钛硅分子筛膜单程催化甲乙酮氨氧化及其程序控制制备机制的研究

Methyl ethyl ketone oxime is an important organic fine chemicals in national economics. There is not excellence performance of methyl ethyl ketone ammoximation over titanium silicalite zeolite in a continuous slurry reactor. This project proposes the methyl ethyl ketone ammoximation over titanium silicalite zeolite membrane as a flow through catalytic membrane. Catalytic contact time between reactants and zeolite membrane thus is under controlled, and claimed as a priority of the zeolite catalytic membrane. This critically depends on preparation of the titanium silicalite zeolite membrane with especial structure (namely multi-layers, orientation, hydrophobic/hydrophilic), associated with excellent catalytic performance. The project thus suggests a programmed preparation strategy. A periodical secondary growth method, based on the secondary growth, then is proposed for preparing the zeolite membrane. Its crystallization temperature is periodically controlled, to obtain these especial membrane structure. These especial membrane structure will be revealed by XRD, SEM, and gas permeance etc. Based on such research, the project will also focus on adjusting the flow through contact time between the reactants and titanium silicate zeolite membrane, as well as optimizing reaction conditions namely reaction temperature, to improve the catalytic performance of the zeolite membrane. These research would reveal the flow through catalytic reaction principle and the programed preparation mechanism of the titanium silicalite zeolite. This is full of creative and scientific meaning for the non-traditional reaction process and materials’ chemical engineering.

甲乙酮肟是国民经济中重要的有机精细化工产品。在淤浆床等传统反应器中，钛硅分子筛催化甲乙酮氨氧化制备甲乙酮肟却存在性能不足。为提高催化性能，本项目提出钛硅分子筛膜单程催化甲乙酮氨氧化。膜催化优点在于它能控制反应物与分子筛膜催化剂的接触时间。它的关键前提是制备出具有特殊结构(如多层结构、取向性、亲/疏水性等)的钛硅分子筛膜，从而提高催化性能。对此，本项目提出了程序控制制备分子筛膜的策略，以及基于该策略的周期性二次生长法。这是指改进二次生长法，以周期的形式控制晶化过程的温度，从而获得特殊膜结构。此特殊结构将通过XRD、SEM、气体渗透等表征方法阐明。在此基础上，项目重点研究内容还包括调控反应物与钛硅分子筛膜的单程接触时间，并优化反应温度等工艺条件，以提高催化反应性能。上述研究将阐明钛硅分子筛膜的单程催化反应规律，及其程序控制制备机制。该研究在非传统反应过程及材料化学工程领域极具创新性和科学价值。

甲乙酮肟是国民经济中重要的有机精细化工产品。本项目研究了钛硅分子筛膜单程催化甲乙酮氨氧化。它的关键前提是制备出具有特殊结构(如多层结构、取向性、亲/疏水性等)的钛硅分子筛膜，从而提高催化性能。对此，本项目主要研究了程序控制制备分子筛膜的策略，以及基于该策略的周期性二次生长法。这种改进二次生长法，以周期的形式控制晶化过程的温度，调控了分子筛膜的生长，从而获得特殊的多层膜结构。此方法制备钛硅分子筛膜的过程中，与传统实心钛硅分子筛相比，空心钛硅分子筛能引导生长出具有（303）取向型多层结构钛硅分子筛膜，且具有较好的疏水性能。此特殊结构可以通过XRD、SEM、气体渗透等表征方法阐明。对此分子筛膜进行恰当的碱处理，能形成多级孔型分子筛膜。在获得上述分子筛膜的基础上，项目主要研究了调控反应物与钛硅分子筛膜的单程接触时间，用以提高催化反应性能。上述研究阐明了钛硅分子筛膜程序控制制备生长机制，并探索了非传统反应过程——单程膜催化反应的可行性。