【作者】 许秀丽；

【导师】 谭世语；

【作者基本信息】 重庆大学 ， 应用化学， 2008， 硕士

【摘要】 工业生产6-硝基-1,2-重氮氧基萘-4-磺酸(简称6-硝)主要采用碱溶法合成,总体收率为58~60%,且生产过程中产生大量废水,色泽深,有机物浓度高,酸性强且难于生化降解。本论文主要从改变合成工艺条件入手,通过改变亚硝化反应条件来提高收率,同时力求从源头减少废水的排放。由于2-萘酚不溶于水,易溶于乙醇、乙醚、氯仿、甘油等有机溶剂,拟用水-醇混合溶剂来代替液碱溶解2-萘酚进行亚硝化反应。影响亚硝化反应主要因素是有机溶剂的选择、反应温度、硫酸浓度、加酸速度等,并在亚硝化后对物料采取过滤、水洗、风干等后处理,实验结果表明亚硝化反应的最佳条件为:以30g2-萘酚为原料,亚硝化温度为0~3℃,亚硝化时间为4h,与500g.l-1硫酸22ml进行亚硝化,有机溶剂乙醇用量为100ml时,稀释硫酸用水量为100ml即硫酸浓度取9%时,亚硝化保温时间为1h,在亚硝化反应后进行过滤水洗并在空气中风干6h。亚硝化反应后所得废水由电渗析进行脱盐处理,本文探讨了电压和出水流量对电渗析脱盐率的影响,得出电渗析的脱盐条件:电压40V,脱盐的淡水流量为24L/h时,所得淡水脱盐率达94.89%,完全可以回用,而剩余的废水量仅为碱溶法工艺废水量的1/5。由于乙醇在亚硝化反应完成后已经精馏回收,在进行下一步的加成和磺化时体系内不含乙醇,本实验针对物料的用量、反应时间、催化剂的用量、反应温度等对加成反应和磺化反应的影响做了一系列的对比实验,得出最佳的实验条件:取亚硫酸氢钠的摩尔用量为2-萘酚的摩尔用量的2.5倍,在1.5h内进行媒介绿反应,并选择硫酸铜做催化剂,在55~60℃转位6h。改进后的生产工艺在原料消耗、产品的收率、产生的废水量以及经济效益都比改进前有较明显的改善。醇溶法所需的原料均比碱溶法要少,1-氨基-2-萘酚-4-磺酸(简称1,2,4-酸)产率由68～70%提高到74.5%,亚硝化废水减少到原工艺的1/5,每合成1000kg1,2,4-酸节约生产成本约3290.4元,是一种经济可行的工艺,有利于工业化生产。更多还原

【Abstract】 6-Nitro-1,2-diazoxynaphthalene-4-sulfonic acid is mainly synthesized from base-dissolving method in dyestuff industry whose total product yield is 58~60%.There has been plenty of wastewater during the production process, and the waste water has the characteristic of dark color, high organic matter concentration, strong acidity and hardly in biodegradation. The thesis is to begin with the change in synthetic technology conditions, through changing the condition of nitration reaction to improve the yield and try to reduce the discharge of waste water at the same time.Forβ-naphthol is insoluble in water and soluble in organic soluent such as ethanol,ether,chloroform,glycerol etc .We plan to use water-ethanol binary mixtures to take place of the liquid alkali to dissolveβ-naphthol for nitration reaction. The main factors influencing the total product yield in nitration are the selection of organic soluent, reaction temperature, sulfuric acid concentration, the speed of acidification etc. Measures such as filtration、washing and air drying should be taken to materials after nitration. It is showed that the optimal experimental conditions for nitration reaction are determined by the following points: reaction temperature(0~3℃) , reaction time(4 hours), nitration reaction with a mixture of 30gβ-naphthol and 22ml sulfuric acid whose concentration is 500g.l-1 in 100ml ethanol medium. When the diluent water consumption is 100ml, namely the sulfuric acid concentration is 9%, heart-preservation time of the nitration reaction is 1 hour, then it has a filtration, washing and six-hour air drying after reaction. Wastewater from the nitration reaction is desalted by electrodialysis. The effects that Voltage and outlet flow rate have on the desalination by electrodialysis technology are discussed in this thesis. And conditions of the desalination by electrodialysis are concluded: Voltage 40V, fresh waster flow rate of desalination 24L/h, desalination rate of the freshwater reaches 94.89% which can be totally recycled. The residual wastewater is only 1/5 from the base-dissolving method. As ethanol has been distillated after the nitration reaction, so ethanol is not contained in the next addition reaction and sulfonation reaction. A series of comparison experiments are done according to a lot of factors that effect addition reaction and sulfonation reaction. Such as material amount、reaction time、catalyst amount、reaction temperature, etc. And best experiment conditions are concluded: take the amount of sodium bisulfite 2.5 times that ofβ-naphthol for addition reaction in 1.5h , choose CuSO4 as catalyst and translocate for 6h when the temperature reaches 55~60℃.The production technology process has obvious improvement on material consumption, product yield, wastewater amount of product and economic benefit after modification. Ethanol-solution method needs less materials than that of base-dissolving method, and the yield of 1-amino-2-naphthol-4-sulfonic acid(1,2,4-acid for short) has improved from 68～70% to 74.5%, wastewater of nitration reaction has reduced to 1/5 of the original process, thus it will save production cost for about 3290.4 yuan for synthesize every 1000kg 1,2,4-acid .So it is a economical and feasible process , good for industrial production.更多还原