Solid-Catalyzed Reactions in Supercritical Reaction Media

摘要：本项目将合理利用超临界（sc）反应介质，为酸催化1-丁烯/异丁烷烷基化制汽油、正丁烷骨架异构化制异丁烷、负载催化剂上选择性官能团加氢等重要催化反应开发新的、环保的、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（最近在我们实验室开发），以在高丁烯转化率下获得更高的烷基酸收率；（ii）原位sc脱焦概念的应用，以延长低温固体-酸骨架异构化催化剂的寿命；（iii）通过压力调节溶剂和近临界区域的输运性质来优化固体催化sc加氢过程，以达到理想的产物选择性和加氢速率。除了对sc介质中流体/固体非均相催化的物理化学过程提供更好的基础理解外，本研究开发的催化剂系统还可能通过最大限度地减少化学废物，同时优化催化剂的选择性、效率和寿命，对炼油和化学工业产生影响。具体来说，固体酸催化的烷基化和异构化工艺具有更高的活性和产品收率，可以作为商业上可行的、更环保的液体酸基工艺的替代品。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产生，提高了反应速率，并且由于反应器中有害试剂的滞留率降低而具有固有的安全性，这可能成为官能团加氢的一个有吸引力的过程，这对精细化学品，制药和食品工业至关重要。

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.