Solid-Catalyzed Reactions in Supercritical Reaction Media

摘要-Subramaniam-9816969本研究计划将合理利用超临界(Sc)反应介质，为酸催化的1-丁烯/异丁烷烷基化生产汽油、正丁烷骨架异构化为异丁烷以及负载型催化剂上的选择性官能团加氢等重要催化反应开发新的、环境安全和选择性的工艺。目标包括(I)优化基于助溶剂的超临界固体酸烷基化工艺(本实验室最近开发的)，以在高丁烯转化率的情况下获得更高的烷基化油收率；(Ii)应用原位sc脱焦概念来延长低温固体酸骨架异构化催化剂的寿命；以及(Iii)通过压力调节近临界区域的溶剂和输送性质来优化固体催化sc加氢工艺，以获得所需的产品选择性和加氢速率。除了对sc介质中多相流体/固体催化的物理化学过程有更好的基础了解外，本研究开发的催化剂系统还可能通过在优化催化剂选择性、效率和寿命的同时最大限度地减少化学废物来影响炼油和化工行业。具体地说，固体酸催化的烷基化和异构化过程具有更高的活性和产物产率，可以成为基于液体酸的过程的商业上可行的、环境安全的替代品。Sc介质中的连续固体催化加氢具有压力可调的选择性，最大限度地减少了废物的形成，提高了反应速度，并且由于减少了危险试剂在反应器中的滞留而固有的更安全的操作，对于官能团的加氢可能成为一种有吸引力的过程，这是对精细化工、制药和食品工业至关重要的主题。

Abstract - Subramaniam - 9816969 This research program will rationally exploit supercritical (sc) reaction media to develop new, environmentally-safer and selective processes for such important catalytic reactions as acid catalyzed 1-butene/isobutane alkylation to produce gasoline, skeletal isomerization of n-butane to isobutane and selective functional groups hydrogenations on supported catalysts. The goals include (i) the optimization of the cosolvent-based supercritical solid-acid alkylation process (recently developed in our laboratory) to obtain enhanced alkylate yields at high butene conversion; (ii) the application of the in situ sc decoking concept to extend the life of low-temperature, solid-acid skeletal isomerization catalysts; and (iii) the optimization of solid-catalyzed sc hydrogenation process by pressure-tuning solvent and transport properties in the near-critical region to achieve desired product selectivity and hydrogenation rates. Besides providing a better fundamental understanding of the physicochemical processes underlying heterogeneous fluid/solid catalysis in sc media, the catalyst systems developed in this research are likely to impact the refining and chemical industries by minimizing chemical waste while optimizing catalyst selectivity, efficiency and lifetime. Specifically, solid-acid catalyzed alkylation and isomerization processes with enhanced activity and product yields could emerge as commercially-viable, environmentally-safer alternatives to liquid-acid based processes. Continuous solid-catalyzed hydrogenation in sc media - characterized by pressure-tunable selectivities minimizing waste formation, enhanced reaction rates, and inherently safer operation due to decreased holdup of hazardous reagents in the reactor - could emerge as an attractive process for functional groups' hydrogenations, a subject critical to the fine chemicals, pharmaceutical and food industries.