表面接力催化低碳分子转化制备甲基丙烯酸甲酯的新催化体系研究

The transformation of low-carbon molecules to high-carbon and multifunctional chemicals is an efficient way for resource utilization. Methylmethacrylate is an important organic industrial product. So far, the synthesis of methylmethacrylate still has some disadvantages, such as generating pollution unavoidably and turn out to be a waste of resources. Thus, it is imperative to develop new routes for the synthesis of methylmethacrylate efficiently and environmentally-friendly. In our previous work, we found that the heterogeneous catalyst Ru/CeO2 could realize the synthesis of methyl propionate via the carbonylation of ethylene. The interfacial Lewis-acid base pair plays a key role in this reaction. Here, we propose to get as many Lewis acid-base pairs as possible by the maximization of the interface between Ru and CeO2 support. And then the great amount of Lewis acid-base pairs could catalyze the carbonylation of ethylene efficiently. Multifunctional micro-environment including interfacial Lewis acid-base sites and VPO acid sites will also be designed and prepared to realize the carbonylation of ethylene and Aldol condensation of methyl propionate and formaldehyde in one-pot. And finally, methylmethacrylate will be obtained by the "surface relay". Techno-economic analysis and life cycle assessment will be applied to evaluate the economic feasibility, energy consumption and environmental impact to guide the further research for this catalytic system.

由低碳分子构筑高碳、多官能团的高附加值化学品是资源优化利用的有效途径。甲基丙烯酸甲酯是一种重要的化工产品，目前，其制备方法不可避免产生污染和资源浪费，新技术的探索势在必行。我们前期发现多相Ru/CeO2可高效催化乙烯的羰基化反应制备丙酸甲酯，其中Ru与缺陷氧化铈界面处路易斯酸碱对起关键催化作用。本项目拟以乙烯等低碳小分子为原料，通过Ru与缺陷氧化铈之间的界面最大化，形成含量丰富的界面路易斯酸碱对，进而实现乙烯的羰基化反应高效制备丙酸甲酯；通过构建多中心协同的微化学环境，耦合乙烯的羰基化过程以及丙酸甲酯与甲醛Aldol缩合，通过“表面接力”，制备甲基丙烯酸甲酯；并通过该多相催化体系下的技术经济性与环境友好性分析，评估市场竞争力，指导优化该反应过程。

甲基丙烯酸甲酯是重要的化工原料，主要用于生产有机玻璃、表面涂料等，是高端材料的基础原料。然而，目前国内对于甲基丙烯酸甲酯的生成技术相对落后，生产原料来源受限或是过于依赖石油化工。因此，针对中国“富煤少油”的基本国情，研究煤基甲基丙烯酸甲酯的制备新技术势在必行。本项目首先以煤基甲醇、乙烯、一氧化碳等低碳小分子为原料，基于金属-氧化物多相催化剂的设计，发展出Ru基双金属体系，催化乙烯的甲氧基羰基化反应制备丙酸甲酯，同等条件下，催化活性与稳定性优于现有均相Pd基催化体系；在优选催化剂与条件下实现了反应体系从30mL到5L的规模放大；进而采用钒磷氧与铌基催化剂打通了丙酸甲酯与甲醛的缩合过程。上述研究为发展煤基甲基丙烯酸甲酯的多相催化制备新技术奠定基础。