联产哌嗪和N-乙基哌嗪的工艺研究

发布时间：2018-03-13 12:16

本文选题：哌嗪　切入点：N-乙基哌嗪　出处：《浙江大学》2016年硕士论文　论文类型：学位论文

【摘要】：哌嗪和N-乙基哌嗪是重要的有机中间体,广泛用于医药、染料、材料等领域,国内外需求量大。文献报道的N-乙基哌嗪的工艺路线是以哌嗪为原料,与卤代烷、乙醇或乙醛催化反应,经精馏得到纯品。该工艺使用的原料哌嗪价格较高,合成工艺复杂。因此开发一条经济、环保、高效的N-乙基哌嗪的生产工艺意义重大。为了解决上述问题,为N-乙基哌嗪提供一条适合工业生产的工艺路线,本文探索了以N-p-羟乙基乙二胺(下文以AEEA代称)和乙醇为起始原料,在自主研发的Cu3oCr10/γ-Al_2O_3催化体系经分子内催化氨化、N-乙基化合成哌嗪和N-乙基哌嗪,经过精馏提纯获得两个产品,具有成产成本低、过程较简单、节约投资等优点。本文研究了AEEA与乙醇为原料联产哌嗪和N-乙基哌嗪工艺的适宜催化剂。得到了合适的催化剂参数,分别是催化剂的活性成分金属Cu的含量为30wt%,助催化剂金属Cr的含量为10%,载体为γ-Al_2O_3,催化剂的制备方法为捏合挤条法。在该Cu_(30)Cr_(10)/γ-Al_2O_3催化剂的催化作用下与适宜的反应条件下,原料AEEA的转化率达99.2%,哌嗪的选择性为70.1%,N-乙基哌嗪的选择性为27.4%。本文开发了AEEA与乙醇溶液制备哌嗪联产N-乙基哌嗪的工艺。在Cu_(30)Cr_(10)/γ-Al_2O_3的脱氢/加氢催化体系,实现了AEEA分子催化胺化制备哌嗪联产N-乙基哌嗪。得到了最佳反应条件：使用Cu_(30)Cr_(10)/γ-Al_2O_3催化剂,催化剂体积51 mL,在200℃和3 MPa的氢压下,40%的AEEA-乙醇溶液以0.5 ml/min的速度通过催化剂床层。通过小试精馏,得到哌嗪和N-乙基哌嗪的精馏温度范围分别为145～148℃和154～156℃。在该温度点提纯得到620g哌嗪和257g N-乙基哌嗪,产品总计877g,且两种产品含量均为99.5%以上。本文对Cu_(30)Cr_(10)/γ-Al_2O_3在AEEA与乙醇催化氨化合成哌嗪联产N-乙基哌嗪的工艺中进行稳定性试验。结果表明,该催化剂在分子内醇催化胺化合成哌嗪的反应中不仅表现出了较高的活性而且具有良好的催化剂稳定性；此催化体系是一个非常优异分子内醇的催化胺化合成环胺的反应体系,可用于工业化生产,并非常有必要进行推广研究。本文在中试车间进行了放大生产,采用直径为100cm,高度为150cm的高压固定床,500L高压反应釜,以及塔节直径为300mm的精馏塔进行反应。适宜的工艺参数为：反应温度范围195～205℃,氢气压力范围2.9～3.3 MPa,原料AEEA与乙醇比例为40%,原料进料速度为150～200 L/h。在该工艺条件下,哌嗪和N-乙基哌嗪的收率为88%。通过中试生产确定该工艺适用于工业大生产。
[Abstract]:Piperazine and N- ethyl piperazine is an important organic intermediate, widely used in medicine, dye, materials and other fields, the demand at home and abroad. The process route N- ethyl piperazine is reported using piperazine as raw materials, and alkyl halides, ethanol or acetaldehyde catalytic reaction, the pure product is obtained by distillation. The process of the use of raw materials piperazine synthesis process is complex. The price is higher, so the development of an economy, environmental protection, production process N- ethyl piperazine efficient material. In order to solve the above problems, provide a suitable industrial production process for N- Ethylpiperazine, this paper explores N-p- hydroxyethylethylenediamine (hereinafter AEEA etc.) and ethanol as starting materials in Cu3oCr10/, gamma -Al_2O_3 catalytic system developed by intramolecular catalytic amination, N- synthesis of ethyl piperazine and N- ethyl piperazine by distillation and purification to obtain two products, has low production cost, simple process Single, saving investment and other advantages. This paper studies the AEEA and ethanol as a suitable catalyst for coproduction of piperazine and N- Ethylpiperazine process. The catalyst suitable parameters are obtained, the active component content of metal Cu catalyst is 30wt%, content of catalyst metal Cr 10% carrier gamma -Al_2O_3, catalyst preparation method the kneading extrusion method. In the Cu_ (30) Cr_ (10) / -Al_2O_3 catalyst under the catalysis of gamma and the optimum reaction conditions, the conversion of raw material AEEA rate was 99.2%, the selectivity of piperazine was 70.1%, selectivity of N- ethyl piperazine developed technology of AEEA and ethanol solution preparation and N- ethyl piperazine piperazine 27.4%. this paper. In the Cu_ (30) Cr_ (10) / -Al_2O_3 gamma dehydrogenation / hydrogenation catalyst system, realized the AEEA molecular catalytic amination preparation of piperazine N-ethylpiperazine. N- and the optimal reaction conditions were obtained: the use of Cu_ (30) Cr_ (10) / gamma -Al_2O_3 reminder Agent, catalyst volume of 51 mL at 200 DEG C and 3 MPa hydrogen pressure, AEEA- 40% ethanol solution at the speed of 0.5 ml/min through the catalyst bed. Through the test by distillation, distillation temperature range of piperazine and N- ethyl piperazine were 145~148 degrees and 154~156 degrees. In the temperature of purified 620g piperazine 257g and N- Ethylpiperazine products, a total of 877g, and the two content of the product was more than 99.5%. The Cu_ (30) Cr_ (10) / gamma -Al_2O_3 test for stability in the process of synthesis of piperazine AEEA and ethanol catalytic amination of ethyl piperazine in CO production of N-. The results showed that the catalyst in the intermolecular catalytic amination of alcohols synthesis piperazine reaction not only show high activity and stability of catalyst has good catalytic reaction system; this system is a very excellent catalytic amination of intramolecular cyclic amine alcohol synthesis, can be used for industrial production, not Often is necessary to promote research. Based on the test of large scale production, with the diameter of 100cm, height of high pressure fixed bed 150cm, 500L high pressure reactor, and the tower section diameter 300mm column reaction. The suitable process parameters are as follows: the reaction temperature range of 195~205 DEG C, hydrogen pressure range 2.9 ~ 3.3 MPa, AEEA and ethanol feedstock ratio was 40%, feed rate is 150~200 L/h. under the conditions, piperazine and N- ethyl piperazine yield 88%. through pilot production to determine the process is suitable for industrial production.

【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626

【相似文献】