【作者】 崔海龙；

【导师】 章亚东；

【作者基本信息】 郑州大学 ， 化学工艺， 2007， 硕士

【摘要】 本文为河南省重点科技攻关资助项目（项目编号：523050300）。己二酸是一种重要的二元脂肪酸，主要用于尼龙-66，聚氨酯等高分子材料的合成。己二酸传统生产工艺存在环境污染问题，而近年新开发的双氧水直接氧化环己烯合成己二酸工艺因双氧水价格高、产品生产成本高之重大缺陷，尚不具有工业应用价值。鉴于烯烃易于与臭氧发生反应之特点，本文间接利用分子氧，将氧气经臭氧发生器使其部分生成臭氧，开辟了一个以环己烯、w（H₂O₂）=30％的双氧水溶液以及氧气为主要原料，经臭氧化及氧化分解反应合成己二酸的新方法。本文开展的主要工作如下：在臭氧化反应过程，选择以塔高径比为10：1（塔外径为30mm），气体分布器为G4玻璃砂芯的鼓泡反应塔为臭氧化反应器。考察了溶剂种类、用量、臭氧化时间、臭氧化温度对反应的影响，确定了制备臭氧化中间体的适宜的反应条件，具体为：V（环己烯）：V（乙酸）=1：10（以2.8 mmol，约3ml环己烯计），反应时间1.5 h，O₂流量200 mL/min，臭氧发生器效率100％，反应温度为5-10℃。在氧化分解臭氧化中间体合成己二酸过程中，首先采用质量百分浓度w（H₂O₂）=30％的双氧水溶液为氧化剂，开展了氧化分解臭氧化中间体的研究。考察双氧水溶液氧化分解中H₂O₂与环己烯的摩尔比、氧化分解温度、氧化分解时间等因素对合成己二酸反应的影响，确定了H₂O₂氧化分解臭氧化中间体的最佳反应条件，具体为：n（H₂O₂）：n(C₆H₁₀)=2.4：1（以2.8 mmol环己烯计），氧化分解温度为75℃，氧化分解时间为3.5 h时，经三组平行试验检验，产品己二酸的平均收率约80.4％。双氧水作为氧化剂虽是绿色氧化剂，但成本较高。鉴于此，开展了以氧气为氧源氧化分解臭氧化中间体的研究。探讨了氧化分解温度、氧化分解时间、催化剂种类、催化剂加入量、氧气气速等主要影响因素对氧化分解反应的影响。采用两次正交试验对反应条件进行优化，得出了最佳反应条件为：氧化分解温度为75℃，氧化分解时间为3.5h，钼金属用量1 mmol（折合三氧化钼质量0.144 g），氧气气速为40 mL/min，己二酸的收率可达到79.5％，乙酸回收收率可达到70％。本研究特点在于全部采用清洁氧源，以代替现行有重大污染的工业路线。从上述结果看：以O₂为氧源氧化分解所得的己二酸收率虽较H₂O₂略低，但从原料成本上讲O₂为氧源更具有优越性，具有较好的潜在应用前景。更多还原

【Abstract】 This dissertation was financial supported by the Key Scientific and Technological Project Funds of Henan Province （523050300）.Adipic acid is an important dicarboxylic acid, which mainly in making some of polymers, such as 6,6-nylon, polyurethane and so on. There is pollution problem in the traditional technology of synthesis adipic acid. And in recent years, hydrogen peroxide is used to synthesize adipic acid by oxidating cyclohexene directly. for higher price of H₂O₂, this new technology can not be applied in industry. It is well-known that olefin is easy to react with ozone, so this paper uses O₂ indirectly, some of the O₂ is transformed into O₃ in a ozonizer, this is a new way to synthesize adipic acid with cyclohexene, 30 wt% H₂O₂ and oxygen as raw materials. Main results obtained on research work are as follows:In the process of the ozonation reaction, the bubble column, whose ratio of column height to diameter was 10 : 1 and the gas distributer was G4 glass sand core, was adopted as the ozonation reaction column. Several factors which influence the ozonation reaction, such as, sorts and volumes of solvent, ozonolysis temperature had been investigated. The proper ozonolysis condition was confirmed, that is, V(C₆H₁₀) : V（C₂H₄O₂）=1:10 （based on 2.8 mmol of cyclohexene, approx 3 ml）, ozonolysis time 1.5 h, flux of oxygen 200 mL/min, efficiency of zonator 100 %, ozonolysis temperature 5-10℃.In the process of synthesis adipic acid by oxygenolysis of the ozonized intermediate, firstly, 30 wt% H₂O₂ was used as oxidant. Effects of some factors were investigated in oxygenolysis of ozonized intermediate, such as, molar ratio of hydrogen proxide to cyclohexene, oxygenolysis temperature and time. The proper oxygenolysis condition was n（H₂O₂） : n(C₆H₁₀)=2.4 : 1 （based on 2.8 mmol of cyclohexene）, oxygenolysis temperature 75℃, oxygenolysis time 3.5 h. Under this optimum condition, the average yield of adipic acid synthesized by three parallel tests was about 80.4 %. Although H₂O₂ is an important "green" oxidant, its price is higher than general oxidants. And then oxygen is natural, cheap and rich oxidant, therefore, O₂ was choosed as an oxidant from some oxygen sources in oxygenolysis of the ozonized intermediate. The main factors which influence the reaction, such as, oxygenolysis temperature and time, sorts and weights of catalysts and flux of oxygen. Twice orthognol test was adopted to optimize the reaction conditions, the optimal oxygenolysis condition was as follows: oxygenolysis temperature 75℃, oxygenolysis time 3.5 h, amount of molybdenum in molybdenum trioxydatum 1 mmol, flux of oxygen 40 mL/min. Under the condition, the yield of adipic acid was 79.5 %, the recovery rate of acetic acid was 70 %.Clean oxidant was used in this work to replace the traditional industry process, which would pollute the environment seriously. The results showed, in oxygenolysis of ozonized intermediate, the yield of adipic acid was synthesized by using O₂ as oxidant is a little lower than that of by using H₂O₂. Considering the cost of oxidants, it is sure that the former is better than the latter, and so technology of O₂ as oxidant possesses more potential foreground in application of industrial fields.更多还原