Wang Chengwei, Jin Zhiliang, Guo Lisheng, Yamamoto Osami, Kaida Chiharu, He Yingluo, Ma Qingxiang, Wang Kangzhou, Tsubaki Noritatsu
Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama, 930-8555, Japan.
School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan, 750021, P. R. China.
Angew Chem Int Ed Engl. 2024 Oct 14;63(42):e202408275. doi: 10.1002/anie.202408275. Epub 2024 Sep 12.
In the case of CO thermal-catalytic hydrogenation, highly selective olefin generation and subsequent olefin secondary reactions to fuel hydrocarbons in an ultra-short residence time is a huge challenge, especially under industrially feasible conditions. Here, we report a pioneering synthetic process that achieves selective production of high-volume commercial gasoline with the assistance of fast response mechanism. In situ experiments and DFT calculations demonstrate that the designed NaFeGaZr presents exceptional carbiding prowess, and swiftly forms carbides even at extremely brief gas residence times, facilitating olefin production. The created successive hollow zeolite HZSM-5 further reinforces aromatization of olefin diffused from NaFeGaZr via optimized mass transfer in the hollow channel of zeolite. Benefiting from its rapid response mechanism within the multifunctional catalytic system, this catalyst effectively prevents the excessive hydrogenation of intermediates and controls the swift conversion of intermediates into aromatics, even in high-throughput settings. This enables a rapid one-step synthesis of high-quality gasoline-range hydrocarbons without any post-treatment, with high commercial product compatibility and space-time yield up to 0.9 kg ⋅ kg ⋅ h. These findings from the current work can provide a shed for the preparation of efficient catalysts and in-depth understanding of C1 catalysis in industrial level.
在一氧化碳热催化加氢的情况下,在超短停留时间内实现高选择性烯烃生成以及随后烯烃向燃料烃的二次反应是一项巨大挑战,尤其是在工业可行条件下。在此,我们报道了一种开创性的合成工艺,该工艺借助快速响应机制实现了高产量商用汽油的选择性生产。原位实验和密度泛函理论计算表明,所设计的NaFeGaZr具有卓越的碳化能力,即使在极短的气体停留时间下也能迅速形成碳化物,促进烯烃生成。所制备的连续中空沸石HZSM - 5通过优化沸石中空通道内的传质,进一步增强了从NaFeGaZr扩散出的烯烃的芳构化。受益于其在多功能催化体系中的快速响应机制,这种催化剂即使在高通量条件下也能有效防止中间体过度氢化,并控制中间体迅速转化为芳烃。这使得无需任何后处理即可快速一步合成高质量汽油馏分烃,具有高商业产品兼容性,时空产率高达0.9 kg ⋅ kg ⋅ h。当前工作的这些发现可为工业级高效催化剂的制备以及对C1催化的深入理解提供启示。