【作者】 柳艳修；

【导师】 宋华；

【作者基本信息】 大庆石油学院 ， 化学工艺， 2006， 硕士

【摘要】 高铁酸钾和过氧化氢都是绿色、无污染、和高活性的氧化剂。本文分别以高铁酸钾和过氧化氢作为氧化剂,研究了它们氧化环己醇合成环己酮的反应,考察了溶剂种类、催化剂种类和用量、温度、氧化剂用量及反应时间等因素对氧化反应的影响。通过正交试验,系统研究了高铁酸钾、过氧化氢氧化环己醇合成环己酮的最佳反应条件。 实验结果表明:(1)在高铁酸钾氧化环己醇合成环己酮的反应中,超稳分子筛和HPA-1组成一个较好的催化体系,在反应条件:环己烷20mL,环己醇0.2mL,超稳分子筛0.5g,HPA-10.15mL,高铁酸钾0.396g,反应温度40℃,反应时间12h,环己酮产率达到51.7%。(2)在30%双氧水氧化环己醇合成环己酮的反应中,提出了以钨酸钠为主催化剂,加入各种酸性配体氧化环己醇合成环己酮的新工艺路线。其中,HPA-2的助催化性能较好。在反应条件:钨酸钠1.2mmol,HPA-20.12mmol,环己醇2mL,30%双氧水2.5mL,反应温度80℃,反应时间6h,环己酮产率可达98.2%。本实验所采用的催化剂体系,在反应时间缩短6h的情况下,温度低5℃～10℃的条件下,环己酮产率比文献产率高3%。(3)探索了自制的几种催化剂对双氧水氧化环己醇合成环己酮反应的催化性能,发现PW-1的催化性能比较好。在催化剂用量仅为0.02g,环己醇2mL,30%双氧水3mL,反应温度80℃,反应时间8h的条件下,环己酮产率就达76.4%。 高铁酸钾和过氧化氢都是极具潜力的绿色氧化剂,关键任务是要寻找合适的催化体系与之匹配协调,以充分发挥它们的氧化能力。本论文的工作为氧化合成其它有机物探索出了一条可循之路,具有一定的参考价值。更多还原

【Abstract】 Potassium ferrate and hydrogen peroxide are all non-pollution green oxidant environment friendly, and have powerful oxidization and high selectivity. The reaction of oxidizing cyclohexanol to cyclohexanone by potassium ferrate and hydrogen peroxide were studied, and the effect of solvent kind、 catalyst kind and amount、 assistant-catalyst kind、 reaction temperature、 oxidant amount and reaction time were investigated in this text. The optimal reaction conditions determined by the orthogonal experiment were also involved.The results shows:（1）In the reaction of oxidizing cyclohexanol to cyclohexanone by potassium ferrate,the catalyst system of ultra-stable zeolite and HPA-1 shows good catalyst ability.With the conditions:cyclohexane of 20mL,cyclohexanol of 0.2mL, ultrastable zeolite of 0.5g,phosphoric acid of 0.15mL,potassium ferrate of 0.396g,reaction time of 12h,the yield of cyclohexanone reach 51.7%;（2）In the reaction of oxidizing cyclohexanol to cyclohexanone by hydrogen peroxide,we put forward a new method,that is taking sodium tungstate and assistant acid as catalyst system,and the catalyst ability of HPA-2 is best. With the conditions: cyclohexanol of 2mL, sodium tungstate of 1.2mmol, HPA-2of 0.12mmol, 30% hydrogen peroxide of 2.5mL,the reaction temperature of 80℃,reaction time of 6h, the yield of cyclohexanone reach 98.2%.The method used our catalyst reduced the reaction time by 6 h,reduced the reaction temperature by 5℃¹0℃and improved the yield of cyclohexanone of the reference^[49]by 3%.（3）The effect of several self-made catalyst on the reaction were studied.Among all the self-made catalyst,the catalystic ability of PW-1 is best,which the yield of cyclohexanone could reach 76.4% in the conditionxyclohexanol of 0.2mL,hydrogen peroxide of 3mL,PW-1 of 0.02g,the reaction temperature of 80℃,reaction time of 8h.Potassium ferrate and hydrogen peroxide are all potential oxidant,how to develop suitable catalyst system is the key job.This work opened up a new way that can be followed by green synthesis of other organic compounds and has a certain reference value.更多还原