【作者】 王朝进；

【导师】 蒋登高； 章亚东；

【作者基本信息】 郑州大学 ， 化学工艺， 2003， 硕士

【摘要】 邻苯二酚作为重要的有机中间体，广泛地应用于医药，农药，香料，化学助剂等方面，国内对其需求很大，但主要依赖于进口。因此有必要对邻苯二酚的合成方法进行研究。我们参考了国内外研究进展，同时考虑到自身的原料优势，选用了由1，2—环己二醇催化脱氢制备邻苯二酚的工艺路线。 本工艺路线的关键步骤是脱氢催化剂的选择，活性较好的脱氢催化剂有Pd、Pt、Ni等，考虑到催化剂的制备成本，选定了Ni作为脱氢催化剂活性组份。 首先对催化剂的载体进行了考察。通过对比实验，选定了活性碳作为催化剂的载体。以活性炭为载体，用普通浸渍法制成的催化剂效果较好。 接着探讨了不同助剂对催化剂性能的影响，发现了碱金属Na、K等有助于提高催化剂的选择性；同时还发现金属Pd、Sn、Cu等更能提高催化剂的选择性。最后选定了Na和Sn作为助催化剂，添加量分别为w（Na），2％ w（Sn），1％。同时还对干燥过程的影响进行了探讨，采用了分阶段逐步干燥的方式。 在以上实验讨论的基础上，用均匀设计的方法对催化剂制备的条件进行了优化。分析比较了各因素的影响，选定Ni含量，焙烧温度，焙烧时间，活化温度，活化时间，H₂用量等六个因素作为考察因素。对均匀实验的结果用程序进行了回归分析处理，发现Ni含量和焙烧温度的影响最大。接着采用了单因素实验对这两个因素进行了重点考察。通过有关实验，得到催化剂制备的较优条件为：w（Ni），12％ w（Na），2％ w（Sn），1％；焙烧温度673k，焙烧时间3h；还原温度643k，还原时间6h，H₂用量30ml／min。 本文还对邻苯二酚的制备工艺条件进行了优化。利用单因素实验对催化剂的颗粒度、载气流量、反应温度、以及催化剂负荷进行了考察。确定了较佳的工艺条件为：催化剂粒径20～40目，反应温度623k，载气流量20ml／min，进料量0.2ml／min。在该工艺条件下，采用本文制备的催化剂，邻苯二酚的收率可达70％左右。更多还原

【Abstract】 As an important organic intermediate, catechol is used extensively in many fields, such as medicine, pesticide, spice and chemical assistant. The domestic demand for it is so large that a majority of it need be imported to meet the demand. So, it is necessary for us to study the synthesis technology of catechol. Taking advantage of the abundant crude material of the Shen Ma Group and referencing a lot of contribution home and abroad, we put forwards a new technology route of dehydrogenization of 1,2-cyclohexanediol to catalyze the synthesis of catechol.The key to dehydrogenize of 1,2-cyclohexanediol to synthesize catechol is how to produce an appropriate catalyst. Platinum metals, palladium, nickel and so on are found having good performances in the literatures. But the cost of platinum and palladium are too high. Considered this, nickel is selected to be the active component in the catalyst.At first, after doing some contrast experiments among different catalyst carriers and preparation methods, we find that catalysts prepared by the method of precipitation on activated carbon which is served as catalyst carrier, the catalyst activity is higher, and selectivity is better.Then, we study the influence of different assist catalyst on catalyst activity and selectivity. We find that alkali metal addition can raising selectivity of the catalyst obviously. At the same time, the metals of palladium, copper and tin are found that they can also improve the selectivity. So, natrium and tin are select to be assist catalyst, the ratio of them is as followed: w(Na),2% and w(Sn),l %. At the same time, we discussed the step of drying how to influence the reaction. The grading drying method was determined.In the light of the above information, we adopt the method of homogeneous design to optimize the condition of producing catalyst. Several influencing factors are analyzed and compared, which are the addition amount of Ni, temperature of calcinations, time of calcinations, temperature of activation, time of activation, the velocity of H2. According to the coefficients in the equation of regression, the addition of nickel and temperature of calcinations have the greatest effect. As a result, these two factors are studied. Through single element experiment, the factors are determined as followed: w(Ni),12% w(Na),2% w(Sn),1%; temperature of calcinations is 673k, time of calcinations is 3 h; temperature of deoxidation is 643k, time of deoxidation is 6h, quantity of gas in deoxidation is 30ml/min, the result is the best.Afterward, the technological conditions using selected catalyst is optimized.. Some aspects are discussed, such as graininess of catalyst, flow of carrier gas, reacting temperature, and load of catalyst, using single element experiment. The optimum conditions are as follows: graininess of catalyst is 20-40 mesh, velocity ofcarrier gas is 20 ml/min, velocity of reacting liquid is 0.2 ml/min, reacting temperature is 623k. Under the condition, the yield can exceed 70%.更多还原