Production of methanol from СО2 on Cu-Zn-catalysts applied on commercial supports: impact of support and reaction conditions

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Abstract

Catalytic properties of Cu-Zn-catalysts on various commercial supports such as Al2O3, SiO2, ZrO2(La), TiO2, ZnO, and activated carbon in the reaction of CO2 hydrogenation with methanol production are studied. The CuZn/Al2O3 catalyst is found to show the highest CO2 conversion; the highest selectivities to methanol equaling 99% and 97.5% are observed in CuZn/ZrO2(La) and CuZn/SiO2 catalysts, respectively, and high CH3OH selectivities of 90–95% are achieved in the temperature range of 175-275°C; and the CuZn/ZrO2(La) catalyst had the highest methanol productivity of 547 g/(kgcat h). The synthesized catalysts are characterized by methods of low-temperature nitrogen adsorption, X-ray phase analysis, and SEM-EDX.

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About the authors

A. M. Batkin

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: kyst@list.ru
Russian Federation, Moscow, 119991

M. A. Tedeeva

M. V. Lomonosov Moscow State University

Email: kyst@list.ru

Department of Chemistry

Russian Federation, Moscow, 119991

K. B. Kalmykov

M. V. Lomonosov Moscow State University

Email: kyst@list.ru

Department of Chemistry

Russian Federation, Moscow, 119991

A. V. Leonov

M. V. Lomonosov Moscow State University

Email: kyst@list.ru

Department of Chemistry

Russian Federation, Moscow, 119991

N. A. Davshan

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: kyst@list.ru
Russian Federation, Moscow, 119991

P. V. Pribytkov

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences; M. V. Lomonosov Moscow State University, Department of Chemistry

Email: kyst@list.ru

M. V. Lomonosov Moscow State University, Department of Chemistry

Russian Federation, Moscow, 119991; Moscow, 119991

S. F. Dunaev

M. V. Lomonosov Moscow State University, Department of Chemistry

Email: kyst@list.ru

Department of Chemistry

Russian Federation, Moscow, 119991

I. P. Beletskaya

M. V. Lomonosov Moscow State University

Email: kyst@list.ru

Department of Chemistry

Russian Federation, Moscow, 119991

A. L. Kustov

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences; M. V. Lomonosov Moscow State University, Department of Chemistry

Author for correspondence.
Email: kyst@list.ru

M. V. Lomonosov Moscow State University, Department of Chemistry

Russian Federation, Moscow, 119991; Moscow, 119991

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Supplementary files

Supplementary Files
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2. Fig. 1. Nitrogen adsorption–desorption isotherms of CuZn/carrier catalysts.

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3. Fig. 2. Diffraction patterns of the samples of the Al2O3 support and CuZn/Al2O3 catalyst (a), the SiO2 support and CuZn/SiO2 catalyst (b), the TiO2 support and CuZn/TiO2 catalyst (c), the ZrO2(La) support and CuZn/ZrO2(La) catalyst (d), the C support and CuZn/C catalyst (e), the ZnO support and CuZn/ZnO catalyst (e), as well as data from the JCPDS database for crystalline CuO (JCPDS89–5895) and ZnO (JCPDS33783).

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4. Fig. 3. Micrographs of the catalyst samples

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5. Fig. 4. Maps of copper and zinc distribution

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6. Fig. 5. X-ray microanalysis data of the catalyst surfaces of CuZn/Al2O3 (a), CuZn/SiO2 (b), CuZn/TiO2 (c), CuZn/ZrO2(La) (d), CuZn/C (d) and CuZn/ZnO (e).

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7. Fig. 6. Dependences of CO2 conversion (a) and CH3OH selectivity (b) on the reaction temperature at P = 50 atm. for CuZn/carrier samples.

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8. Fig. 7. Dependence of selectivity for CH3OH on temperature for CuZn/SiO2 catalyst in the temperature range of 170–270°C at two different pressures of 40 and 50 atm.

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9. Fig. 8. Dependences of selectivity for CH4 (a) and CO (b) on reaction temperature at P = 50 atm. for CuZn/carrier samples.

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10. Fig. 9. Dependences of CH3OH productivity on reaction temperature at P = 50 atm. for CuZn/carrier samples.

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