二氯丙醇环化合成环氧氯丙烷固体碱催化剂的合成及性能研究

发布时间：2018-03-02 21:33

本文选题：环氧氯丙烷　切入点：二氯丙醇　出处：《太原理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：环氧氯丙烷是一种含有广泛应用价值的有机中间体。目前,工业生产环氧氯丙烷的工艺均存在严重的“三废”问题,处理时需要投入大量的人力、物力和财力,且石油资源愈发紧缺,世界环境问题也引起人们的高度重视,严重依赖石油资源的前两种工艺将遇到发展瓶颈,而甘油法依赖生物能源,同时还得到国家环境保护和可持续发展政策的大力支持,因此,甘油法有很好的发展前景。近年来,环氧氯丙烷已呈现出产能过剩的态势,故甘油法生产工艺亟待优化,改进设备与工艺的不足之处,研发新型、高效催化剂,以便更加环保的、有效的生产高质量的环氧氯丙烷,科研工作者为此做了大量的研究工作,并取得一定的进展。本课题主要研究二氯丙醇脱HCl合成环氧氯丙烷工艺,该工艺采用气-固非均相反应体系,摆脱了传统的皂化工艺,反应条件温和、工艺简单、流程短;副产物少、不产生工业废液、环保无污染;催化剂易于分离、再生等优点。本文以氧化铝为载体的催化二氯丙醇脱HCl制备ECH的工业化应用为最终目标来进行研究,考察了载气流速、二氯丙醇气化温度以及固体碱催化剂的制备条件对二氯丙醇脱HCl反应转化率、选择性和收率的影响以及催化剂的寿命,并通过XRD、氮吸附脱附、程序升温脱附、碱强度测定等对其物化性质进行表征,探究了固体碱的比表面积和碱度等因素对二氯丙醇脱HCl反应的影响,我们在最佳的实验条件:常压下,载气流速100 ml/min,二氯丙醇气化温度80°C,管路保温套温度110°C下,优选出催化效果较好的固体碱催化剂。主要得出以下结论:(1)通过探究氧化钾的不同阴离子前驱体制备的α-Al_2O_3负载型固体碱的催化性能,K2O(10%KOH)/α-Al_2O_3催化性能最佳。(2)通过探究不同金属阳离子的硝酸盐为前驱体制备的γ-Al_2O_3负载型固体碱的催化性能,发现10%BaO/γ-Al_2O_3催化效果最好。少量的弱碱性位点及大量的强碱性位点是影响其催化活性的重要因素。(3)通过探究不同金属阳离子的氯化物为前驱体制备的γ-Al_2O_3负载型固体碱的催化性能,发现10%MgCl2/γ-Al_2O_3催化效果最好。少量的弱碱性位点及大量的强碱性位点是影响其催化活性的重要因素。(4)通过探究固体碱催化剂寿命得出:10%BaO/γ-Al_2O_3稳定性最好。
[Abstract]:Epichlorohydrin is an organic intermediate with wide application value. At present, the industrial production of epichlorohydrin has serious "three wastes" problem, which requires a great deal of manpower, material and financial resources. Moreover, oil resources are becoming increasingly scarce, and environmental problems in the world have aroused great attention. The first two processes that rely heavily on petroleum resources will encounter bottlenecks in development, while glycerol methods rely on bioenergy. At the same time, it is supported by the national environmental protection and sustainable development policy. Therefore, glycerol method has a good development prospect. In recent years, epichlorohydrin has shown a situation of overcapacity, so the production process of glycerol process needs to be optimized. Improvement of equipment and process deficiencies, research and development of new, efficient catalysts to more environmentally friendly and effective production of high quality epichlorohydrin, researchers have done a lot of research work, In this paper, the process of synthesizing epichlorohydrin from dichloropropanol HCl was studied. The process used gas-solid heterogeneous reaction system to get rid of the traditional saponification process, the reaction conditions were mild, the process was simple and the process was short. There are few by-products, no industrial waste liquid, environmental protection and no pollution, the catalyst is easy to be separated and regenerated. In this paper, the industrial application of catalytic decalcification of dichloropropanol to ECH with alumina as the carrier was studied. The effects of gas flow rate, gasification temperature of dichloropropanol and the preparation conditions of solid base catalyst on the conversion, selectivity and yield of dichloropropanol HCl, as well as the lifetime of the catalyst were investigated. The adsorption and desorption of dichloropropanol by XRD, nitrogen adsorption and temperature programmed desorption were carried out. The physical and chemical properties were characterized by alkali strength measurement, and the effects of specific surface area and alkalinity of solid base on the HCl reaction of dichloropropanol were investigated. The carrier airflow velocity is 100 ml / min, the gasification temperature of dichloropropanol is 80 掳C, the temperature of pipe insulation is 110 掳C, The main conclusions are as follows: 1) by exploring the catalytic performance of 伪 -Al2O3 supported solid base prepared by different anion precursors of potassium oxide, the catalytic performance of K _ 2O-10KOHU / 伪 -Al _ 2O _ 3 / 伪 -Al _ 2O _ 3 solid base / 伪 -Al _ 2O _ 3 is optimized by exploring the catalytic performance of 伪 -Al _ 2O _ 3-supported solid base / 伪 -Al _ 2O _ 3. Catalytic properties of 纬 -Al _ 2O _ 3 supported solid base prepared with nitrate of metal cations as precursor, It is found that 10O / 纬 -Al2O3 has the best catalytic effect. A small number of weakly basic sites and a large number of strong alkalinity sites are important factors affecting its catalytic activity.) 纬 -Al _ 2O _ 3 supported solid prepared from chlorides of different metal cations as precursors is investigated. Catalytic activity of body bases, It is found that 10MgCl _ 2 / 纬 -Al _ 2O _ 3 catalyst has the best catalytic effect, and a small number of weak basic sites and a large number of strong basic sites are important factors affecting its catalytic activity.) by exploring the lifetime of solid base catalyst, it is concluded that 10O / 纬 -Al _ 2O _ 3 has the best stability.
【学位授予单位】：太原理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ223.26;O643.36

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