聚合离子液体微凝胶可控合成及催化烷烃-烯烃偶联新过程

Alkylate is an essential ingredient in the quality upgrading and clean utilization of gasoline. However, the existing sulfuric acid and hydrofluoric acid alkylation processes generally have serious environmental pollution problems. This project focused on the controllable synthesis of polymerized ionic liquids microgel to solve the low product selection and difficult recycling problems in current ionic liquid catalysis of alkane-olefin coupling process. This polymerized ionic liquids microgel catalyst combines the dual advantages of anion and cation scavenging of ionic liquid and the stable and controllable structure of polymer. The catalytic activity and selectivity was effectively controlled by adjusting the acidity of the anions, the coordination of the cations, and the polarity of the polymerized ionic liquids. The controllable synthesis method of the polymerized ionic liquid microgel was established. The structure-activity relationship between its structure control and the catalytic performance was investigated and the catalytic mechanism of alkane-olefin coupling reaction was obtained. This research work will provide theoretical guidance and technology support for the development of alkane-olefin coupling process.

烷基化油是汽油品质升级和清洁化不可或缺的调和组分。而现行的硫酸法和氢氟酸法烷基油生产工艺环境污染问题严重。本项目结合离子液体单体阴阳离子可调变和聚合物结构稳定可控的双重优点，开发聚合离子液体微凝胶新型催化剂，解决目前离子液体催化烷烃-烯烃偶联过程中普遍存在的产品选择性低、催化剂循环利用困难的问题。通过调节阴离子的酸性、阳离子的配位性及聚合离子液体的极性实现对其催化活性和选择性的有效调控，建立聚合离子液体微凝胶的可控合成方法及催化性能定向调控机制，研究催化剂结构与偶联反应性能之间的构效关系，探明聚合离子液体微凝胶催化烷烃-烯烃偶联反应机理，为烷烃-烯烃偶联反应催化剂开发和工艺绿色化提供理论指导和技术支撑。

以异辛烷为主要成分的烷基化油是汽油品质升级和清洁化不可或缺的调和组分。现行硫酸和氢氟酸工艺设备腐蚀严重、潜在环境污染危害大。开发环境友好的新型碳四偶联催化体系一直是世界炼油工业最具挑战性的课题。本项目针对异丁烷/丁烯偶联过程，设计合成离子液体及聚合离子液体催化体系，研究阴阳离子结构对催化体系酸性调节的规律，离子液体结构与催化性能之间构效关系，并结合分子模拟对催化体系的偶联作用机制进行解析。研究结果表明，B-L双酸体系催化效果更佳，其中Et3NHCl·1.6AlCl3与hfipOSO3H体系催化下，复合体系中B酸作用下羟基氢解离更容易，催化活性增强，2-丁烯的转化率为98.7%，C8和TMP选择性分别为83.8%和75.3%，烷基化油RON值为95.3。乙烯基咪唑酸性聚合离子液体与Et3NHCl·1.6AlCl3·CuCl复合体系活性稳定，连续反应50min产物RON值可维持在90以上。酸性聚合离子液体催化异丁烯偶联反应转化率接近100%，二聚体和三聚体选择性大于90%，有望在烯烃偶联反应中发挥更大的作用。