表面活性剂的合成及其在铜电解中的应用研究

【作者】 张丽；

【导师】 李坚；

【作者基本信息】 昆明理工大学 ， 冶金物理化学， 2004， 硕士

【摘要】 本论文主要针对表面活性剂的结构对其性能产生的影响进行研究，并通过电解试验结果进一步讨论该添加剂在铜电解精炼中运用的可行性，同时与阿维同-A进行比较。阿维同-A是美国杜邦公司生产的产品。国外很多铜电解精炼厂将其作为添加剂与明胶、硫脲、盐酸同时使用；但在国内，目前只有金隆铜业股份公司使用。使用厂家认为，它在高电流密度的条件下，对电解铜阴极表面晶粒的细化起到积极的促进作用。随着国内铜电解生产向更大型化的发展、以及艾萨电解法的采用，提高铜电解生产的电流密度就是提高生产效率。因此对在高电流密度下能够改善阴极质量的添加剂产生了需求。项目的前期工作已经遴选出基本符合要求的新型添加剂。本论文在前期工作的基础上，自行合成结构类似的表面活性剂，并就表面活性剂的结构对性能产生的影响进行研究和探讨，找出主要影响因素，并将自行合成的表面活性剂应用于铜电解精炼，进一步说明了结构改进后的新型添加剂性能优于阿维同-A，可以作为阿维同-A的替代品，并且可以作为高电流密度下铜电解精炼的添加剂。本研究主要包括三个步骤：(1) 表面活性剂的合成：表面活性剂的合成过程中，需要自行制取符合结构要求的原料，即不同碳链长度的烷烃。本次试验通过对液体石蜡减压蒸馏取不同温度段的三个馏分，获得了三种包含不同碳链长度烷烃的馏分1#、2#、3#。馏分1#、2#、3#通过氯磺化反应制取三种同系物表面活性剂1#、2#、3#。(2) 表面活性剂理化性能测定与分析：表面活性剂理化性能的测定与分析过程中，对同系物表面活性剂1#、2#、3#的理化性质进行对比，并通过分析得出结论：表面活性由高到低依次为：活性剂3#、活性剂2#、活性剂1#，即疏水端碳链越长表面活性剂活性越高。(3) 表面活性剂在铜电解精炼中的应用：铜电解精炼试验过程中，遴选出较佳电解工艺条件，在此条件下对不加添加剂、加入活性剂1#、2#、3#和阿维同-A的电解阴极表面状况作对比，通过金相显微镜放大400倍的照片可以得出结论：不加添加剂的电解阴极片表面平整度和晶粒结晶情况较差；加入添加剂的电解阴极片中，添加剂3#情况最优，添加剂2#和阿维同-A效果相接近，添加剂1#效果较差。此外，又对不同电流密度下各种添加剂的性能做了对比，试验结果表明，在较高电流密度下，添加剂3#效果仍为最佳，添加剂2#和阿维同-A效果相接近，添加剂1#效果较差。昆明理工大学硕士学位论文摘要2004.1 最后我们得到结论:疏水端碳链长度增长提高了表面活性剂的活性，这种活性的提高同时改善其作为铜电解精炼添加剂的性能。碳链长度在14~19的磺酸盐性能差于阿维同一A，碳链长度在17一22的磺酸盐性能接近于阿维同一A，碳链长度在22~26的磺酸盐性能优于阿维同一A。活性剂3#可以作为阿维同一A替代品使用，亦可以应用于高电流密度下的电解精炼。更多还原

【Abstract】 It was studied in this article what influences will bring out when the molecular structure of the surfactant be changed. And it was discussed the possibility of this kind of surfactant being additive applying in the copper electrolysis according to the result of the experiments of the copper electrolysis. Also, it was compared the differences between this surfactant and Avitone-A. Avitone-A is produced by Du Pont Company of United States and is used for additive by a lot of foreign copper electrolysis refineries. While it is used only by one plant which is Jinlong Copper Company in China. And it is considered be effective by Jinlong Copper Company in improving the quality of catholic deposit of copper under high current density. In China, as the produce scale of copper is trending to mass production and ISA electrolytic technology is adopted more and more, it is advantage to enhance the current density during the eletrorefining process in order to increase the productivity of copper. So a new active additive which is effective under high current density will be needed. It is discussed in this paper that what influences resulting from the molecular structure’ s change will bring out on the character of the surfactant which is selected in the early research of this subject. The major influence element is found. Applying the new additive to the copper electrolysis refining ,it can be confirm basing on the result of the electrolytic experiments that the new additive is more active than Aviton-A, and it behave excellently during the copper electric refining under high electric current density .The new additive can be the substitute of Avitone-A.There are three steps involved in the research. Firstly, synthesizing the surfactants; Secondly, testing and analyzing thecharacters of the surfactants; Thirdly, applying the surfactants to the copper electrolysis. During the first step, it is requested to prepare three kinds of alkanes which are different in the length of the hydrocarbon chains. The suited alkanes which are numbered 1#,2#,3# are acquired by the vacuum distillations of paraffin. After chlorosulfonation .three kinds of surfactants are acquired which are named surfactant 1#, 2#,3#. In the second step, the physicochemical properties are compared among the homologous series 1#, 2#,3# and the conclusion are got that the surface activity of the additives from high to low in turn is :3#,2#, 1#, i. e. the longer the carbon chain is, the more active the additive is .During the third process, it is requested to select the better technological conditions. Under the conditions, the quality of catholic deposit of copper are compared between without surfactant and with additive 1#,2#,3#, Avitone-A during the eletroref ining process. The metallographs which are zoomed in 400 times show that when the electrolytic process without additive, the surface conditions of the catholic copper are poorer than when the process with additive. It also tell that the additive 38 is the best, and the additive 28 is approximate to Avitone-A, in contrast the additive in is baddish. The quality of the cathode also be compared under different current density. The results of the experiments indicate that under high current density, the additive 3# still is the best one, the additive 2# is approximate to Avitone-A, the additive 18 is baddish. Finally, the conclusion can be drawn that the surface activity can be enhance as a result of increasing the length of the hydrophobe hydrocarbone chain,at the same time improving the properties of the additive Itself being addition agent during the copper eletrorefining process. The property of the sulfonate which aliphatic hydrocarbons containing from 14 to 19 carbone atoms is poorer than the property of Avitone-A. The sulfonate which aliphatic hydrocarbons containing from 17 to 22carbon atoms is approximate to Avitone-A. The sulfonate which aliphatic hydrocarbons containing from 22 to 26 carbon atoms is better than Avitone-A. The additive 3# can be substitute of Avitone-A and it still can be effect更多还原