【作者】 黄秋锋；

【导师】 林深；

【作者基本信息】 福建师范大学 ， 物理化学， 2004， 硕士

【摘要】 1，4-丁炔二醇（BD）经催化加氢制备的1，4-丁二醇（BDO）是一种重要的有机合成中间体，用于生产γ-丁内酯（GBL），四氢呋喃（THF），聚二苯二甲酸丁二醇酯（PBT）等。近年来因PBT等衍生物的需求骤增，我国对BDO的需求量大幅度增长。BD可由甲醛乙炔化合成，我国发展BD生产起步较晚，生产规模小，工艺也比较落后，并且催化剂主要从国外进口，价格昂贵。因此，采用自行研制的高效乙炔化催化剂是降低生产成本的关键。本文采用淤浆床低压法，用浸渍法制备了以HZSM-5、H-β-zeolite、活性炭为载体的铜铋复合氧化物催化剂，研究了它们对甲醛乙炔化反应的催化性能，结果表明以H-ZSM-5为载体的铜铋复合氧化物催化剂对甲醛乙炔化反应具有很好的催化活性。在363K、常压、催化剂和甲醛（37％）用量比为5g:50ml的条件下，1，4-丁炔二醇产率约92％，选择性98.8％，催化活性优于有关文献报道的水平，并且具有选择性好、活性稳定、制备简单等优点，具有工业化应用化前景。同时以CuO／Bi₂O₃／ZSM-5为催化剂，在淤浆鼓泡床中对甲醛乙炔化反应的工艺条件（反应温度、空速、催化剂用量、甲醛初浓度等）进行了优化，并对该反应的动力学做了初步探讨，结果表明：在消除内、外扩散影响的情况下，反应对甲醛呈现一级反应。 采用X射线粉末衍射（XRD）、红外光谱（IR）、程序升温还原（TPR）、紫外-可见漫反射（DRS）、热重（TG）等分析手段对催化剂进行了表征。着重探讨了不同Cu和Bi负载量对催化剂结构的影响以及对催化活性和选择性的影响。更多还原

【Abstract】 As an important organic intermediate, l,4-butynediol(BD) is widely applied to manufacture a variety of chemicals such as -butanolide (GBL), tetrahydrofuran (THF), polybutylene terephthalate(PBT). The technology of ethynylation for producing BD developed in recent years in China, and the catalysts for this reaction process are mainly depend on import. The highly active catalysts for ethynylation are the key to lower production cost.In this thesis, the CuO/Bi2O3/ZSM-5 catalyst with high activity and selectivity for synthesis of BD by slurry bed was prepared. The reaction was carried out at 363K and atmospheric pressure, 5g catalyst and 50ml formaldehyde (37%)solution were loaded into the reactor, giving a 92% yield of BD with nearly 98.8% BD selectivity. The yield and selectivity of BD are much higher than the other catalysts that have been presented in the literature.The effect of the reaction kinetics conditions on ethynylation of formaldehyde was investigated. Under the conditions without inside and outside diffusion, the curves of the concentration of formaldehyde versus time over the CuO/Bi2O3/ZSM-5 catalyst were measured. It was founded that the reaction exhibits first order as for formaldehyde.The catalysts were characterized by BET, XRD, TPR, UVDR , TGtechniques.更多还原