物理化学学报 >> 2018, Vol. 34 >> Issue (8): 858-872.doi: 10.3866/PKU.WHXB201802061

所属专题: 绿色化学

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二氧化碳多相催化加氢制C2及以上烃类和醇的研究进展

高云楠,刘世桢,赵振清,陶亨聪,孙振宇*()   

  • 收稿日期:2018-01-05 发布日期:2018-04-03
  • 通讯作者: 孙振宇 E-mail:sunzy@mail.buct.edu.cn
  • 作者简介:SUN Zhenyu is currently a full professor in the College of Chemical Engineering at Beijing University of Chemical Technology (China). He completed his Ph.D. in the Institute of Chemistry, Chinese Academy of Sciences in 2006. He did postdoctoral research in Trinity College Dublin (Ireland) from 2006 to 2008, at Ruhr University Bochum (Germany) from 2011 to 2014, and University of Oxford from 2015 to 2016. He has obtained a Humboldt Research Fellowship for Experienced Researchers (Germany). His current research focuses on energy conversion reactions using two-dimensional materials
  • 基金资助:
    有机无机复合材料国家重点实验室人才培育资助项目(oic-201503005);北京化工大学引进人才经费(buctrc201525);北京分子科学国家实验室开放课题基金(BNLMS20160133)

Heterogeneous Catalysis of CO2 Hydrogenation to C2+ Products

Yunnan GAO,Shizhen LIU,Zhenqing ZHAO,Hengcong TAO,Zhenyu SUN*()   

  • Received:2018-01-05 Published:2018-04-03
  • Contact: Zhenyu SUN E-mail:sunzy@mail.buct.edu.cn
  • Supported by:
    the State Key Laboratory of Organic-Inorganic Composites, China(oic-201503005);Fundamental Research Funds for the Central Universities, China(buctrc201525);Beijing National Laboratory for Molecular Sciences, China(BNLMS20160133)

摘要:

通过可再生能源得到的氢气将二氧化碳转化为高附加值的燃料和化学品,对于缓解全球变暖、改善生态环境和解决化石资源日益枯竭的难题具有重要的意义。通过加氢反应合成碳氢化合物,尤其是C2+烃类和含氧化合物愈来愈引起大家的研究兴趣。设计制备兼具二氧化碳活化和碳-碳键耦合的多功能催化剂仍然是一较大的挑战。本文总结了二氧化碳加氢合成长链烷烃、低碳烯烃、高级醇的最新研究进展,探讨了二氧化碳加氢所涉及的相关反应的热力学和动力学、反应机理和反应路径,并对现阶段报道的多相催化剂进行了归纳和分析,最后指出未来在二氧化碳加氢的多相催化过程中所面临的问题和发展方向。

关键词: 二氧化碳加氢, 多相催化, C2+化合物

Abstract:

The increasing anthropogenic emission of CO2 leads to global warming, to address which three strategies can be considered: (1) decrease fossil fuel consumption through increased utilization efficiency and lower per capita consumption; (2) replace fossil fuels with renewable energy sources like wind, tidal, solar, and biomass energies; (3) utilize CO2 efficiently. Despite efforts to reduce energy use and increase the use of carbon-neutral biofuels, it seems that fossil fuels will continue to be a major energy source for the next few decades. Tremendous effort is therefore being focused on developing effective technologies for CO2 capture and transformation. In particular, the transformation of CO2 into fuels and chemicals via reduction with renewable hydrogen is a promising strategy for mitigating global warming and energy supply problems. The hydrogenation of CO2, especially to C2+ hydrocarbons and oxygenates, has sparked growing interest. The C2+ species can be used as entry platform chemicals for existing value chains, thus providing more advantages than C1 compounds. However, optimizing catalyst design by integrating multifunctionalities for both CO2 activation and C-C coupling remains an ongoing challenge. Here, we provide a timely review on the recent progress that has been made in the hydrogenation of CO2 to higher-order alkanes, olefins, and alcohols by various heterogeneous catalysts. The thermodynamics and kinetics, as well as possible reaction pathways for CO2 hydrogenation, are discussed. The hydrogenation of CO2 to hydrocarbons usually involves the initial generation of CO via a reverse water-gas shift (RWGS) reaction followed by hydrogenation of the CO intermediate. The RWGS reaction proceeds through a redox route and an associative pathway. "CHx" insertion (carbide-type) and "CO" insertion are two proposed mechanisms for this Fischer-Tropsch-like synthesis. Fe-or Co-based catalysts have been widely used to catalyze the hydrogenation of CO2 to C2+ hydrocarbons via the CO intermediate. C2+ hydrocarbons can also be obtained by combining CH3OH synthesis with the methanol-to-hydrocarbon process (MTH). This reaction pathway has been realized over bifunctional systems comprising a CH3OH synthesis catalyst and an MTH catalyst. Alternatively, CO2 hydrogenation can occur via a RWGS reaction to the CO intermediate, and subsequent formation of higher alcohols from syngas. Higher alcohols (mostly CH3CH2OH) have been produced by using a hybrid tandem catalyst. Understanding of the activation mechanism, precise C-C coupling, and synergy control between the two active components requires further research. In the final part, we describe the future challenges and opportunities in heterogeneous catalysis of CO2 hydrogenation. The combination of calculations (precise theoretical models) and experiments (in-situ spectroscopic techniques) will facilitate the design of advanced catalysts to achieve both high CO2 conversion and C2+ product selectivity.

Key words: CO2 hydrogenation, Heterogeneous catalysis, C2+ species

MSC2000: 

  • O643