State Key Laboratory of Catalysis, National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, P. R. China.
Chem Rev. 2021 Jun 9;121(11):6588-6609. doi: 10.1021/acs.chemrev.0c01012. Epub 2021 May 25.
Syngas chemistry has been under study since Fischer-Tropsch synthesis (FTS) was invented in the 1920s. Despite the successful applications of FTS as the core technology of coal-to-liquid and gas-to-liquid processes in industry, the product selectivity control of syngas conversion still remains a great challenge, particularly for value-added chemicals such as light olefins. Recent studies show that the catalyst design concept of OXZEO (oxide-zeolite-based composite) enables direct syngas conversion to mixed light olefins with a selectivity reaching 80% and to ethylene with a selectivity of 83% among hydrocarbons. They both well-surpass the limits predicated by the Anderson-Schultz-Flory model via the conventional FTS route (58% and 30%, respectively). Furthermore, this catalyst concept allows one-step synthesis of gasoline-range isoparaffins and aromatic compounds, which is otherwise not possible in conventional FTS. A rapidly growing number of studies demonstrate the versatility of this concept and may form a technology platform for utilization of carbon resources including coal, natural gas, and biomass via syngas to a variety of basic chemicals and fuels. However, the selectivity control mechanism is far from being understood. Therefore, we focus mainly on the catalytic roles of the bifunctionalities of OXZEO while reviewing the development of bifunctional catalysts for selective syngas conversion by taking syngas-to-light olefins as an example. With this, we intend to provide insights into the selectivity control mechanism of the OXZEO concept in order to understand the challenges and prospects for future development of much more active and more selective catalysts.
自 20 世纪 Fischer-Tropsch 合成(FTS)发明以来,合成气化学一直受到研究。尽管 FTS 作为煤制油和天然气制油工艺的核心技术在工业中得到了成功应用,但合成气转化的产物选择性控制仍然是一个巨大的挑战,特别是对于轻烯烃等附加值化学品。最近的研究表明,OXZEO(基于氧化物-沸石的复合材料)催化剂设计概念能够将合成气直接转化为混合轻烯烃,选择性达到 80%,在烃类中,乙烯的选择性达到 83%。这两个数值都远远超过了传统 FTS 路线预测的安德森-舒尔茨-弗洛里模型限制(分别为 58%和 30%)。此外,该催化剂概念还允许一步合成汽油范围内的异链烷烃和芳烃,而在传统 FTS 中则不可能。越来越多的研究表明了该概念的多功能性,并可能形成一个利用包括煤、天然气和生物质在内的碳资源通过合成气生产各种基础化学品和燃料的技术平台。然而,选择性控制机制还远未被理解。因此,我们主要关注 OXZEO 的双功能催化作用,同时以合成气制轻烯烃为例,综述了用于选择性合成气转化的双功能催化剂的发展。通过这种方式,我们旨在深入了解 OXZEO 概念的选择性控制机制,以便了解未来更具活性和选择性的催化剂的发展挑战和前景。