稀土复合氧化物乙烷氧氯化催化剂设计与协同匹配作用

Integrating the comprehensive utilization of associated gas from natural gas of Inner Mongolia with the rich resources such as rare earth, Cu, Mn and Fe in our country, we plan to prepare several new rare-earth composite oxides by the glucose sol-gel method such as La2CuMnO6 and La2CuO4 which have not been reported for the novel ethane oxychlorination catalytic reaction to vinyl chloride. The aim of this design is to steady Cu ion by setting it in the lattice of rare-earth composite oxides, and to get over disadvantages of volatilization of traditional chloride catalysts at higher temperature. By changing the synthesis conditions ,doping, loading and compounding, we can study their catalytic activity on this reaction and optimize the design of the catalysts, explore the mechanism of catalytic reaction and improve their catalytic efficiency. We aimed at reveal their catalytic mechanism by means of mastering some rules on the preparation condition and designing of rare-earth complex oxides. In addition, we intend to explore the relationship between electromagnetic property of catalysts and their catalytic performance to lay the foundation of the preparation of rare-earth oxides catalysts for ethane oxychlorination reaction. The accomplishment of this project will promote the vinyl chloride industry and rare-earth chemical engineering, natural gas chemical engineering, coal chemical industry, environmental conservation and the deep processing of ore resources in China.

结合我国我区天然气中的伴生物乙烷的综合利用和内蒙古丰富稀土及铜、铁、锰等资源优势,拟选择葡萄糖溶胶-凝胶等方法设计制备在乙烷氧氯化制氯乙烯新型催化反应中未见研究报道的几种新型La2CuMnO6和La2CuO4等稀土复合物催化剂，将活性Cu离子镶嵌在稳定的稀土复合氧化物晶格中，增加Cu离子的稳定性，克服传统金属氯化物催化剂高温下容易挥发的缺点。通过制备条件的改变，离子掺杂、负载与复合手段对所制备的催化剂进行优化设计，研究其对乙烷氧氯化反应的催化活性和催化剂协同匹配作用,探索其催化反应机理。掌握一些稀土复合氧化物型乙烷氧氯化催化剂的制备和设计规律，揭示稀土复合氧化物催化剂在乙烷氧氯化反应的催化机制。阐述催化剂磁电性能和催化性能之间的关系。为研制和设计稀土复合氧化物型乙烷氧氯化催化剂奠定科学基础。项目的完成会对我国氯乙烯工业和稀土化工、天然气化工、煤化工、环境保护及矿产资源深加工有促进作用。

本四年期地区项目主要开展了五个方面的研究工作，一是钴系稀土负载型钙钛矿催化剂的制备、改性及其对乙烷氧氯化反应的催化性能的研究；二是锰系稀土负载型钙钛矿催化剂的制备、掺杂、修饰及其对乙烷氧氯化反应的催化性能的研究；三是氯化铁基催化剂的制备、改进及其对乙烷氧氯化反应的性能研究；四是尖晶石型催化剂的制备、掺杂及其对乙烷氧氯化反应的性能研究；五是稀土锆基复合氧化物对乙烷氧氯化反应性能初步探索。研究过程中取得了一些成果和关键的数据：研制了不同种类的稀土复合氧化物如双钙钛矿型催化剂La2BCoO6-CuCl2-γ-Al2O3(B=Fe，Al，Mn)，以及K掺杂的La1.7K0.3NiMnO6-CuCl2-γ-Al2O3催化剂，对这类催化剂合成方法有了一定的掌握，乙烷转化率可达100%，氯乙烯选择性达到59.4%，另外拓展了乙烷氧氯化反应催化剂的研究范围，制备了铁基催化剂和尖晶石型催化剂，其中氯乙烯选择性最高可达74%，阐述了这些催化剂的催化性能及机理，解释了其协同匹配作用。研究期间在《Journal of Catalysis》，《Dalton Transactions》，《Journal of Industrial and Engineering Chemistry》期刊上发表论文共3篇。已授权国家发明专利1项（题目：一种负载型钙钛矿乙烷氧氯化制氯乙烯催化剂的制备方法，专利号：ZL201510411645.9），公开国家发明专利3项（题目：一种应用于乙烷氧氯化制氯乙烯反应的铁基催化剂制备方法，申请公布号：CN107469842A；题目：一种乙烷氧氯化制氯乙烯尖晶石型催化剂制备方法，申请公布号：CN110479298A；题目：一种乙烷氧氯化制氯乙烯稀土锆基催化剂制备方法，申请公布号：CN110479324A）。在第二十一届全国催化学术会议等国内国际会议上有7篇论文进行学术交流。