乙炔和甲酸甲酯催化合成丙烯酸甲酯研究.doc

...页眉....页脚乙炔和甲酸甲酯催化合成丙烯酸甲酯的研究——镍基催化剂的制备及丙烯酸甲酯常压合成初探摘要随着甲酸甲酯工业化的实现, 加速开发利用其下游产品日益成为普遍关心的研究课题。自从 198 3 年, Sneeden 等人的开创工作以来, 利用甲酸甲酯与不饱和的加氢酯化反应合成酯, 在近二十年来逐渐受人关注。利用甲酸甲酯替代 CO/CH 3 OH 参与相当成熟的 Reppe 反应: CH 2 =CH 2 +CO +CH 3 OH CH 3 CH 2 COOCH 3 CH 2 =CH 2+ HCOOCH 3 CH 3 CH 2 COOCH 3 一方面解决了 CO 的存储和运输问题,另一方面反应的工艺条件在一定程度上得到优化。在甲酸甲酯与乙炔加氢酯化均相催化结果的基础上,我们对本反应进行更进一步探索: CH ≡ CH +HCOOCH 3 CH 2 =CHCOOCH 3 本实验室利用固定床反应器,对甲酸甲酯与乙炔的加氢酯化反应进行了探索性研究。通过大量的催化剂筛选工作,发现只有镍催化剂对目标反应有较好的活性,而且氧化态的镍是催化反应的活性中心,金属态的镍对目标反应没有催化活性。对载体也进行了一定的筛选,载体不仅起到稳定活性组份的作用,而且其与活性组分的作用对反应性能也有一定的影响。对本反应的工艺条件进行了优化,反应温度、反应总压、原料配比、反应时间对反应都有很大影响。甲酸甲酯与乙炔的加氢酯化反应和甲酸甲酯的脱碳反应是一对竞争反应,当丙烯酸甲酯的选择性高时, 甲醇的产物就少。相反地, 大量的甲酸甲酯发生脱碳反应时, 丙烯酸甲酯的选择性就低。因此丙烯酸甲酯的选择性与甲醇的生成具有相关性。关键词: 甲酸甲酯乙炔丙烯酸甲酯加氢酯化...页眉....页脚 C atalytic S ynthesis ofM ethyl M ethacrylate by Acetylene and M ethyl F ormate —— Preparation of Nickel-based C atalysts and Low Pressure Synthesis of acrylic acid methyl ester Undergraduate:QIN Jinfeng Advisor:WANG Wei Abstract With the industrial realization of methyl formate , considerable attention has been paid to the uses and developments of its downstream products . Since the pioneering work of Sneeden and co-workers in1 986 , special attention has also been devoted to the hydroesterification of alkene using methyl formate instead of CO/CH 3 OH for synthesis of esters in two decades . The Reppe reaction by using methyl formate instead of CO/CH 3 OH was given as follows : CH 2 =CH 2 +CO +CH 3 OH CH 3 CH 2 COOCH 3 CH 2 =CH 2+ HCOOCH 3 CH 3 CH 2 COOCH 3 Via methyl formate , firstly the transport and handling CO/CH 3 OH at locations where the latter are difficult to obtain or to handle can be simplified ; Secondly the reaction condition was optimized . The hydroesterification of acetylene with methyl formate for synthesis of methyl acrylate has been found to proceeds uccessfully , We make further study on the reaction in fixed-bed : CH ≡ CH + HCOOCH 3 CH 2 =CHCOOCH 3 The hydroesterification of acetylene with methyl formate for synthesis of