported by:
Supported by the National High Technology Research and Development Program of China (2008AA03Z3472294,2009AA302410);the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2010);the Guangdong Province Sci & Tech Bureau (2006B12401006, 2008A080800024);the Chinese Universities Basic Research Founding

Direct Synthesis of Dimethyl Carbonate from CO₂ and CH₃OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst^*

陈惠玲¹, 王栓紧¹, 肖敏¹, 韩冬梅¹, 卢一新², 孟跃中¹

1. The Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province; State Key Laboratory of Optoelectronic Materials and Technologies, Sun Yat-sen University, Guangzhou 510275, China;
2. Department of Chemistry & Medicinal Chemistry Program, Office of Life Sciences, National University of Singapore, 3 Science Drive, Singapore 117543, Republic of Singapore

通讯作者: MENG Yuezhong,E-mail:mengyzh@mail.sysu.edu.cn
基金资助:
Supported by the National High Technology Research and Development Program of China (2008AA03Z3472294,2009AA302410);the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2010);the Guangdong Province Sci & Tech Bureau (2006B12401006, 2008A080800024);the Chinese Universities Basic Research Founding

Abstract

Abstract: The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO₂ and CH₃OH were prepared and investigated. The synthesized catalysts were fully characterized by BET, XRD (X-ray diffraction), TPR (temperature programmed reduction), IR (infra-red adsorption), NH₃-TPD (temperature programmed desorption) and CO₂-TPD (temperature programmed desorption) techniques. The results showed that the surface area of catalysts decreased with increasing metal content, and the metals as well as Cu-Ni alloy co-existed on the reduced catalyst surface. There existed interaction between metal and carrier, and moreover, metal particles affected obviously the acidity and basicity of carrier. The large amount of basic sites facilitated the activation of methanol to methoxyl species and their subsequent reaction with activated carbon dioxide. The catalysts were evaluated in a continuous tubular fixed-bed micro-gaseous reactor and the catalyst with bimetal loading of 20% (by mass) had best catalytic activities. Under the conditions of 393 K, 1.1 MPa, 5 h and gas space velocity of 510 h^-1, the selectivity and yield of DMC were higher than 86.0% and 5.0%, respectively.

Key words: molecular sieve, Cu-Ni bimetal catalysis, dimethyl carbonate, carbon dioxide, methanol

摘要： The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO₂ and CH₃OH were prepared and investigated. The synthesized catalysts were fully characterized by BET, XRD (X-ray diffraction), TPR (temperature programmed reduction), IR (infra-red adsorption), NH₃-TPD (temperature programmed desorption) and CO₂-TPD (temperature programmed desorption) techniques. The results showed that the surface area of catalysts decreased with increasing metal content, and the metals as well as Cu-Ni alloy co-existed on the reduced catalyst surface. There existed interaction between metal and carrier, and moreover, metal particles affected obviously the acidity and basicity of carrier. The large amount of basic sites facilitated the activation of methanol to methoxyl species and their subsequent reaction with activated carbon dioxide. The catalysts were evaluated in a continuous tubular fixed-bed micro-gaseous reactor and the catalyst with bimetal loading of 20% (by mass) had best catalytic activities. Under the conditions of 393 K, 1.1 MPa, 5 h and gas space velocity of 510 h^-1, the selectivity and yield of DMC were higher than 86.0% and 5.0%, respectively.

关键词: molecular sieve, Cu-Ni bimetal catalysis, dimethyl carbonate, carbon dioxide, methanol

CHEN Huiling, WANG Shuanjin, XIAO Min, HAN Dongmei, LU Yixin, MENG Yuezhong. Direct Synthesis of Dimethyl Carbonate from CO₂ and CH₃OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst^*[J]. Chin.J.Chem.Eng., 2012, 20(5): 906-913.

陈惠玲, 王栓紧, 肖敏, 韩冬梅, 卢一新, 孟跃中. Direct Synthesis of Dimethyl Carbonate from CO₂ and CH₃OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst^*[J]. Chinese Journal of Chemical Engineering, 2012, 20(5): 906-913.

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Direct Synthesis of Dimethyl Carbonate from CO₂ and CH₃OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst^*

Direct Synthesis of Dimethyl Carbonate from CO₂ and CH₃OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst^*

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