介孔分子筛催化剂上亚油酸甲酯与纤维素共催化制备烷基苯及正构烷烃的基础研究

Linoleic acid glyceride was one of main components in lipids including microalgae oil and crop oil. In this project, the co-catalysis of linoleic acid methyl ester and cellulose was taken as a model reaction to simulate the co-catalysis of biomass and oil grease so that the whole reaction network could be simplified. Alkyl benzenes and n-alkanes were obtained via this new chemical conversion model. The mesoporous molecular sieves (MCM-41) supported carbide catalysts with high selectivity and catalytic activity for the co-catalytic reaction of linoleic acid methyl ester and cellulose were prepared and screened. The key issue was about the control of the length of carbon - carbon chain (include alkyl and alkane chains) through the control of catalysts structure and morphology ，structural design，process intensification of the co-catalytic reaction of linoleic acid methyl ester and cellulose. In this study, the effect of some important factors (including the composition of the catalyst component, the electronic state and microstructure, as well as the dispersion and distribution of active component on the carrier) on the co-catalytic reaction of linoleic acid methyl ester and cellulose would be focused. The implementation of this project could not only provide basic research on the preparation of novel shape selective catalysts, but also provide new ideas and theoretical basis for the exploration of the ecological utilization of bulk chemicals from biomass resources , especially for the conversion of microalgae and oil crops.

亚油酸脂是油脂，包括微藻油脂及含油作物油脂的主要成分之一。本课题以亚油酸甲酯与纤维素生成烷基化苯及正构烷烃为模型反应，模拟油脂与生物质共催化反应，以简化其反应网络。采用介孔分子筛催化剂（MCM-41）为载体，金属碳化物为活性组分，制备和筛选高效选择性介孔分子筛负载型催化剂。旨在通过催化剂的孔结构及形貌的调控、结构设计以及亚油酸甲酯与纤维素共催化反应的过程强化与控制，实现反应过程中，催化剂对苯环上的碳链长度以及正构烷烃碳链长度可控性的关键问题。研究过程中将着重探索催化剂活性组分的组成、电子状态和微观结构，以及活性组分在载体上的分散与分布等对亚油酸甲酯与纤维素共催化过程的影响，尤其是对正构烷烃及高附加值烷基苯的碳链长度分布及得率的调控。本项目的实施将为进一步研究高效择型催化剂奠定基础，同时也为 '实现以生物质及油脂为原料制备大宗化学品的资源生态化的有效利用'提供理论基础及新的思路。

本项目主要是以亚油酸甲酯（植物油脂的组分之一）作为模拟化合物， 将其与纤维素共脱氧液化制备烷烃类化合物，为生物质转化制备液体燃料提供理论指导。通过本项目基金的资助，本项工作在转化机理，产物分析，催化剂的筛选，优化烷烃燃油的热值及含氧量等方面取得了重要进展。 通过研究发现，在转化过 程中，水的生成至关重要，导致了苯环的烷基化取代了苯环的酚羟基化，最终产物主要以烷基苯为主，完全去除了酚类产物。这一重要结论为催化剂的研究与筛选提供了重要的科学依据。 为进一步抑制烷基与苯环的烷基化，促进其与其他烷基的耦合，形成烷烃类燃油产品，又开展了分子筛负载碳化物的催化剂的研究，进一步对产物进行优化，最终确定 W2C/MCM-41 催化剂因其合适的孔径及催化 活性，成为优化脱氧燃油的最佳催化剂。 该项工作，该项工作，提出了新的可再生生物质资 源转化成燃油的工艺路线，并为合理的优化该项工艺合成的脱氧燃油的提供了可 行的催化设计方案，作为现有化石能源燃料的补充，该项目的顺利完成具有重要 的现实意义。