甘油转化为环氧氯丙烷新工艺的分析-化学工程专业论文.docx

贵州大学 贵州大学 2009 届硕士学位论文 PAGE PAGE 1 摘 要 本论文以生物柴油副产物甘油为原料，采用甘油法制备环氧氯丙烷，着眼于 筛选出适合于制备环氧氯丙烷的活性高、产率好和低成本的固体碱催化剂，并对 环氧氯丙烷制备工艺进行了优化。采用人造沸石、氧化锌、氧化钙及 γ型三氧化 二铝为载体，各种碱金属和碱土金属氢氧化物和盐为活性组分，制备出了 28 种 负载型催化剂。以甘油为原料，通过两步法制备环氧氯丙烷，筛选出活性较高的 催化剂，并从制备方法、活性中心/载体配比、煅烧温度和煅烧时间等因素对活 性较高的催化剂制备条件进行优化。其中，催化剂 NaOH/人造沸石制备的最佳 条件为：浸渍法制备、活性组分与载体配比 7:10、煅烧温度 400 ℃、煅烧时间 3 h；并利用 Hammett 指示剂滴定法及红外光谱法对其进行了表征和催化机理的研 究。对 NaOH/人造沸石催化 1,3-二氯-2-丙醇制备环氧氯丙烷工艺进行了优化。 甘油制备 1,3-二氯-2-丙醇的最佳工艺条件为：在常压下，以乙酸为催化剂，催化 剂用量 3%wt、氯化氢与甘油摩尔比 6:1、反应温度 105 ℃，反应时间 5 h，在该 条件下 1,3-二氯-2-丙醇产率 55.0%以上；1,3-二氯-2-丙醇制备环氧氯丙烷的最佳 工艺条件为：在常压下，乙醚做溶剂，溶剂与 1,3-二氯-2-丙醇质量比 1:1，催化 剂与 1,3-二氯-2-丙醇摩尔比 1.1:1，反应温度 40 ℃,反应时间 4 h，在最佳工艺条 件下，环氧氯丙烷的产率在 50.0%以上。 关键词：甘油，1,3-二氯-2-丙醇，环氧氯丙烷，固体碱催化剂，表征 Abstract This paper mainly focused on optimizing the process of epichlorohydrin preparation using biodiesel by-product glycerol as meterial and selecting a solid base catalyst with high catalytic activity, good yield of Epichlorohydrin and low cost. Using artificial zeolite, ZnO, CaO and γ-Al2O3 as carrier, hydroxides and salts of alkali metals or alkali earth metals as active ingredients, 28 supported solid base catalysts were prepared. Catalyst with high catalytic activity was screened out in the process of epichlorohydrin preparation using glycerol as meterial by a two-step reaction, and the preparation of the catalyst with high catalytic activity was optimized in preparation method, ratio of active ingredients to carrier, calcination temperature and calcination time. Among all catalysts, the optimal preparation conditions of catalyst NaOH/artificial zeolite were as follows: inpregnation, ratio of active ingredients to carrier 7:10, calcination temperature 400 ℃ and calcination time 5 h.The characterization and catalytic mechnism researches of NaOH/artificial zeolite were carried out by means of Hammett indicator titration and IR spectroscopy. The preparation process of epichlorohydrin from glycerol catalyzed by NaOH/ artificial zeolite was optimized. The