本文選題：2-巰基苯并噻唑 + 功能化離子液體　； 參考：《山東大學(xué)》2017年碩士論文

【摘要】：在全球性資源緊缺以及環(huán)境污染問題日益嚴(yán)重的境況下,低碳環(huán)保及有限資源的高效利用日益成為人們關(guān)注的焦點。儲量的有限性及應(yīng)用的廣泛性,決定了鉑族金屬離子的萃取回收、循環(huán)利用愈發(fā)重要。離子液體作為一種綠色無污染的有機鹽,獨特的熱力學(xué)性質(zhì)使得其被廣泛的應(yīng)用在有機化學(xué)反應(yīng),電化學(xué),脫硫以及萃取分離領(lǐng)域并且成為當(dāng)前熱點研究體系之一。近年來,離子液體在鉑族金屬分離萃取體系中的應(yīng)用取得了很大的突破,同時也暴露了較大的不足,而此瓶頸轉(zhuǎn)而限制了離子液體在萃取領(lǐng)域的廣泛應(yīng)用。常規(guī)的離子液體缺乏特定的官能團具有較弱的鉑族金屬螯合能力,再者鉑族系金屬具有相似的物理化學(xué)特性,使得鉑族系金屬之間的分離面臨著巨大的困難。故而,發(fā)展合成兼具特定選擇性和高萃取效率的功能化離子液體成為分離鉑族金屬的有效手段之一,并亟待進一步豐富發(fā)展。2-巰基苯并噻唑功能化離子液體是將2-巰基苯并噻唑引入到普通的咪唑類離子液體的陰離子構(gòu)筑而得,合成的功能化離子液體具有較強的鉑族金屬的絡(luò)合能力,對鉑族金屬表現(xiàn)出良好的選擇性�；谝陨�,本論文設(shè)計并合成了系列2-巰基苯并噻唑功能化離子液體,將其應(yīng)用在單個鉑族金屬(鈀,釕)離子的萃取分離并且實現(xiàn)了鈀、鉑的高效分離。主要研究內(nèi)容和結(jié)果如下:一、2-巰基苯并噻唑功能化離子液體([C10(mim)2]2+2[MBT]-)的合成以及其構(gòu)筑液液萃取體系分離鈀的研究。首先探究了一系列影響鈀萃取行為的因素,例如:2-巰基苯并噻唑功能化離子液體濃度,鹽酸濃度,氯化鈉濃度,氫離子濃度以及硝酸鈉濃度。同時,詳細(xì)推斷驗證了鈀萃取的機理并且證實了此體系為一種特殊的金屬絡(luò)合機理。除此之外,相同條件下萃取Ni(Ⅱ),Al(Ⅲ),Co(Ⅱ),Pt(Ⅳ),Ru(Ⅲ)和Rh(Ⅲ)金屬具有較低的萃取效率。采用0.5 M硫脲/1.0 M鹽酸作為反萃劑可以快速高效將鈀從疏水性離子液體相反萃出來。因此,2-巰基苯并噻唑功能化離子液體對鈀的萃取具有兼高萃取效率和高選擇性。二、將2-巰基苯并噻唑功能化離子液體引入到一種新興的環(huán)境友好型濁點萃取體系用來從水溶液中萃取釕到富集相。此濁點萃體系(?)作為表而活性劑和2-巰基苯并噻唑功能化離子液體([C6mim]+得。首先研究了一系列影響釕萃取行為的因素,例如:2-巰基苯并噻唑功能化離子液體的濃度,鹽酸和硝酸的濃度,TX-114的質(zhì)量分?jǐn)?shù),TX-114的體積,氯化鈉的濃度。在優(yōu)化的條件下,釕的萃取率可以達到82%,此時體系的富集系數(shù)為40。借以Job法,紫外光譜以及紅外光譜分析詳細(xì)闡釋了釕的萃取機理,系統(tǒng)性地證實了釕在濁點萃取過程中的金屬絡(luò)合機理。與相關(guān)的萃取釕體系比較之下,2-巰基苯并噻唑功能化離子液體參與的濁點萃取體系對釕表現(xiàn)出較高的萃取效率。三、探究2-疏基苯并噻唑功能化離子液體為萃取劑構(gòu)筑的液液萃取體系分離鈀、鉑的過程。萃取條件的篩選優(yōu)化—萃取平衡時間,水相與有機相的體積比,2-巰基苯并噻唑功能化離子液體的濃度,鹽酸的濃度,氯化鈉的濃度。在優(yōu)化的條件下,鈀、鉑的分離系數(shù)可以達到1558,相較于類似鈀、鉑分離體系的文獻報道,此方法的分離系數(shù)較大,可以實現(xiàn)二者的快速有效分離。同時,通過紅外光譜探究了鈀、鉑的萃取機理,研究發(fā)現(xiàn)在此體系中鈀、鉑的萃取機理都均是金屬絡(luò)合機制。綜上,2-巰基苯并噻唑功能化離子液體構(gòu)筑的液液萃取方法可以快速的將鈀、鉑分離,為鈀、鉑高效的分離提供了一種新的分離方法。
[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.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O645.1;O658.2

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