【作者】 李红霞；

【导师】 吴素芳；

【作者基本信息】 浙江大学 ， 化学工程， 2003， 硕士

【摘要】 甲基异丁基酮（MIBK）是一种重要的化工原料，应用十分广泛。近年来国内对MIBK的需求量日益增加，开发合成MIBK的国产化技术已十分必要和迫切。本文的目的在于开发有效的催化剂及在间歇与连续反应器中对催化剂进行评价。 本文首先研究了用于丙酮一步法合成MIBK催化剂的制备方法及用高压反应釜液相反应的评价方法。具体考察了载体、制备方法、焙烧条件、多种金属组分对催化剂活性的影响。研制了以HZSM-5分子筛为载体，负载Pd、Cu、Zn、Ni等多金属活性组分的催化剂。在优化的质量含量分别为Pd 0.2％，Cu 0.5％，Zn0.1％，Ni 0.8％的多金属催化剂作用下，在反应温度160℃，反应压力18kg/cm²的液相反应条件下，丙酮的转化率为42.7％，MIBK的选择性最高可达95.6％。 其次，利用所研制的多金属催化剂，在液相反应条件下，研究并得到了丙酮一步催化加氢制备MIBK的反应动力学为：该动力学方程首次量化了氢气在反应中的作用，对生产实践有重要的指导意义。 本文进一步将开发的多金属催化剂用于固定床反应器进行评价，同时优化了丙酮气相状态下的反应条件。得到最佳工艺条件为：反应温度190℃，反应压力16kg/cm²，氢气—丙酮比例为4:1，空速为2.4h^-1。在此条件下，MIBK收率可达75g.h^-1.gcat^-1。 催化精馏具有提高转化率及降低能耗等显著优点。丙酮一步法合成MIBK的反应符合催化精馏所要求的必要条件，本文探索了该反应在催化精馏装置下连续进行反应的可行性。实验结果表明，催化精馏大大提高了丙酮的转化率。在相应的反应条件下还考察多金属催化剂的寿命，实验表明：在100h内，催化剂的活性没有显著的改变；催化剂加速失活后，经简单的焙烧、氢化还原，催化剂又能恢复原有的活性。 对丙酮一步法生产MIBK的双功能催化剂及其工艺条件的实验研究表明：本文所研究的多金属催化剂具有良好的工业应用前景，并可适用于催化精馏工艺。更多还原

【Abstract】 Methyl isobutyl ketone ( MIBK) is one of the most important chemical products, which is widely used in the field of chemical engineering. With the rapidly increasing need of MIBK in China, it is important and necessary to develop the technology of producing MIBK. The purpose of the study is to develop one kind of efficient catalysts and evaluate the catalyst in an autoclave and a fixed-bed reactor.Firstly, the bifunctional catalyst for synthesizing MIBK was prepared, and its activity has been evaluated in liquid reaction condition using an autoclave. The effects of supports, preparing methods and the calcination temperatures on the activity of catalysts were studied. In addition, the influence of metal compositions and contents on catalytic properties was also investigated. While using HZSM-5 as a support, the optimum catalyst containing metal 0.2%Pd^ 0.5Cu%^ 0.1 Zn% and 0.8Ni% was evaluated under the operation conditions of temperature 160癈 and pressure l.SMpa. The conversion of acetone and the selectivity of MIBK reached to 42.3% and 95.6% respectively.Secondly, the kinetics of the combination of the condensation and hydrogenation reaction was studied by using the multi-metal catalyst. A kinetic equation was determined as following:The reaction orders of acetone and Ha were 2 and 0.3 respectively. A valuable quantifiable research was made about influence of the fb, it is important for the direction of the industrial production.More further, the multi-metal catalysts have been evaluated in a fixed-bed reactor, and the experimental condition was optimized. The influence of the temperature, pressure, ratios of reactants, and WHSV in the column has been conducted. At the following optimal operation condition, the temperature 190癈, the pressure 16kg/cm , the ratio of hydrogen to acetone 4 to 1, and the WHSV 2.411"1, the yield of MIBK wasThe catalytic distillation technology has advantages such as increasing conversion and decreasing the energy combustion. The paper briefly studied the operation conditions of one-step synthesis of MIBK from acetone under the catalytic distillation conditions. Experimental results indicated that the conversion of actone was greatly increased compared to the normal reaction conditions. The life testing experiments of the multi-metal catalysts showed stable activity for lOOhrs. The catalysts can be regenerated by calcination and hydrogenation after rapidly decreasing the activity.In a word, the multi-metal catalysts with the catalytic distillation technology showed a good possibility for the industrial application of the one-step MIBK synthesis from acetone.更多还原