【作者】 李明；

【导师】 丁军委；

【作者基本信息】 青岛科技大学 ， 化学工程（专业学位）， 2013， 硕士

【摘要】 醇钾作为催化剂因具有选择性好、活性高的优点被广泛应用于医药、农药等的有机反应中。但由于存在纯度低、游离碱含量高等缺点限制了其发展。为解决上述问题,本文研究了电解法制备甲醇钾和醇交换法制备叔丁醇钾这两种工艺,通过实验,确定了这两种方法的最佳工艺条件。电解法制备甲醇钾的工艺分为两部分：电解部分和催化反应部分。电解部分对各种影响实验结果的因素进行了分析,以电解过程中的电流效率为标准,通过单因素实验和正交实验,确定了电解的最佳条件：电解温度为20℃、钾汞齐浓度0.2%、电解液碳酸钾溶液的浓度为1mol·L-1、阴极电流密度为1.6KA·m-2,此条件下电解10min以上,电流效率即可达到95%以上。催化反应部分采用碳化钼催化剂催化钾汞齐与甲醇反应生成高纯度的甲醇钾。以甲醇钾的含量为标准,通过单因素实验和正交实验,确定了催化反应部分的最佳条件为：反应温度为60℃、催化剂用量为0.5%、反应时间为10分钟。将电解制备汞齐和催化反应两步联合操作,并采用部分采出、部分返回反应器重新反应的方式,采出比为1：1。从结果可以看出,在最佳电解条件下生成的钾汞齐与甲醇反应可以得到较高的收率,生成的甲醇钾含量达到29%以上,水分含量在0.5%左右,可以满足电解-合成反应联合生产的要求。甲醇钾与叔丁醇通过醇交换法制备叔丁醇钾,该实验通过反应精馏技术来实现。塔内叔丁醇循环利用,塔釜采出高质量的叔丁醇钾产品。以产品叔丁醇钾的纯度为标准,通过单因素实验和正交实验,确定了醇交换反应的最佳工艺条件：即塔顶压力为0.5MPa、叔丁醇与甲醇钾的进料摩尔比为12:1、回流比为7、进料总量为65mL·min-1、塔釜温度为145℃,此条件下可得到高纯度的叔丁醇钾。更多还原

【Abstract】 Potassium alcoholate was widely used in the organic reactions of pharmaceuticals and pesticides because of it’s good selectivity and high activity. But the drawbacks of low purity and high content of free alkali limitted it’s development. In order to solve these problems, this paper studied the process of producing potassium methylate by electrolytic method and the process of producing potassium t-butoxide by alcohol exchange method. The optimum reaction conditions of the two methods were obtained through experiments.The electrolytic method of preparing potassium methylate is divided into two parts:electrolysis and catalytic reaction. The electrolysis part has took all the factors which have an effect on the results of the experiments into consideration. Take the current efficiency as standards, via analyzing the results of single factors experiments and orthogonal experiments, the optimum reaction conditions were obtained:the electrolytic temperature is20℃, the potassium’s content of amalgam potassium is0.2%, the molar concentration of potassium carbonate solution is1mol·L-1, the cathode current density is1.6KA·m-2, the electrolytic time is more than10minutes. Under this condition the current efficiency can be above95%.Mo2C catalyst was used in the catalytic reaction of potassium amalgam and methanol to produce high-purity potassium methylate. Take the content of potassium methylate as standards, via analyzing the results of single factors experiments and orthogonal experiments, the optimum reaction conditions of this part were obtained: the reaction temperature is60℃, the weight ratio of catalyst to potassium amalgam is0.5%, the reaction time is10minutes.The electrolytic preparation of potassium methylate is a two-step joint operation, and we use reflux device on the bottom of the tower, the recovery ratio is1:1. The results show that the reaction of potassium amalgam producing from the electrolytic device and methanol can get a high yield, the content of potassium methylate can be above29%and the content of water is about0.5%. basically unchanged. So it can meet the requirement of the process for potassium methylate with electrolytic method.The alcohol exchange reaction of potassium methylate and t-butoxide can be achieved through reactive distillation technology. The t-butoxide was recycled in the tower and the high-quality product was mined from the bottom of the tower. Take the purity of potassium tert-butoxide as standards, via analyzing the results of single factors experiments and orthogonal experiments, the optimum reaction conditions were obtained:the pressure at the top of the tower is0.5MPa, the feed mole ratio of tert-butoxide and potassium methoxide is12:1, the reflux ratio is7, the total feed flow is65mL-min-1, the temperature on the bottom of the tower is145℃High purity of potassium t-butoxide can be abained under this condition.更多还原