【作者】 赵明；

【导师】 许春建； 王志侃；

【作者基本信息】 天津大学 ， 化学工程， 2013， 硕士

【摘要】 9-芴酮是重要的精细化工中间体，具有非常高的经济价值，在医药、农药、染料、塑料等领域有着广泛的应用，主要由芴催化氧化制得。芴是煤焦油的主要组分之一，主要从煤焦油的洗油中提取。从洗油中提取芴，并以芴为原料制取9-芴酮，将显著提高煤焦油的附加值。寻找合适的液相催化氧化芴制取9-芴酮工艺具有广阔的应用前景和重要的现实意义。本文研究了芴液相催化氧化制取9-芴酮工艺，以氧气为氧化剂，1,3-二甲基-2-咪唑啉酮(DMI)为溶剂，采用D296强碱性离子交换树脂、稀土元素Ce改性的氧化锰八面体分子筛Ce-OMS-2、NaOH三种不同的催化剂，考察了催化剂种类、催化剂用量、溶剂种类、溶剂用量、氧气流量、温度、反应时间、搅拌速率等因素对芴转化率和9-芴酮收率的影响，同时考察了催化剂回收再利用情况，得出最佳工艺条件。实验表明：D296强碱性离子交换树脂不易失活，可以重复使用四次以上，但是催化效果较差，芴转化率为51.06%，9-芴酮收率为44.23%；使用回流法制备的Ce-OMS-2具有比OMS-2更好的催化性能，可以重复使用四次以上，催化性能优于D296强碱性离子交换树脂，芴转化率为62.92%，9-芴酮收率为61.03%；NaOH的催化氧化工艺最佳，在该工艺条件下，芴的转化率和9-芴酮收率最高，分别为99.26%和95.35%，催化剂NaOH可以重复使用。此外，该工艺还具有操作简便、反应条件温和，反应速度快、催化剂用量少等优点，而且NaOH价廉易得，适合9-芴酮的规模化生产，具有良好的工业应用价值。更多还原

【Abstract】 9-Fluorenone is an important fine chemical intermediate and of very higheconomical value, which is mainly prepared by catalytic oxidation of fluorene.9-Fluorenone is an important organic synthetic material, which has a wide applicationin medicine, pesticides, dyes and plastics. Fluorene is one of the main components ofcoal tar, mainly extracted from wash oil of coal ta. Extracting fluorene from the washoil and then preparing9-fluorenone can significantly improve the value of the coal tar.Finding the right process of9-fluorenone synthesis by liquid-phase catalyzedoxidation of fluorene has both broad prospects for application and important practicalsignificance.In this article,9-fluorenone synthesis by liquid-phase catalyzed oxidation offluorene was studied. In the experiment, three different catalyst, strong-base ionexchange resin, Ce-OMS-2and NaOH were explored with oxygen as oxidant andDMI as solvent. The effect of catalyst and catalyst dosage, solvent and solvent dosage,oxygen flow, temperature, reaction time, stirring rate were investigated. At the sametime, catalyst recycling experiment was carried out. The optimal catalyst and reactionconditions were involved.When strong-base ion exchange resin of D296as catalyst, the catalyst is not easydeactivated and can be recycled more than four times. But the catalytic performance isbad, conversion of fluorene and yield of9-fluorenone reach51.06%and44.23%,respectively. Cerium-incorporated OMS-2catalyst was synthesized through refluxingmethod. It has much better catalytic activities than OMS-2and can be recycled morethan four times. The catalytic performance is better than strong-base ion exchangeresin of D296, conversion of fluorene and yield of9-fluorenone reach62.92%and61.03%, respectively. The results show that the process of NaOH catalytic oxidationis the best. Under this process, conversion of fluorene and yield of9-fluorenone arethe highest,99.26%and95.35%, respectively. NaOH can be recycled. The processhas many advantages, such as easy to operate, gentle reaction condition, fast reactionrate, low catalyst dosage and low price of the catalyst, which is suit for the scaleproduction of9-fluorenone and has good industrial application value for the future.更多还原