负载型固体酸碱催化餐饮废油制备生物柴油的工艺研究

发布时间：2018-04-29 01:22

本文选题：生物柴油 + 地沟油　；参考：《哈尔滨工业大学》2015年硕士论文

【摘要】：全球正面临能源短缺的问题,生物柴油作为一种新型的清洁能源引起了广泛的关注。生物柴油最初以植物油为原料,但是随着原料油价格的不断上涨,生物柴油生产企业进入发展的困难时期,以餐饮废油作为原料是一种切实可行的办法。目前关于以废弃油脂为原料制备催化剂的研究大多以液相酸碱为催化剂,生产过程中会产生废酸碱液,而且副产物甘油不能有效利用。本实验室已经制备了新型固体酸碱,其中固体酸催化酯化反应已经形成了固定床反应体系,但关于溶剂等方面仍需要改进,对于固体碱催化酯交换反应还没有形成具有应用的价值的反应体系,因此本课题主要从以下几个方面展开了研究,并取得了相应的研究成果。本课题对实验室已经构建的固体酸催化体系进行了改进,主要是共溶剂的选择,考察了不同物质作为共溶剂时对酯化反应的影响。最终确定价格相对便宜的丁酮和正己烷混合物作为共溶剂,同时对酯化反应条件进行了优化。以丁酮和正己烷混合物为共溶剂时的最佳工艺条件为:反应温度65℃,反应时间120 min,醇油摩尔比20:1。除此之外还对催化剂的寿命和再生进行了考察,以乙醇作为清洗剂时催化剂的使用寿命为560 h。固定床是固体酸碱制备生物柴油的常用反应器,因此本课题搭建了一套固体碱催化酯交换反应的固定床反应装置,包括原料主反应系统、余热原料预加热系统、产物分离系统和副产物甘油油浴加热系统等。本课题对Mg-Zr固体碱催化剂的固载化进行了研究。经过对不同载体的考察,选择了蜂窝状活性氧化铝作为催化剂载体,同时考察了浸渍液浓度、焙烧温度、物料配比等制备条件对催化剂性能的影响,确定催化剂的最佳制备条件为浸渍液浓度8 mol/L、焙烧温度500℃、Mg、Zr摩尔比为3:1。最后,选择最优催化剂,利用搭建的碱催化固定床反应器进行酯交换反应条件的优化和催化剂寿命的考察。酯交换反应最佳条件为反应温度220℃、反应时间180 min。以乙醇作为再生清洗剂时固体碱催化剂的寿命达到225 h。以搭建的小试实验装置核算生物柴油的生产成本为973.83元/吨。本课题搭建的固定床体小试实验装置为固体酸碱制备生物柴油工业化做了铺垫。
[Abstract]:The whole world is facing the problem of energy shortage. Biodiesel has attracted wide attention as a new kind of clean energy. Biodiesel is originally used as raw material of vegetable oil. But as the price of raw oil continues to rise, biodiesel production enterprises enter the difficult period of development, and the waste oil as raw material is a practical method. At present, most of the studies on the preparation of catalyst with waste oil as raw materials are liquid acid and alkali as the catalyst, and the waste acid and alkali solution will be produced in the production process, and the by-product glycerol can not be used effectively. There is still a need to improve the solvent and so on. For the solid base catalyzed transesterification, there is no application value reaction system. Therefore, this topic has been mainly studied from the following aspects and obtained the corresponding research results. This topic has improved the solid acid catalytic system which has been constructed in the laboratory, mainly co - dissolving. The effect of different substances on the esterification was investigated when the different substances were used as co solvents. Finally, the relatively cheap butanone and n-hexane mixture were used as co solvent and the conditions of esterification were optimized. The optimum process conditions for the co solvent with butanone and n-hexane mixture were 65 C reaction temperature and 120 reaction time. Min, alcohol and oil mole ratio 20:1. also investigated the life and regeneration of the catalyst. The service life of the catalyst with ethanol as a detergent is 560 h. fixed bed, which is a common reactor for solid acid and alkali preparation of biodiesel. Therefore, a set of fixed bed reactor for solid alkali catalytic transesterification is set up, including a set of fixed bed reactor. The main reaction system of raw materials, the preheating system of waste heat raw materials, the product separation system and the glycerol oil bath heating system of the by-products. This subject has studied the immobilization of the Mg-Zr solid base catalyst. After the investigation of different carriers, the honeycomb activated alumina was selected as the catalyst carrier, and the concentration of the impregnated liquid and the calcination temperature were also investigated. The effect of the preparation conditions on the performance of the catalyst was determined. The optimum preparation conditions of the catalyst were the concentration of 8 mol/L, the calcination temperature 500, the molar ratio of Mg, Zr was 3:1., the optimum catalyst was selected, the ester exchange reaction conditions were optimized and the catalyst life was investigated by the built alkali catalyzed fixed bed reactor. The best condition of the exchange reaction is the reaction temperature of 220 C, the reaction time 180 min. and the life of the solid base catalyst when the ethanol is used as the regenerative cleaning agent. The life of the solid base catalyst is 225 h.. The production cost of the biodiesel is 973.83 yuan / ton. The fixed bed small test device for the fixed bed body is prepared for the solid acid and alkali preparation of the biodiesel. Industrialization has made a paving.

【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE667

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