负载型锆盐催化剂催化酯化反应的研究-化学；物理化学专业论文.docxVIP

摘 摘 要 摘 要 乙二醇单乙醚乙酸酯（EGEEA）是一种具有双官能团的应用广泛的优良溶剂，柠 檬酸三丁酯（TBC）是目前应用最广泛的增塑剂之一，这两种产品工业上多以浓硫酸作 催化剂直接酯化合成。然而，用硫酸作催化剂存在着设备腐蚀、污染环境、副反应多、 产品分离精制困难等缺点，因此用固体酸催化剂取代硫酸是合成工艺改革的关键。 本论文通过浸渍法制备了系列负载型锆盐催化剂，用于酯化反应合成乙二醇单乙醚 乙酸酯（EGEEA）和柠檬酸三丁酯（TBC）。采用 FT-IR、XRD、氮气吸附-脱附、EDS 等技术对催化剂进行了表征；用红外光谱、折光率和气相色谱对酯化产物进行了测定； 研究了催化剂的酸性、结构和组成对反应选择性和催化剂寿命的影响；并对酯化合成工 艺进行了优化，考察了不同载体、硫酸锆负载量、催化剂用量、反应温度、原料配比等 因素对酯化反应的影响，筛选出了最佳的催化剂组成和酯化反应条件。实验结果表明： 最佳载体为中性的活性炭（AC）和介孔分子筛 SBA-15；硫酸锆可在这些载体上充分分 散，而不影响载体的结构。这样的负载型硫酸锆催化剂具有中等酸强度（-11.4≤H0≤ -8.2），保证了在上述两个酯化反应中，目标酯产物的选择性均为 100％。在最佳负载量 的催化剂和最佳的酯化反应条件下，乙二醇单乙醚乙酸酯和柠檬酸三丁酯的产率均可达 98%～99%。催化剂可回收重复利用多次。 由于克服了工业用硫酸催化剂、均相催化剂以及其它固体酸催化剂的不足，加之具 有高活性、高选择性和可重复使用的特点，我们制备的负载型硫酸锆催化剂极具推广价 值和工业应用前景。 关键词：乙二醇单乙醚乙酸酯，柠檬酸三丁酯，硫酸锆，酯化反应 I Ab Abstract Abstract 2-ehoxyethanol acetate(EGEEA) is a excellent solvent which have double functional group and a wide range of application, tributyl citrate(TBC) is one of the most important plasticizing agents, the both products are synthesized by concentrated sulfuric acid catalyst. However, the concentrated sulfuric acid has many disadvantages, such as equipment corrosion, environmental pollution, many side-reactions and difficulties in separation of the products, one way to solve these problems is to use the solid acid catalyst in place of concentrated sulfuric acid. In this thesis, a series of supported zirconium sulfate catalysts were prepared by impregnation and were used in the synthesis of 2-ehoxyethanol acetate(EGEEA), tributyl citrate(TBC). The catalysts were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), N2 adsorption-desorption and x-ray energy dispersive spectrometry (EDS); the products were tested by infrared spectroscopy (FT-IR), refractive index method, gas chromatography (GC); the acidity, structure, composition of catalyst to the effect of selectivity and recycle performance were studied; the technological parameters were optimized, the influences of synthesis conditions such as different support, the loading, the quanti