Solid-Catalyzed Reactions in Supercritical Reaction Media

摘要- Subramaniam - 9816969 本研究计画将合理开发超临界反应介质，以开发对环境更安全、选择性更高的新工艺，应用于酸催化1-丁烯/异丁烷烷基化制汽油、正丁烷骨架异构化制异丁烷、负载型催化剂上选择性官能团加氢等重要催化反应。 目标包括：（1）共溶剂型超临界固体酸烷基化过程的优化（ii）原位SC除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;和（iii）通过在近临界区域中压力调节溶剂和传输性质来优化固体催化的SC氢化方法，以获得所需的产物选择性和氢化速率。 除了提供了一个更好的基本了解的物理化学过程的非均相流体/固体催化在sc介质中，在这项研究中开发的催化剂系统可能会影响炼油和化学工业，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。 具体地，具有增强的活性和产物产率的固体酸催化的烷基化和异构化方法可以作为基于液体酸的方法的商业上可行的、环境上更安全的替代方案出现。 在sc介质中的连续固体催化氢化-其特征在于压力可调的选择性，最大限度地减少废物形成，提高反应速率，以及由于反应器中危险试剂的滞留量减少而固有的更安全的操作-可能成为官能团氢化的有吸引力的方法，这是精细化学品，制药和食品工业的关键主题。

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.