间氨基苯酚制备及产物分离工艺的研究_张敏

摘要

间氨基苯酚（MAP）是一种重要的精细化工原料和有机中间体，在石油化学工业、农药、医药、染料等领域的应用十分广泛。到目前为止，开发出了多种合成间氨基苯酚的工艺，主要有硝基苯磺化碱熔法、间苯二酚氨解法、间硝基苯酚电解法、苯胺羟基化法和间苯二胺盐酸水解法等，但它们大都分别存在着工艺落后、污染严重、成本较高和对设备要求较高等的问题。

本文重点研究了间苯二胺硫酸水解制备间氨基苯酚的合成新工艺和水解产物结晶分离制备MAP的纯化工艺两部分。具体研究内容和结果如下：

通过单因素实验和正交实验，考察了反应时间、温度、物料配比和酸的浓度对间苯二胺水解反应的影响，确定了最佳的工艺条件为：酸的浓度为23%，反应温度为190 ℃，间苯二胺与浓硫酸的摩尔比为1:2.10，反应时间为20 h。在此条件下间苯二胺的转化率达到了99.0%，间氨基苯酚的收率为43.8%，间苯二酚的收率是54.4%。通过动力学实验，分别得到了在190 ℃、200 ℃、210 ℃温度条件下间苯二胺水解反应的速率方程，并求得水解反应的频率因子和活化能。

鉴于间苯二胺硫酸水解制备间氨基苯酚工艺的水解产物包含间氨基苯酚、间苯二酚和少量间苯二胺三种组分的情况，先用乙酸丁酯萃取分离间苯二酚，然后对间苯二胺和MAP进行结晶分离得到纯净的MAP，并确定了结晶工艺条件。其条件为：溶液的pH值为7.08，结晶温度为15 ℃，结晶时间为40 min，搅拌转速为500 r·min-1。

本文提出了硫酸法水解制备间氨基苯酚的新工艺，优化了水解工艺条件，得出不同温度条件下的间苯二胺水解反应的速率方程，并对产物进行先萃取后结晶的分离工艺进行研究。对此未见国内外文献报导，为该工艺的深入研究打下了基础。

关键词：间氨基苯酚 间苯二胺 间苯二酚 萃取 结晶

Abstract

m-Aminophenol(MAP), an important chemical raw material and organic intermediate, has been widely used for many fields such as, petrochemical industry, agricultural chemicals, pharmacy, and dyestuff. Now so many methods had been discovered to prepare MAP, which included nitrobenzene sulfonated alkali fusion, resorcinol liquid ammonolysis solution, m-nitrophenol electrolysis, hydroxylation of aniline, and m-phenylenediamine hydrolysis with HCl, but those technics have many limitations such as, outdated technics, serious pollution, high costs, high equipment requirement and so on.

The paper mainly studied two parts which were the new technics for MAP by m-phenylenediamine hydrolysis with H2SO4 and the separation of hydrolyzate. The contents and results were as follows.

The synthetic process of MAP was reviewed, and the optimal reaction conditions were

℃confirmed as follow: the concentration of acid 23%, reaction temperature 190 , the mole ratio of m-phenylenediamine to acid 1:2.10, reaction time 20 h. Under these conditions the conversion of m-phenylenediamine acid reach up to 99.0%, the yield of MAP was 43.8%and the yield of resorcinol was 54.4%.In addition, the rate equations of m-phenylenediamine hydrolysis at different temperature of 190 ℃,200 ℃,and 210 ℃ were also obtained through kinetic experiment and achieved the activation energy and frequency factor of the hydrolysis reaction.

In view of process of the preparation of m-aminophenol by hydrolysis of m-phenylenediamine with sulfuric acid contained three components, product of m-aminophenol, resorcinol and a small number of m-phenylenediamine. using butyl acetate to extract resorcinol, and then pure MAP can be accquired by separated the m-phenylenediamine and MAP through crystallization. The crystallization conditions are as follows: the solution

℃ min, stirring speed pH 7.08, the crystallization temperature15 , the crystallization time 40

500 r·min-1.

In this acticle, the new technics for MAP by m-phenylenediamine hydrolysis with H2SO4 was recored, the separation of hydrolyzate with the method of solvent extraction was studied, the reaction condition was optimized,and rate equation under different temperature was obtained. Those results had not been reported with any literature, and lay foundation for the in-depth research on this process. In addition the product of resorcinol of separation is also an important organic chemical intermediates, so the process is a line of zero emissions of green technology.

Key words: m-Aminophenol, m-Phenylenediamine, Resorcinol, Hydrolysis