2-羟基-5-特辛基苯乙酮肟的合成、表征及其萃取性能的研究

发布时间：2018-05-25 18:10

本文选题：2-羟基-5-特辛基苯乙酮肟 + 合成优化　；参考：《江西理工大学》2014年硕士论文

【摘要】：我国铜冶炼以处理高品位铜矿的火法冶炼技术为主。经过几十年的生产,我国很多铜矿已进入开采后期,富矿、易选矿资源己近枯竭,火法冶炼进入了无原料生产的困境,这使大力发展适宜处理低品位铜矿的湿法冶铜技术成为必要。萃取作为湿法冶铜的一个重要组成部分,有着十分重要的研究意义。其中,萃取剂的选取起着决定性的作用。目前,我国湿法冶铜工业所用的萃取剂很大程度上依赖进口。进口铜萃取剂价格昂贵,因此,研究利用国产化工原料,大力开发具有自主知识产权的铜萃取剂,对我国湿法冶铜技术发展有着现实而深远意义。本文在芳香族羟酮肟萃取剂的结构基础上,用特辛基对其芳环上的烷基取代基进行结构修饰,合成了2-羟基-5-特辛基苯乙酮肟。探讨了其合成最佳工艺条件及其在酸性溶液中对铜的萃取条件及萃取效率。以四氯乙烯为溶剂,对特辛基苯酚、乙酰氯、无水Al Cl3和盐酸羟胺为主要原料,采用分步合成法合成了2-羟基-5-特辛基苯乙酮肟。对特辛基酚在80℃下,与乙酰氯反应2.5 h,形成酚酯。接着升高温度至100℃,在无水Al Cl3催化条件下,进行Frise重排反应3.5 h,得到了2-羟基-5-特辛基苯乙酮。后者与盐酸羟胺在无水碳酸钠作缚酸剂的条件下进行肟化反应,合成了目标产物2-羟基-5-特辛基苯乙酮肟。正交试验优化反应条件后,其平均收率达到68.4%。对合成产物进行傅里叶红外光谱、紫外光谱、核磁共振和高效液相色谱检测,综合检测表明合成产物为目标产物2-羟基-5-特辛基苯乙酮肟。高效液相色谱检测表明产物纯度大于99%。研究了2-羟基-5-特辛基苯乙酮肟在酸性溶液对铜的萃取与反萃性能。实验结果表明:在温度25℃,初始水相p H值=4,Cu2+浓度为4 g·L-1,2-羟基-5-特辛基苯乙酮肟铜萃取剂在稀释剂中浓度为10%,水相和有机相的体积比(A/O)=1:1.5,振荡时间3 min的条件下,铜萃取剂对铜的单级萃取率达到95.45%。在温度25℃,H2SO4浓度为180 g·L-1,有机相与水相的相比(A/O)=1:1,反萃时间5 min的条件下,铜的单级反萃率达到94.35%。本文进一步完善了羟肟类萃取剂萃取铜的理论研究。所合成的萃取剂对铜有较好的萃取效果,可以作为进口铜萃取剂的候补;有望优化羟肟萃取剂的复配体系;对提高湿法炼铜生产效率有很好的促进作用。
[Abstract]:After several decades of production, many copper mines in our country have entered the later period of mining, rich ore, easy mineral resources have been exhausted, and fire smelting has entered the difficult situation of raw material production, which makes it necessary to develop wet metallurgy technology suitable for treating low grade copper mines. As an important part of the wet metallurgy copper, it has a very important research significance. Among them, the selection of extractants plays a decisive role. At present, the extractant used in the wet metallurgy industry in China is largely dependent on the import. The imported copper extractant is very expensive. Therefore, the research and utilization of domestic chemical raw materials have been developed with great efforts. The copper extraction agent of the main intellectual property has a realistic and profound significance to the development of wet metallurgy of copper in China. On the basis of the structure of the aromatic hydroxyketoxime extractant, the structure modification of the alkyl substituents on the aromatic ring of the aromatic hydroxyketoxime was constructed and the 2- hydroxy -5- terocyl acetophenone oxime was synthesized, and the optimum synthesis conditions and its application were discussed. The extraction conditions and efficiency of copper in acid solution. Using four chloroethylene as the solvent, 2- hydroxyl -5- terocinyl acetophenone oxime was synthesized by step synthesis by step synthesis, with teocylphenol, acetyl chloride, anhydrous Al Cl3 and hydroxylamine hydrochloride as the main raw materials. The reaction of teocylphenol to acetyl chloride was 2.5 h, and the phenol ester was formed at 80 C. Then the temperature was raised to 10. At 0 C, under the condition of water free Al Cl3, Frise rearrangement reaction was 3.5 h, and 2- hydroxy -5- teoctyl acetophenone was obtained. The latter was oximed with hydroxylamine hydrochloride under the condition of anhydrous sodium carbonate as an acid binding agent. The target product 2- hydroxy -5- teroctyl acetophenone oxime was synthesized. The average yield of the product was 68.4 after the orthogonal test. The synthetic products were detected by Fourier transform infrared spectroscopy, ultraviolet spectroscopy, nuclear magnetic resonance and high performance liquid chromatography, and the synthetic products were detected as the target product 2- hydroxy -5- teoctyl acetophenone oxime. High performance liquid chromatography showed that the purity of the product was greater than 99%. and the extraction of 2- hydroxy -5- tertyl Acetophenone oxime in acid solution to copper The experimental results show that at 25 C, the initial water phase P H value =4, Cu2+ concentration is 4 g. L-1,2- hydroxyl -5- acetophenone oxime oxime copper extractant in the diluent concentration is 10%, the volume ratio of the water and organic phase (A/O) =1:1.5, oscillation time 3 min, copper extraction agent to copper single stage extraction rate to 95.45%. in the temperature 25 The concentration of H2SO4 is 180 G. L-1, the organic phase is compared with the water phase (A/O) =1:1, and the stripping time is 5 min. The single stage stripping rate of copper reaches 94.35%.. This paper further perfects the theoretical study on the extraction of copper by hydroxamic acid extractant. The synthesized extractant can be used as a candidate for copper extractant. The complex system of hydroxyl oxime extractant can improve the production efficiency of copper hydrometallurgy.
【学位授予单位】：江西理工大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：TF811;TQ421.12

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