有机硅单体合成反应新型Cu-CuCl-CuCl2催化剂及其作用机理的基础研究

Dimethyldichlorosilane (M2) was the most important monomer in organosilane industry, which is synthesized via Rochow reaction with gas MeCl and solid Silicon over copper-based catalysts together with some trace promoters. The continuous change of the composition of mixed solid reactant and catalysts during reaction process leads to the difficulty in fully understanding the catalytic mechanism, which is a big challenge for academic research and organosilane industry. Based on the new copper-based composite catalyst (Cu-CuCl-CuCl2) developed in our previous work, this project will investigate the effects of size, morphology, and crystal face of copper-based catalyst particles on the catalytic properties. The molecular adsorption and desorption behavior of reactants and products on the surface of catalysts, as well as their conversion characteristics, will be measured for understanding the molecule diffusion within the solid structures and obtaining the reaction dynamics. With the assistance of online product analysis and surface reaction of butadiene pulse technologies, the distribution, concentration, and stability of active species on the surface of contact masses were examined to disclose the evolution and synergistic effect of multiple components. The intensive exploration of the Rochow catalytic reaction in this project will contribute to the complicated gas-solid catalytic theory and will be significant in the development of copper-based catalyst with high performance for organosilane industry.

二甲基二氯硅烷（M2）是有机硅行业最重要的单体，通过气(MeCl)-固(Si粉+Cu基催化剂+助催化剂)相催化反应进行合成。由于反应过程涉及Si粉消耗，混合固相化学组成不断变化，致使该反应催化剂作用机理研究难度较大，阻碍了有机硅行业单体合成的进一步提高。本申请拟在已开发新型Cu-CuCl-CuCl2催化剂的基础上，通过调控组元粒径、形貌和晶面，改变表面反应物和产物分子的吸-脱附及其反应行为，探索催化剂结构与气固相扩散系数及其反应性能的对应关系；结合在线性能评价、丁二烯脉冲表面反应和触体表面物性分析，考察表面活性物种类型、浓度及其稳定性，研究单组元作用规律及其协同效应，探索CuCl2组元对单体合成反应稳定期和M2选择性的影响规律。本申请的完成将深化气-固催化理论和实验研究方法，对新型高效铜催化剂的研制意义重大。

有机硅材料广泛应用于国民经济各个领域。二甲基二氯硅烷（M2）是有机硅行业最重要的单体，目前，M2选择性和稳定运行周期有待于进一步改善。本项目开发了新型Cu-CuCl-CuCl2体系催化剂，分别采用球磨法和溶剂热合成法进行了片状铜粉和规整形貌CuCl的可控合成，形貌均一、大小可控，制备方法简单易行，适合于大规模生产；结合性能评价，片状铜粉有利于增加表面反应几率，规整形貌CuCl则表现出高暴露度的活性晶面（200），两者可促进活性CuxSi合金相的形成，加速单体合成反应的发生。在优化制备的Cu-CuCl-CuCl2体系催化剂上，表现出较高的硅粉转化率41.0%和M2选择性87.9%，这将为有机硅单体合成催化剂的研究提供了一条新思路。