哌嗪的合成研究

【作者】 鲍金勇；

【导师】 刘荣杰；

【作者基本信息】 西北大学 ， 化学工艺， 2004， 硕士

【摘要】 本文简要介绍了无水哌嗪的物理化学性质、生产状况以及相关用途。本研究在查阅国内外文献的基础上，对目前各种合成工艺路线进行了分析与比较，最终选定以乙二胺为原料常压气固相催化合成哌嗪的工艺路线。通过离子交换法制备了Ca-ZSM-5型分子筛催化剂，并定量讨论了分子筛的硅铝比值、交换的离子以及制备条件对反应的影响。通过单因素试验和正交试验对合成过程的影响因素进行了研究，确定了合成无水哌嗪的最佳工艺条件。以气固相反应动力学的相关理论为指导，建立了该反应过程的宏观动力学模型。最后以试验相关数据为依据，对建成年产300吨无水哌嗪的工厂作了经济前景预测和分析，本文对该工艺的系统研究为该工艺工业化生产提供了理论依据和实验基础。 结果表明： 1．采用离子交换法制备的Ca-ZSM-5催化剂作为脱氨环化反应的催化剂具有较好的活性和选择性。通过实验所确定的最佳制备条件为：硅铝比值为50的ZSM-5型分子筛；1.0mol／L的CaCl₂溶液在25℃下浸渍48hr：在110℃条件下干燥3hr左右：最后在500℃下活化6hr。 2．合成实验所确定的适宜工艺条件为：原料液浓度40％（质量分数），反应温度360±5℃，反应空速为0.016mol·g^-1·hr^-1。在此工艺条件下，乙二胺转化率为95.30％，哌嗪收率为65.44％，三乙烯二胺收率为25.66％，总收率为91.10％；哌嗪的纯度为99.3％，三乙烯二胺的纯度为98.4％ 3．对该反应进行的动力学研究表明该反应的级数近似为1.45级，在330℃-360℃下装置所在的条件内，宏观动力学模型为 Rm=3.10×10⁶exp（-8.624×10³/T）C_m^1.45。 4．以乙二胺为原料常压气相法合成无水哌嗪的工艺路线是可行的，经济前景预测和分析表明该产品具有较好的经济效益和社会效益。更多还原

【Abstract】 The paper has reviewed physical and chemical properties, production status and related uses of piperazine. Based on consulting the domestic and international reference documents, deamination of ethylenediamine on normal pressure is determined by a comparison of processes available. Modified Ca-ZSM-5 zeolite catalysts are prepared with the method of ion-exchange. The effects of the ratio of silicon to aluminum, ions used to exchange and preparation conditions on the reaction was discussed in quantity. Then monofactor method and multifactor orthogonalizing design method are applied to get the optimum processing conditions in preparation of piperazine. After that the macrokinetics model on the gas-liquid reaction is established based on related theories. Finally, the economic analysis on production of 300t/a piperazine was made on the basis of the results in the experiment.The following have been obtained through lots of experiments.1. Higher activity and selectivity of Ca-ZSM-5 catalyst prepared by the methodof ion-exchange was obtained. The optimum conditions for preparing catalysts: H-ZSM-5 zeolite catalysts with the ratio of silicon to aluminum 50; infused for 48 hours at 25℃ in 1.0mol/L CaCl2; dried for 3 hours at 110℃; activated for 6 hours at 500℃.2. The optimum processing conditions: the concentration of EDA 40%(mass fraction); reaction temperature 360±5℃; space velocity 0.016mol.g-1.hr-1. In these conditions, the conversition of EDA is 95.30%, the yield of PA is 65.44%, the yield of TEDA is 25.66% and the total is 91.10%. At the same time, the purity of PA is 99.3% and the purity of TEDA is 98.4%.3. The study of macrokinetics shows that the apparent reaction kinetics is approximately in 1.45-order. The established model in 330℃-360℃ is as follow:4. It is possible to synthesize piperazine using EDA as raw material. The economic analysis on production of 300t/a piperazine shows that the process has great social and economic benifits.更多还原