本文關鍵詞： 高純鈷 離子交換 樹脂Monophos 雜質(zhì)鐵 電解精煉　出處：《河南科技大學》2017年碩士論文　論文類型：學位論文

【摘要】：高純鈷具有優(yōu)良的半導體性質(zhì)、磁性能及導電性能,是制備磁記錄介質(zhì)、磁記錄磁頭、光電器件、磁傳感器和集成電路等元器件的重要材料。5N及以上純度的高純鈷則主要用來制造超大規(guī)模集成電路行業(yè)用濺射靶材。目前限于技術原因,5N及以上高純鈷需要大量進口,因而開發(fā)具有自主知識產(chǎn)權的高純鈷制備技術尤為重要。本文通過離子交換提純+CoSO4水溶液電解的方法制備高純鈷,并針對鈷鹽溶液中主要雜質(zhì)元素Fe難以去除的共性問題,嘗試采用新型螯合樹脂Monophos吸附鈷料液中的雜質(zhì)元素Fe,并通過系統(tǒng)實驗分析確定樹脂Monophos吸附Fe的最佳工藝條件和CoSO4體系電解法制備高純鈷的穩(wěn)定生產(chǎn)工藝。通過靜態(tài)吸附試驗,考察料液pH、脂液比、溫度、接觸時間對樹脂吸附痕量Fe的影響。結(jié)果表明:螯合樹脂Monophos對Fe有很強的吸附能力,在pH=3、溫度30~60℃、脂液比1:5~1:8、吸附時間不低于90min條件下,硫酸鈷料液中Fe去除率達70%,溶液中雜質(zhì)Fe含量從約為2.0mg/L降到約為0.4mg/L。分別采用三種不同的酸HEDPA(一種有機膦酸)、HCl以及H2SO4對Monophos樹脂進行動態(tài)解吸,結(jié)果表明,H2SO4對Monophos樹脂不具備解吸能力,0.5mol/L的HEDPA解吸效果強于6mol/L的HCl。但是經(jīng)過HEDPA解吸過樹脂的再吸附能力不如鹽酸。當采用HCl作為解吸液時,HCl的濃度直接影響到解吸的效果,當HCl濃度不低于5mol/L時解吸效果較好。洗脫再生后的樹脂Monophos具有較好的重復使用性,再生能力較強,使用壽命長,是較為理想的吸附鈷鹽溶液中雜質(zhì)Fe的離子交換樹脂。通過對樹脂Monophos吸附雜質(zhì)Fe機理的探究發(fā)現(xiàn):樹脂中起主要吸附作用的官能團為磷酸基團,并通過紅外光譜分析確定了P-O-H中的氫與金屬離子發(fā)生了交換,使金屬離子進入了樹脂中與氧原子間通過離子鍵形式結(jié)合。對動力學吸附曲線的實驗數(shù)據(jù),分別采用擬一級動力學方程和擬二級動力學方程進行擬合,結(jié)果表明樹脂Monophos吸附雜質(zhì)Fe的過程符合擬二級動力學過程�？刂茩C理的研究結(jié)果表明雜質(zhì)Fe在樹脂Monophos上吸附過程的控制步驟為顆粒擴散。分別采用Langmiur和Freundlich吸附等溫模型對等溫平衡吸附數(shù)據(jù)進行擬合,結(jié)果表明Langmiur方程能更準確地反映樹脂Monophos對雜質(zhì)Fe的吸附過程。吸附過程的熱力學研究表明:雜質(zhì)Fe在樹脂Monophos上的吸附過程是自發(fā)的(△G0),吸熱的(△H0),熵變?yōu)檎?△S0)的過程,因此升高溫度有利于吸附過程的進行。實驗表明,硫酸鈷體系下電解制備高純鈷的最佳工藝條件為:鈷離子濃度60~70g/L;pH值為3~4;陰極的電流密度為100~300A/m2;電解溫度為40℃~60℃。在該工藝條件制得的陰極鈷片,經(jīng)過GDMS分析,純度達到了5N。
[Abstract]:High purity cobalt has excellent semiconductor properties, magnetic properties and conductive properties. It is used to prepare magnetic recording medium, magnetic recording head and optoelectronic device. High purity cobalt, which is an important material of magnetic sensors and integrated circuits, is mainly used to manufacture sputtering targets in VLSI industry. At present, it is limited to technical reasons. 5N and above high purity cobalt need to be imported in large quantities, so it is very important to develop high purity cobalt preparation technology with independent intellectual property rights. In this paper, high purity cobalt is prepared by ion exchange purification of CoSO4 aqueous solution electrolysis. Aiming at the common problem that the main impurity element Fe in cobalt salt solution is difficult to be removed, a new chelating resin Monophos is used to adsorb the impurity element Fe in cobalt solution. The optimum process conditions for adsorption of Fe by resin Monophos and the stable production process for preparation of high purity cobalt by electrolysis of CoSO4 system were determined by systematic experimental analysis. The static adsorption test was carried out. The effects of pH, ratio of lipids to liquid, temperature and contact time on the adsorption of trace Fe by chelating resin Monophos were investigated. The results showed that chelating resin Monophos had a strong adsorption ability on Fe in pH=3. The removal rate of Fe in cobalt sulfate solution was 70% when the temperature was 30 ~ 60 鈩，

本文編號：1462995