分散反萃取相支撐式液態薄膜分離回收電解液內銦(In3+)和錫(Sn2+)離子之研究

Separation and Recovery of Indium (In3+) Ions and Tin(Sn2+) from Electrolyte by a Supported Liquid Membrane

林祺笙(Chi-Sheng Lin)

指導教授 ： 游勝傑 ； 王雅玢

中原大學/工學院/環境工程學系/碩士(2019年)

https://doi.org/10.6840/cycu201900142

摘要

本研究使用分散反萃取相支撐式液膜（Supported Liquid Membrane with Strip Dispersion，SLMSD），以兩步驟程序回收並純化電解廢液中之稀土金屬銦。近年來銦金屬廣泛應用在各類光電產品中，其中以銦錫氧化物（Indium Tin oxide，ITO）佔的比例最高，而隨著製造量的增加，大量含銦錫的蝕刻廢液也越來越多，再加上稀有金屬銦之價格近年來波動劇烈，故銦金屬之回收與純化濃縮所帶來的經濟效益不容小覷。
本研究根據含銦錫廢液之全量分析結果為基礎，利用批次萃取實驗、批次反萃取實驗取得SLM最佳操作參數並進行模廠操作。
以萃取劑為0.5 M D2EHPA，油水比15ml廢液：13 ml萃取劑、油水比20ml萃取劑/5ml反萃取劑、並以3N HCl作為反萃取劑以支撐式液態薄膜回收銦離子，錫離子在萃取劑中之純度約有74%，銦離子之回收效率為62%、銦離子純度由25% 提升為71%，銦離子濃度由進料濃度2700ppm提升至7800ppm，濃縮倍數為2.89倍。
以萃取劑為0.5 M D2EHPA，油水比20ml廢液：10 ml萃取劑、油水比20ml萃取劑/5ml反萃取劑、並先以5N H2SO4作為反萃取劑以支撐式液態薄膜抓取錫離子，增加銦離子在萃取劑中之純度，再進一步回收銦離子，反應後含銦萃取劑銦純度約有10%，而反萃取劑中之錫離子純度及濃度分別為98%、30,000ppm左右；而以相同參數進行較大規模SLM實驗，所得結果與小規模差異不大，可以小規模實驗結果，推估實場之經濟效益。
在銦離子純化回收過程中，銦錫離子濃度比例差異過大，即使先抓取錫離子，萃取劑中銦離子純度也只有10%，但回收過程所得之氫氧化亞錫及高純度之含錫反萃取劑，推估實場之經濟效益發現，以日處理水量25CMD來估算，一年可以獲得11,137,375元的收益。

關鍵字

分散反萃取相支撐式液膜 ； 銦 ； 錫 ； 萃取 ； D2EHPA

並列摘要

In this study, supported-liquid-membrane with-strip dispersion (SLMSD) was used to recover and purify rare-earth metals of indium from the electrolytic waste solution in a two-step process. Indium oxide has been widely used in various types of optoelectronic products in recent years, among which Indium Tin Oxide (ITO) accounts for the highest proportion, and as the amount of manufacturing increases, a large amount of etching waste liquid containing indium is also increasing. More, coupled with the recent fluctuations in the price of rare metal indium, the economic benefits of recycling and purification of indium metal should not be underestimated.
Based on the results of the full analysis of indium-containing waste liquid, this study used batch extraction experiments, indium tin separation experiments, batch back extraction experiments to obtain the best operating parameters of SLM and perform mold operation.
. The extractant is 0.5M D2EHPA, the oil-water ratio is 15 ml of waste liquid: 13 ml of extractant, oil-water ratio 20 ml extractant/5 ml of stripping agent, and 3N HCl is used as a stripping agent to recover indium ions by supported liquid membrane. The purity of tin ions in the extractant is about 74%, the recovery efficiency of indium ions is 62%, the purity of indium ions is increased from 25% to 71%, the concentration of indium ions is increased from 2700ppm to 7800ppm, and the concentration multiple is 2.89 times. .
The extraction agent is 0.5M D2EHPA, the oil-water ratio is 20 ml of waste liquid: 10 ml of extractant, oil-water ratio 20 ml extractant/5 ml of stripping agent, and 5N H2SO4 is used as a stripping agent to hold tin ions by supported liquid membrane to increase the purity of indium ions in the extractant, and further recover the indium ions. After the reaction, the purity of indium ions in the extractant is 10%, and the purity and concentration of tin ions in the stripping agent are 98% and 30,000 ppm. However, the large-scale SLM experiment with the same parameters, the results are almost the same with the small scale,the results of small-scale experiments can be used to estimate the economic benefits of the field.
In the process of purification and recovery of indium ions, t the concentration of tin ions is much higher than Indium ions. Even if the tin ions are first grabbed, the purity of the indium ions in the extractant is only 10%, but the obtained stannous hydroxide and tin-containing solution were used to estimate the economic benefit of the field. It was found that the daily treated water volume was 25 CMD, and the yield of 11,137,375 NT$ was obtained per year.

並列關鍵字

SLMSD ； Indium ； Tin ； Extraction ； D2EHPA

參考文獻

1. López-López, J.A., et al., Liquid membranes for quantification and speciation of trace metals in natural waters. TrAC Trends in Analytical Chemistry, 2010. 29(7): p. 645-653.

2. 吳俊毅*, et al., LCD 含銦廢料與廢液資源化處理技術之可行性評估. 工業污染防治, 2010. 113: p. 13-49.

3. Pradhan, D., S. Panda, and L.B. Sukla, Recent advances in indium metallurgy: A review. Mineral Processing and Extractive Metallurgy Review, 2018. 39(3): p. 167-180.

4. Ogi, T., et al., Recovery of indium from aqueous solutions by the Gram-negative bacterium Shewanella algae. Biochemical Engineering Journal, 2012. 63: p. 129-133.

5. Kang, H.N., J.-Y. Lee, and J.-Y. Kim, Recovery of indium from etching waste by solvent extraction and electrolytic refining. Hydrometallurgy, 2011. 110(1): p. 120-127.