可溶性氟硅酸盐的制备与应用研究

发布时间：2018-03-10 17:22

本文选题：离子交换膜　切入点：阳离子膜电解法　出处：《上海应用技术大学》2017年硕士论文　论文类型：学位论文

【摘要】：近年来随着我国化工产业的强力发展,以及世界工业的快速发展,特别是在高速发展的铝行业的推动下使氟化盐的消耗量大幅度的增加,造成在世界氟化盐市场的消耗量迅速增大。而氟硅酸钠作为磷肥化工行业的副产物,来源简单而且价格比较低廉,易于得到,其中所含的硅资源与氟资源是一种很重要的化工资源,利用氟硅酸钠来回收硅与氟是很有研究价值的。本文首先利用阳离子膜电解法电解氟硅酸钠制备出氟硅酸,然后利用氟硅酸的氨化水解反应制备出白炭黑以及氟化氢铵,回收其中的硅资源与氟资源。再电解氟硅酸来制备可溶性过渡金属氟硅酸盐,并对氟硅酸铜作为镀铜液主盐的可行性来进行探究。本文主要内容包含下面几个方面:1.使用阳离子膜电解的方法,电解氟硅酸钠来制备氟硅酸溶液,制备出氟硅酸。并通过与氨水氨化反应制备二氧化硅与氟化氢铵,来证明电解氟硅酸钠制备的溶液为氟硅酸。通过调节电解制备氟硅酸钠的电流密度梯度,来探究制备氟硅酸的产率,最后发现在电流密度为6. 25mA/cm2时,得到的二氧化硅白炭黑质量最高,氟硅酸浓度最大,氟硅酸钠的转化率最高。使用先前制备的氟硅酸与氨水进行氨化水解反应,制备二氧化硅白炭黑,并且利用XRD、IR以及EDX等表征手段对制备的二氧化硅白炭黑进行表征分析,分析其晶型结构、组分。证明了所制备的二氧化硅白炭黑为无定形非晶体结构,并证明了电解氟硅酸钠制备的阳极液为氟硅酸。使用先前制备的氟硅酸与氨水进行氨化反应制备氟化氢铵,并通过XRD、IR以及EDX对其晶型结构以及组分进行分析,证明所制备的产物为氟化氢铵。2.利用阳离子膜电解氟硅酸钠制备的氟硅酸制备可溶性过渡金属氟硅酸盐。并分别制备出了氟硅酸铜与氟硅酸锌。并且利用XRD分析、热重(TG)分析、EDX能谱分析等表征手段,证明利用阳离子膜电解法电解氟硅酸能制备出可溶性的过渡金属氟硅酸盐。本文首次采用了阳离子膜电解法来电解氟硅酸制备可溶性过渡金属氟硅酸盐,利用电解氟硅酸钠制备的氟硅酸,并成功制备出了氟硅酸铜与氟硅酸锌晶体,对于氟硅酸钠以及氟硅酸的应用与回收提供了一个很好的思路与方法。3.本文利用三电极体系来测试铜在常温下氟硅酸铜溶液中的循环伏安曲线,可以看出该体系为不完全可逆反应,在0. 2067V和0. 3414V出现了两个氧化峰,-0. 102V出现了铜的还原峰。并且随着扫描速率的升高氧化峰电势电位正移,还原峰电势电位负移,且在在扫描速率为80mV/s的条件下,一价铜离子的峰面积明显大于二价铜离子的峰面积,对镀层的质量影响比较大。随着温度的升高,氧化峰的峰宽逐渐变大,易于铜在氟硅酸铜溶液中的溶解。根据铜在常温下氟硅酸铜溶液中的阳极极化曲线可知,铜的电化学溶解区的电势电位范围为0. 053V～0. 243V,且随着温度的增加电化学溶解区的峰宽增大。在40℃的条件下,铜工作电极在氟硅酸铜溶液中的溶解条件最佳。结合以上条件,如果利用氟硅酸铜作为镀铜液的主盐还需要找到合适的条件使得铜在氟硅酸铜体系成为一种可逆体系,使得铜在氟硅酸铜溶液中的溶解与还原达到平衡。
[Abstract]:In recent years, with the strong development of China's chemical industry, and the rapid development of industry, especially to promote the rapid development of aluminum industry in the increasing consumption of substantial fluoride salt, resulting in consumption in the world market. The rapid increase of fluoride and sodium fluoride as a by-product of phosphate chemical industry the source, simple and relatively inexpensive, easy to obtain, the silicon containing fluorine resources and resources is a very important chemical resources, recycling of silicon and fluorine is very valuable to study the use of sodium fluosilicate. Firstly, using the cationic membrane electrolysis electrolysis of sodium fluosilicate prepared fluosilicic acid, and then use the ammoniation of hydrolysis of fluosilicic acid prepared silica and ammonium hydrogen fluoride, recycling the silicon and fluorine resource resources. Electrolytic preparation of fluosilicic acid soluble transition metal fluoride silicate, and copper fluoride as copper plating solution To explore the feasibility of the main salt. The main contents of this paper include the following aspects: 1. using the method of cation exchange membrane electrolysis, electrolysis of sodium fluosilicate to prepare fluorosilicic acid solution, preparing fluosilicic acid and ammonia. And through the amination reaction of preparing silica and ammonium hydrogen fluoride, to permit the electrolytic sodium fluosilicate solution system for the preparation of fluosilicic acid. The current density gradient preparation of sodium fluosilicate regulating electrolytic system, to explore the preparation of fluosilicic acid was finally found in the current density is 6. 25mA/cm2, the highest quality silica silica, the fluoride concentration of sodium fluosilicate, conversion rate is the highest. The use of previous fluorine the preparation of silicic acid and ammonia by hydrolysis, preparation of silica silica, and the use of XRD, IR and EDX characterizations of silica silica were analyzed, the analysis of the crystal structure, composition. The preparation of white carbon black silica is amorphous and amorphous structure, and it is proved that the anode electrolysis of sodium fluosilicate prepared for fluosilicic acid. Using fluosilicic acid and ammonia system previously prepared by amination in preparation of ammonium hydrogen fluoride, and through XRD, IR and EDX to analyze the crystal structure and that group, the prepared product is ammonium hydrogen fluoride.2. by ion membrane electrolysis of sodium fluosilicate preparing fluosilicic acid for preparing soluble transition metal fluoride and silicate. Were synthesized fluosilicic acid copper and zinc silicate. And the use of XRD analysis, thermogravimetric analysis (TG), EDX energy spectrum analysis by means of proof of electrolytic fluosilicic acid by using cation membrane electrolysis to prepare soluble transition metal fluoride silicate. For the first time in this paper using cationic membrane electrolysis to prepare soluble transition metal fluoride silicate to electrolytic fluorosilicic acid, sodium fluosilicate produced by electrolysis Preparation of fluosilicic acid, and successfully synthesized fluosilicic acid copper and zinc silicate crystal, the sodium fluosilicate and fluosilicic acid recovery application and provides a good idea and method of.3. using the three electrode system to test cyclic voltammetry of copper at room temperature fluorine copper silicate solution, can the system is not fully reversible reaction in 0. 2067V and 0. 3414V two oxidation peaks, -0. 102V the reduction peak of copper. And with the scan rate increased the oxidation peak potential shifts positively and the reduction peak potential shifted negatively, and at the scan rate of 80mV/s, peak area the peak area of monovalent copper ions are significantly greater than two copper ion, affecting the quality of the coating is relatively large. With the increase of temperature, the oxidation peak width becomes larger, easy to dissolve in copper fluoride copper silicate solution. According to the copper at room temperature fluorosilicic acid copper solution The anodic polarization curves of liquid in the range of potential electrochemical dissolution of copper in the area of 0. 053V to 0. 243V, and with the increase of temperature the electrochemical dissolution peak width increases. At the temperature of 40 DEG C, the dissolution conditions of copper working electrode in fluosilicic acid copper in the solution. With the best condition, if the use of copper fluoride as the main salt copper liquid also need to find the right conditions makes copper become a reversible system in fluorine copper silicate system, the copper dissolution in fluorine copper silicate solution and restore the balance.

【学位授予单位】：上海应用技术大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ127.2

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