填料型复合氧化物催化合成ε-己内酯反应过程的集成及机理研究

Ε-caprolactone is an important intermediate for organic synthesis and has wide applications.in material field. At present, ε-caprolactone is prepared from indirectly oxidized cyclohexanone by two-steps in a tank reactor. However, there are many problems for this, such as complicated recovery of catalysts, long and non-continuous product process, and easy self-polymerization and hydrolysis of ε-caprolactone during reaction process. These have an effect on industrialization of ε-caprolactone and development of downstream products. In this project, a supported filler-typed catalyst will be prepared and integration of two-steps reaction processes will be realized to synthesis ε-caprolactone from peroxidation of organic acids and oxidation of cyclohexanone in a three-stage catalytic distillation reactor, and so are unit operations for concentration of hydrogen peroxide and separation of reaction solutions. Those will make them possible safe control on continuous production of ε-caprolactone and comprehensive utilization of energy. By some simulation software, such as Aspen-plus and FLUENT6.2, the informations will be gotten about affection of sizes and motion trails of liquid droplets and entrainment on integrated reaction processes, and then strengthening mechanism of integrated reaction processes can be researched for different structure of reactors by taking cold and thermal model during reaction processes, at the same time, it will provide theoretical reference data for industrial design after measurement and association on thermodynamic data of relevant systems as well as study on reaction mechanisms of integrated processes.

ε-己内酯是一种重要的有机合成中间体，在材料领域具有广泛的应用。目前ε-己内酯的合成都采用釜式两步间接氧化环己酮法，但该工艺一直存在催化剂的回收难，不能连续化生产，工艺流程及反应时间很长、反应过程ε-己内酯易自聚合和水解反应等问题，阻碍了ε-己内酯的工业化和下游产品的开发。本项目通过研制一种高效负载型催化剂填料、利用三段式填料催化精馏反应器实现有机酸的过氧化与环己酮氧化合成ε-己内酯两步反应过程的集成，以及双氧水的浓缩与反应液的分离等单元操作的一体化，实现ε-己内酯合成连续化的安全可控和能量的综合利用。借助Aspen-plus、FLUENT6.2模拟软件获取流体液滴、雾沫等的尺寸及运动轨迹对集成后反应过程影响的信息；采用反应过程的冷、热模实验探索不同反应器结构对集成反应过程的强化机理；通过相关物系热力学数据的测定和关联及对过程集成后反应机理的研究为工业化设计提供参考理论数据。

ε-己内酯是一种重要的有机合成中间体，在材料领域具有广泛的应用，但其生产一直采用两步法间接氧化环己酮合成ε-己内酯间歇反应工艺，难以实现规模化生产。本项目研制出了MgxSnyWzO三元复合氧化物涂布负载型蜂窝陶瓷催化剂填料并用于三段式催化精馏反应器，实现了有机酸的过氧化与环己酮氧化合成ε-己内酯两步反应的耦合，以及双氧水的提浓与反应液的分离等单元操作的集成，进而达到了ε-己内酯合成工艺的连续化和能量的综合利用的目的。该工艺下ε-己内酯选择性及环己酮转化率分别为87.89%、90.0%。此外通过热力学和动力学研究分别得到ε-己内酯合成所涉及的相关组分的二元体系的溶液模型参数及本征和宏观动力学方程，通过ASPEN PLUS及 FLUENT6.2模拟软件对年产200吨ε-己内酯连续催化反应精馏生产过程进行模拟，获取了其三段式催化精馏反应器的结构及其工艺参数，为我国ε-己内酯合成的工业化及下游产品的开发提供支撑数据。在项目实施过程发表期刊论文9篇，申请发明专利3项、已授权1项。