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Direct Conversion of Syngas into Light Olefins with Low CO2 Emission

  • Sen Wang
    Sen Wang
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
    More by Sen Wang
  • Pengfei Wang
    Pengfei Wang
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
    More by Pengfei Wang
  • Dezhi Shi
    Dezhi Shi
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
    University of Chinese Academy of Sciences, Beijing 100049, China
    More by Dezhi Shi
  • Shipei He
    Shipei He
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
    University of Chinese Academy of Sciences, Beijing 100049, China
    More by Shipei He
  • Li Zhang
    Li Zhang
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
    University of Chinese Academy of Sciences, Beijing 100049, China
    More by Li Zhang
  • Wenjun Yan
    Wenjun Yan
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
    More by Wenjun Yan
  • Zhangfeng Qin
    Zhangfeng Qin
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
  • Junfen Li
    Junfen Li
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
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  • Mei Dong
    Mei Dong
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
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  • Jianguo Wang
    Jianguo Wang
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
    University of Chinese Academy of Sciences, Beijing 100049, China
    More by Jianguo Wang
  • Unni Olsbye
    Unni Olsbye
    Department of Chemistry, Centre for Materials and Nanoscience (SMN), University of Oslo, P.O. Box 1033, Blindern, Oslo NO-0315, Norway
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  • , and 
  • Weibin Fan*
    Weibin Fan
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, Shanxi 030001, China
    *E-mail: [email protected]. Phone: +86-351-4199009. Fax: +86-351-4041153.
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Cite this: ACS Catal. 2020, 10, 3, 2046–2059
Publication Date (Web):January 2, 2020
https://doi.org/10.1021/acscatal.9b04629
Copyright © 2020 American Chemical Society
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Abstract

Direct conversion of syngas into light olefins over bifunctional catalysts has made significant progress; the C2=–C4= selectivity in hydrocarbons reaches >80%. Nevertheless, a relatively harsh reaction condition (>380 °C, 1.0 MPa) led to producing large amounts of CO2 (>40%) and gave a low olefin/paraffin (O/P) ratio (<10) as a result of significant promotion of water–gas shift (WGS) reaction and overhydrogenation of olefins. In this context, attempts are made here to develop a highly active low-temperature composite catalyst. It was found that a zinc–cerium–zirconium solid solution (ZnxCe2–yZryO4) and a SAPO-34 mixture showed CO conversion, light olefin selectivity in hydrocarbons, and O/P ratios of about 7%, 83%, and 23, respectively, at 300 °C and 1 atm. More interestingly, this catalyst showed CH4 selectivity and CO2 emission lower than 5 and 6%, respectively. A combination of experimental, in situ spectroscopy, and theoretical calculation results reveals that doping Ce in ZnxZr2.0O4 greatly inhibits the WGS reaction by increasing the formation energy barrier of carboxylate intermediate species, but increases surface oxygen vacancy concentration of the composite through formation of a solid solution, and as a consequence, improving the catalytic activity for conversion of syngas at mild conditions by enhancing the interaction of CO with the catalyst, which elongates the C–O bond of the HCO* species.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.9b04629.

  • Catalytic results for conversion of syngas on various ZnxCe2–yZryO4/SAPO-34 composite catalysts; catalytic results for conversion of methanol over the SAPO-34 zeolite; 13C CP/MAS NMR spectrum of carbonaceous species retained in the used SAPO-34; 12C/13C methanol switching experiment in SAPO-34; the STY of methanol obtained over the Zn0.3Ce1.0Zr1.0O4 solid solution and the Zn0.3Ce1.0Zr1.0O4/SAPO-340.025 bifunctional catalyst; the XRD patterns, SEM images, TEM/HRTEM images, XPS spectra, H2-TPR, CO-TPD profiles, and N2 sorption isotherms of the ZnxCe2–yZryO4 solid solution and SAPO-34 zeolite; the in situ DRIFTS, in situ XPS, TPSR, and DFT calculation results for syngas conversion and WGS reaction over the ZnxCe2–yZryO4 solid solutions (PDF)

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