Li Tao, Wang Shuyuan, Sun Zhenye, Wang Yan, Su Jinghong, Lv Yinghui, Zhang Ling, Tao Zhichao, Yang Yong
School of Bioengineering, Shandong Polytechnic, Jinan 250104, China.
Energy Research Institute, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China.
ACS Omega. 2024 Aug 14;9(34):36741-36750. doi: 10.1021/acsomega.4c05594. eCollection 2024 Aug 27.
High-performance amorphous silica-aluminas (ASAs) were prepared prior to the formation of the 10-membered ring (10-MR) ZSM-5 zeolite by regulating the hydrothermal processing time. Their structures, morphologies, acidity properties, and Si-Al coordination were well studied. Particularly, a facile FTIR method of in-situ adsorbing bulky 2,6-dimethlypyridine followed by pyridine adsorption was innovatively utilized to quantify the Brønsted acid sites in micropores. All the ASAs samples were transformed into catalysts by loading with 0.5 wt % Pt. The structure-activity relationship, especially from the strength, density, and location of Brønsted acid sites, was investigated by Fischer-Tropsch synthesis (FTS) wax hydrocracking. The evaluation results showed that the medium strong Brønsted acid sites located on the external surface played a crucial role in the activity. Contrary to the general belief that larger pores favor the production of heavy cracking fractions, the ASAs with a 10-MR microporous structure proved to be more effective for diesel production than those with a 12-membered ring (12-MR). Strong Brønsted acid sites in micropores were less conducive to diesel production mainly due to stronger adsorption at these sites and steric hindrance from the microporous system. Furthermore, the Pt/AS-20 catalyst with few intramicropore Brønsted acid sites exhibited high diesel selectivity (83.3%) at 50.5% conversion under industrially relevant reaction conditions, which provides a significant opportunity to develop FTS wax hydrocracking catalysts more rationally.
通过调节水热反应时间,在十元环(10-MR)ZSM-5沸石形成之前制备了高性能无定形硅铝酸盐(ASA)。对其结构、形态、酸性性质和硅铝配位进行了深入研究。特别地,创新性地采用了一种简便的傅里叶变换红外光谱(FTIR)方法,先原位吸附体积较大的2,6-二甲基吡啶,然后进行吡啶吸附,以定量微孔中的布朗斯台德酸位。所有ASA样品通过负载0.5 wt%的Pt转化为催化剂。通过费托合成(FTS)蜡加氢裂化研究了结构-活性关系,特别是布朗斯台德酸位的强度、密度和位置。评价结果表明,位于外表面的中等强度布朗斯台德酸位对活性起关键作用。与通常认为较大孔有利于重质裂化馏分生成的观点相反,具有10-MR微孔结构的ASA对柴油生产比具有十二元环(12-MR)的更有效。微孔中的强布朗斯台德酸位对柴油生产不太有利,主要是因为这些位点的吸附更强以及微孔系统的空间位阻。此外,在工业相关反应条件下,具有少量微孔内布朗斯台德酸位的Pt/AS-20催化剂在转化率为50.5%时表现出高柴油选择性(83.3%),这为更合理地开发FTS蜡加氢裂化催化剂提供了重要契机。