2-巯基苯并噻唑功能化离子液体构筑的萃取体系分离铂族金属

发布时间：2018-06-12 03:14

本文选题：2-巯基苯并噻唑 + 功能化离子液体　；参考：《山东大学》2017年硕士论文

【摘要】：在全球性资源紧缺以及环境污染问题日益严重的境况下,低碳环保及有限资源的高效利用日益成为人们关注的焦点。储量的有限性及应用的广泛性,决定了铂族金属离子的萃取回收、循环利用愈发重要。离子液体作为一种绿色无污染的有机盐,独特的热力学性质使得其被广泛的应用在有机化学反应,电化学,脱硫以及萃取分离领域并且成为当前热点研究体系之一。近年来,离子液体在铂族金属分离萃取体系中的应用取得了很大的突破,同时也暴露了较大的不足,而此瓶颈转而限制了离子液体在萃取领域的广泛应用。常规的离子液体缺乏特定的官能团具有较弱的铂族金属螯合能力,再者铂族系金属具有相似的物理化学特性,使得铂族系金属之间的分离面临着巨大的困难。故而,发展合成兼具特定选择性和高萃取效率的功能化离子液体成为分离铂族金属的有效手段之一,并亟待进一步丰富发展。2-巯基苯并噻唑功能化离子液体是将2-巯基苯并噻唑引入到普通的咪唑类离子液体的阴离子构筑而得,合成的功能化离子液体具有较强的铂族金属的络合能力,对铂族金属表现出良好的选择性。基于以上,本论文设计并合成了系列2-巯基苯并噻唑功能化离子液体,将其应用在单个铂族金属(钯,钌)离子的萃取分离并且实现了钯、铂的高效分离。主要研究内容和结果如下:一、2-巯基苯并噻唑功能化离子液体([C10(mim)2]2+2[MBT]-)的合成以及其构筑液液萃取体系分离钯的研究。首先探究了一系列影响钯萃取行为的因素,例如:2-巯基苯并噻唑功能化离子液体浓度,盐酸浓度,氯化钠浓度,氢离子浓度以及硝酸钠浓度。同时,详细推断验证了钯萃取的机理并且证实了此体系为一种特殊的金属络合机理。除此之外,相同条件下萃取Ni(Ⅱ),Al(Ⅲ),Co(Ⅱ),Pt(Ⅳ),Ru(Ⅲ)和Rh(Ⅲ)金属具有较低的萃取效率。采用0.5 M硫脲/1.0 M盐酸作为反萃剂可以快速高效将钯从疏水性离子液体相反萃出来。因此,2-巯基苯并噻唑功能化离子液体对钯的萃取具有兼高萃取效率和高选择性。二、将2-巯基苯并噻唑功能化离子液体引入到一种新兴的环境友好型浊点萃取体系用来从水溶液中萃取钌到富集相。此浊点萃体系(?)作为表而活性剂和2-巯基苯并噻唑功能化离子液体([C6mim]+得。首先研究了一系列影响钌萃取行为的因素,例如:2-巯基苯并噻唑功能化离子液体的浓度,盐酸和硝酸的浓度,TX-114的质量分数,TX-114的体积,氯化钠的浓度。在优化的条件下,钌的萃取率可以达到82%,此时体系的富集系数为40。借以Job法,紫外光谱以及红外光谱分析详细阐释了钌的萃取机理,系统性地证实了钌在浊点萃取过程中的金属络合机理。与相关的萃取钌体系比较之下,2-巯基苯并噻唑功能化离子液体参与的浊点萃取体系对钌表现出较高的萃取效率。三、探究2-疏基苯并噻唑功能化离子液体为萃取剂构筑的液液萃取体系分离钯、铂的过程。萃取条件的筛选优化—萃取平衡时间,水相与有机相的体积比,2-巯基苯并噻唑功能化离子液体的浓度,盐酸的浓度,氯化钠的浓度。在优化的条件下,钯、铂的分离系数可以达到1558,相较于类似钯、铂分离体系的文献报道,此方法的分离系数较大,可以实现二者的快速有效分离。同时,通过红外光谱探究了钯、铂的萃取机理,研究发现在此体系中钯、铂的萃取机理都均是金属络合机制。综上,2-巯基苯并噻唑功能化离子液体构筑的液液萃取方法可以快速的将钯、铂分离,为钯、铂高效的分离提供了一种新的分离方法。
[Abstract]:Low carbon environmental protection and the efficient utilization of limited resources have increasingly become the focus of attention in the situation of the shortage of global resources and the increasingly serious environmental pollution problems. The limited and extensive application of reserves determines the extraction and recovery of platinum group metal ions, and the more important the recycling is. Ionic liquid is a green and pollution-free. Organic salts, with their unique thermodynamic properties, have been widely used in the field of organic chemical reactions, electrochemistry, desulfurization and extraction separation, and become one of the most popular research systems. In recent years, the application of ionic liquids in the separation and extraction system of platinum group metals has made great breakthroughs and has also exposed a large number of shortcomings. The bottleneck has limited the wide application of ionic liquids in the field of extraction. Conventional ionic liquids lack specific functional groups with weak platinum group metal chelating capabilities. Moreover, the platinum group metals have similar physical and chemical properties, making the separation between the platinum groups facing huge difficulties. Therefore, the development of synthesis has a specific selection. The functional ionic liquid with high selectivity and high extraction efficiency is one of the effective means to separate the platinum group metal, and it is urgent to further enrich and develop the.2- mercapto thiazole functional ionic liquid, which is constructed by the introduction of 2- mercapto benzothiazole into the ordinary imidazole ionic liquid, and the synthesized functional ionic liquid is stronger. The complexation ability of platinum group metals shows good selectivity for platinum group metals. Based on the above, a series of 2- mercapto thiazole functional ionic liquids are designed and synthesized, which are applied to the extraction and separation of single platinum group metal (palladium, ruthenium) ions and the high efficiency separation of palladium and platinum. The main contents and results are as follows: First, the synthesis of 2- mercapto thiazolazole functional ionic liquid ([C10 (MIM) 2]2+2[MBT]-) and the study of its construction of liquid liquid extraction system for separation of palladium. First, we explored a series of factors affecting the extraction behavior of palladium, such as the concentration of 2- mercapto benzothiazole functional ionic liquid, the concentration of hydrochloric acid, the concentration of sodium chloride, the concentration of hydrogen ion and sodium nitrate. At the same time, the mechanism of palladium extraction was verified and proved to be a special metal complexation mechanism. In addition, the extraction efficiency of Ni (II), Al (III), Co (II), Pt (IV), Ru (III), Ru (III) and Rh (III) metals was lower in the same condition. Palladium could be quickly and efficiently used as a stripping agent with 0.5 M thiourea /1.0 M hydrochloric acid. 2- mercapto thiazole functional ionic liquids have high extraction efficiency and high selectivity for the extraction of palladium from hydrophobic ionic liquids. Two, 2- mercapto thiazole functional ionic liquid is introduced into a new environment friendly cloud point extraction system to extract ruthenium from aqueous solution to enriched phase. The point extraction system (?) is used as a table, active agent and 2- mercapto thiazole functional ionic liquid ([C6mim]+). First, a series of factors affecting the extraction behavior of ruthenium, such as the concentration of 2- mercapto benzothiazole, the concentration of hydrochloric acid and nitric acid, the mass fraction of TX-114, the volume of TX-114, the concentration of sodium chloride, and the concentration of sodium chloride. Under the conditions, the extraction rate of ruthenium can reach 82%, and the enrichment coefficient of the system is 40. by Job method. The extraction mechanism of ruthenium is explained in detail by ultraviolet and infrared spectroscopy. The mechanism of the metal complexation of ruthenium in the process of cloud point extraction is systematically confirmed. In comparison with the related extraction ruthenium system, the function of 2- mercapto thiazolothiazole is functionalized. The cloud point extraction system involved in ionic liquids showed high extraction efficiency for ruthenium. Three, the process of separation of palladium from the liquid extraction system constructed by 2- sparse benzothiazole functional ionic liquids as extractant, the optimization of extraction conditions, the extraction equilibrium time, the volume ratio of water phase to organic phase, and the functionalization of 2- mercapto thiazolyl The concentration of ionic liquid, the concentration of hydrochloric acid, the concentration of sodium chloride. Under the optimized conditions, the separation coefficient of palladium and platinum can reach 1558. Compared with the palladium and platinum separation systems, the separation coefficient of this method is larger, and the rapid and effective separation of the two can be realized. At the same time, the extraction mechanism of palladium and platinum is explored by infrared spectroscopy. It is found that the extraction mechanism of palladium and platinum in this system is all metal complexing mechanism. To sum up, the liquid liquid extraction method of 2- mercapto thiazole functional ionic liquid can quickly separate palladium and platinum, which provides a new separation method for palladium and platinum efficient separation.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O645.1;O658.2

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