离子液体催化碳酸乙烯酯水解合成乙二醇的研究
文献类型：学位论文
| 作者 | 王耀红 |
| 学位类别 | 硕士 |
| 答辩日期 | 2009-06-01 |
| 授予单位 | 中国科学院过程工程研究所 |
| 授予地点 | 过程工程研究所 |
| 导师 | 张香平 |
| 关键词 | 碳酸乙烯酯 离子液体 乙二醇 合成 |
| 其他题名 | Preparation of Ionic Liuqid Catalysts and their Application in the Synthesis of Ethylene Glycol via Hydrolysis of Ethylene Carbonate |
| 学位专业 | 应用化学 |
| 中文摘要 | 乙二醇是一种重要的基础工业原料，主要用于生产聚酯纤维、防冻剂、不饱和聚酯树脂等，是乙烯工业中仅次于聚乙烯、聚氯乙烯的第三大产品。我国目前生产乙二醇主要是采用环氧乙烷直接水合工艺，该方法存在水比高、能耗高、选择性差等问题，严重影响了乙二醇工业的发展和进步。针对该工艺的不足，国内外相继开发了一些新技术，其中碳酸乙烯酯法由于可以大大降低系统水比，而成为乙二醇新技术发展的主流方向。本论文围绕碳酸乙烯酯法生产乙二醇新工艺的开发，设计合成了新型高效离子液体催化剂及负载型催化剂，可以避免现有无机盐/有机催化剂存在的效率低、催化剂易分解、寿命短、易失活等不足。论文的主要研究内容和创新成果如下： 1．研究开发了具有双催化功能的新型高活性复合催化剂，可以同时催化环加成反应和碳酸乙烯酯水解反应，解决了现有工艺两步催化剂所带来的催化剂分离的难题。考察新型复合催化剂对环加成反应、重组分积累以及对碳酸乙烯酯水解反应的影响，优化出催化剂配比、催化剂用量以及工艺条件(温度、压力、时间、物料配比等)，研究表明，复合催化剂具有对环加成和碳酸乙烯酯水解良好的催化效果，转化率达到99.8%，乙二醇的选择性达到99.9%以上，高于现有的文献报道。 2．设计开发出固载化离子液体催化剂，首次应用于碳酸乙烯酯水解反应。结果表明：以固载化碱性离子液体S-[bpim][HCO3]为催化剂，可在温和条件下，达到高效、稳定的活性和简单的分离性能。优化了反应条件，获得最佳工艺条件，在最佳工艺条件下，EC的转化率达到99.7%，EG的选择性接近100%。经过多次循环，催化剂仍保持较高的催化活性和稳定性。 3．将设计合成的催化剂用于10t/a碳酸乙烯酯法合成乙二醇的模式试验装置。考察了催化剂的性能和寿命，结果表明，在260 h 长周期运转的过程中，环氧乙烷平均转化率达到99.3%，碳酸乙烯酯和乙二醇的平均总选择性为99.6%；水解反应的实验结果表明，碳酸乙烯酯的转化率接近100%，乙二醇总选择性为99%。说明本研究开发的催化剂具有良好的催化性能和稳定性，为中试设计提供了重要保障。 |
| 英文摘要 | Ethylene glycol (EG) is an important raw material in organic chemical industrial. It can be used in many applications such as polyester fiber, antifreeze agents and unsaturated resin and it is the third product just less than polyethylene and PVC in ethylene industry. At present, the method of direct hydration of ethylene oxide (EO) is the leading way to synthesis of EG. The main shortcomings of this method are as follows: high water ratio, high energy consumption, low selectivity and so on, which have prevented the development of ethylene glycol industry. In order to solve the deficiency of this method, some new technologies have developed in China and abroad. Ethylene carbonate method has become the main developing trend of synthesis of EG, because this method can greatly reduce the water ratio. High efficient catalysts of ionic liquids and renewable immobilized catalyst were designed and synthesized for the development of a new energy saving process of EG through hydrolysis of ethylene carbonate in this paper, which can solve the problem encountered in inorganic or organic catalysts (such as low efficient, easy decomposition, short life, easy deactivation, etc.). The main research contents and results are as follows: 1. A new composite catalyst with double catalytic functions and high efficiency was prepared, which can catalyze both EO cycloaddition reactions and ethylene carbonate hydrolysis reaction. It could successfully solve the problem of the separation of the different catalysts in the two-step technology. Its effects on cycloaddition reaction, side reaction and the hydrolysis reaction of ethylene carbonate were investigated. Moreover, the optimum addition amount of the composite catalyst, the ratio of Cat.1 to Cat.2 and the reaction parameters (such as reaction temperature, reaction pressure, the molar ratio of H2O to ethylene carbonate) were determined. The result showed that the composite catalyst had good performance both on cycloaddition reaction and hydrolysis of ethylene carbonate. The 99.8% of EO conversion rate and 99.9% of EG yield were achieved by using the composite catalyst. 2. Immobilized ionic liquid catalysts were designed and developed, which were first used as the catalysts for hydrolysis of ethylene carbonate. It was found that high efficiency and high stability could be obtained under mild hydrolysis conditions when immobilized basic ionic liquid (S-[bpim][HCO3]) was used as catalyst and it could be separated with the reaction product easily. 100% of selectivity EG and 99.7% of EC conversion were obtained under the optimized reaction condition: the addition amount of catalyst 0.0511g/mL, 0.4 MPa, 140℃, 3 h, EC:H2O = 1:2. Additionally, no obvious changes of its good performance have been found after reused five times. 3. The composite catalyst was tested by the model experiment of 10t/a EG via hydrolysis of EC. The performance and life of the composite catalyst were investigated. Long-term (260h) run results showed that the cycloaddition reaction results almost achieved the level obtained in the laboratory. The average conversion rate of EO was about 99.3% and the average total selectivity of EC and EG was about 99.6%. The hydrolysis reaction results showed that the conversion rate of EC was 100% and the total average selectivity of EG was above 99%. The above results showed the catalyst we developed had good catalytic performance and stability, which providing an important support for the middle test. |
| 语种 | 中文 |
| 公开日期 | 2013-09-16 |
| 页码 | 95 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/1301]  |
| 专题 | 过程工程研究所_研究所（批量导入） |
| 推荐引用方式 GB/T 7714 | 王耀红. 离子液体催化碳酸乙烯酯水解合成乙二醇的研究[D]. 过程工程研究所. 中国科学院过程工程研究所. 2009. |
入库方式： OAI收割
来源：过程工程研究所
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