【作者】 孙晓敏；

【导师】 刘国际； 雒廷亮；

【作者基本信息】 郑州大学 ， 化学工艺， 2008， 硕士

【摘要】 己二酸的主要用途是作尼龙66和工程塑料的原料。目前工业上主要采用环己烷空气氧化合成己二酸,其中第二步由HNO₃氧化KA油（环己醇和环己酮混合物）合成己二酸,存在环境污染等问题。本文采用清洁氧化剂（过氧化氢）,在无有机溶剂的条件下,以杂多酸为催化剂,环己醇催化氧化合成己二酸,并对产品进行了表征。考察了不同酸性配体对反应收率的影响。结果表明以草酸为配体,效果较好。通过正交实验、单因素实验的实验方法,得出最佳工艺条件。即环己醇:H₂O₂:杂多酸:草酸=100:1760:0.6:2.5;反应温度85℃、反应时间8h,己二酸的最大收率为77.83%。并通过催化剂的重复利用实验,证明催化剂具有良好的循环利用性。本文通过动力学实验,对合成反应表观动力学进行了初步探索。基于气-质联用色谱和气相色谱分析,确定反应为连串反应。反应历程为:其中第一步和第二步均为一级反应。并对实测的动力学数据进行了回归了处理,确定了动力学方程:其中k₁=7.252×10³exp（-43.27×10³/RT）,k₂=178.8exp（-26.74×10³/RT）。经验证在实验范围内本文所确定的反应动力学数学模型准确。更多还原

【Abstract】 Adipic acid is the main used as raw materials of nylon 66 and the engineering plastics. At present, the major synthetic method of adipic acid in industry is oxidation of cyclohexane,in which the second step is oxygenated KA oil into adipic acid. But the second step has no fundamental improvement.Therefore it is necessary to improve the process of from KA oil to adipic acid .At present, the industrial synthetic approach of adipic acid is the oxidation cyclohexanone/cyclohexanol by nitrate. The method for the use of nitrate oxidizer, will cause serious environmental pollution. Today because the widespread promotion of green chemistry, how to reduce the pollution of chemical production on environment is a primary task for the chemical workers. Research and development of clean catalytic oxidation of adipic acid has become an important subject areas of industrial chemicals.In this paper, in the absence of organic solvents and using as heteropolyacid as a catalyst, cyclohexanol can be oxidized into adipic Acid by clean oxidants H₂O₂. The products were characterized. Inspected the different acid ligands on the impact of response. The results indicates that oxalate as the ligand is better. By orthogonal experimental and single-factor test , the optimum conditions has gained,which is cyclohexanol: H₂O₂: heteropoly acid:oxalic =100: 1760: 0.6: 2.5, at the reaction time of 85℃for 8h , the yield of adipic acid goes up to 77.83%. the re-use experiment of catalyst prove that catalyst has a good use of the cycle.Based on the reaction of the dynamics experiments, the preliminary dynamics of the apparent response has explored. The reaetion course is preliminarily studies on the base of MS and GC.The results showed that the reaction is obeyed first-order irrevisible kineties model under the experimental conditions.We determined the Parameters in the equation through the regression of experimental datas. It had been Proved that the fixed reaetion killetics matllenlatieal model in the text was reliable.k₁=7.252×10³exp（-43.27×10³/RT）,k₂=178.8exp（-26.74×10³/RT）。更多还原