氨性溶液中萃取铜及共萃氨的实验研究
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摘要
汤丹铜矿位于云南省东川市附近,铜金属贮量116万t,是一座具有高碱性脉石的难选氧化铜矿,矿石平均品位0.46%,矿石中碱性脉石含量高达40%。若采用酸浸方法,因碱性脉石耗酸量过大,生产成本高。而采用氨浸方法处理此类氧化铜矿具有铜浸出率高、成本低等优点。但采用氨浸—萃取—电积工艺时,萃取过程中萃取剂常常存在较为严重的共萃氨问题。如负载有机相中共萃氨在被贫电解液反萃前没及时被洗涤,这种萃有金属和氨的负载有机相与贫电解液接触时,在电积作业的进料液中生成硫酸铵,在电解残液不断循环至反萃取的过程,若不排放,硫酸铵就会积累,并在电解槽中结晶析出硫酸盐。这种共萃氨现象给整个工艺的后续处理带来诸多不便,同时造成一定量氨的损失。
本论文针对如何降低负载有机相中共萃氨的问题,采用以下两种不同萃取剂进行单因素条件实验研究：(1)采用实验室合成高位阻p-二酮作为萃取剂；(2)向LIX84中添加TBP作为萃取剂。萃取实验过程中针对这两种萃取剂,考察了被萃水相中铜离子浓度、被萃水相中总氨浓度、被萃水相pH值、相比(O/A)、有机相中萃取剂浓度等对铜萃取率及负载有机相中共萃氨量的影响。
研究结果表明：(1)采用实验室合成的高位阻β-二酮作为萃取剂,在被萃水相中铜离子浓度、总氨浓度、相比(O/A)、被萃水相中pH值等较为适当的条件下,铜萃取率高达95%；与此同时,其负载有机相中共萃氨量普遍都非常低,最高时不到40 mg/L。(2)采用LIX84中添加TBP作为萃取剂,与未添加TBP相比,添加TBP后铜萃取率变化较小,且都比较高,最高时接近100%,而负载有机相中共萃氨量则有明显下降。有机相中TBP浓度为0.1mol/L, LIX84浓度为40%,水相铜离子浓度为25 g/L,总氨浓度为3 mol/L,相比为1:1,pH为9.1,萃取时间为30 min时,铜萃取率约为81%,与未添加TBP相比,铜萃取率基本保持不变,而负载有机相中的共萃氨量由未添加TBP时的260mg/L降至添加TBP后的85 mg/L。
Tangdan copper ore, located near Dongchuan City in Yunnan Province, having copper reserve of 1.16×106 tons, is a refractory oxidized ore with high-alkaline gangues. Its average copper content is 0.46%, this oxidized copper mineral has 40% content of alkaline gangue. If acid-leaching method is adopted, it has high production cost because of huge acid consumption of alkaline gangue. In the "ammonia leaching-solvent extraction-electrowinning" process, there was a problem of ammonia extraction in the loaded organic phase when the two phase were contacted. The ammonia presented in the loaded organic phase should be removed before attempting copper stripping with the spent electrolyte. Otherwise, ammonia in the loaded organic phase is transferred to the pregnant electrolyte after copper stripping, which may result in the accumulation and the precipitation of (NH4)2SO4 in the pregnant electrolyte. The extraction of ammonia may bring many problems to the whole process and may be a waste of ammonia.
In this paper, two different extractants were used to decrease the ammonia extraction in the loaded organic phase by deploying simple factor experiments. (1) A laboratory synthesized sterically hinderedβ-diketone was applied as a kind of extractant; (2) The other kind of extractant was LIX84 (a commercial extractant) adding TBP. The effects of the concentration of copper ion, the total ammonia concentration and initial pH in the aqueous phase, the concentration of extractant in organic phase, and the phase ratio on copper extraction ratio and ammonia extraction in loaded organic phase were studied.
The experimental results show as follows:(1) When the laboratory synthesized sterically hinderedβ-diketone was applied, the copper extraction ratio was up to 95% at proper conditions, and the ammonia extraction content was no more than 40 mg/L. (2) Compared with absence of TBP, the high copper extraction ratio was almost unchanged while the ammonia extraction content was decreased manifestly. When the copper concentration in the aqueous phase and total ammonia concentration were 25 g/L and 3 mol/L, respectively, the pH of aqueous phase was 9.1. The organic phase was LIX84 concentration of 40% adding TBP of 0.1 mol/L. The phase ratio was 1:1. The contact time was 30 min. The result showed that the copper extraction ratio was 81% and the ammonia extraction in the loaded organic phase was 85 mg/L. While the copper extraction ratio and ammonia extraction in the loaded organic phase in the absence of TBP were 81% and 260 mg/L.
本论文针对如何降低负载有机相中共萃氨的问题,采用以下两种不同萃取剂进行单因素条件实验研究：(1)采用实验室合成高位阻p-二酮作为萃取剂；(2)向LIX84中添加TBP作为萃取剂。萃取实验过程中针对这两种萃取剂,考察了被萃水相中铜离子浓度、被萃水相中总氨浓度、被萃水相pH值、相比(O/A)、有机相中萃取剂浓度等对铜萃取率及负载有机相中共萃氨量的影响。
研究结果表明：(1)采用实验室合成的高位阻β-二酮作为萃取剂,在被萃水相中铜离子浓度、总氨浓度、相比(O/A)、被萃水相中pH值等较为适当的条件下,铜萃取率高达95%；与此同时,其负载有机相中共萃氨量普遍都非常低,最高时不到40 mg/L。(2)采用LIX84中添加TBP作为萃取剂,与未添加TBP相比,添加TBP后铜萃取率变化较小,且都比较高,最高时接近100%,而负载有机相中共萃氨量则有明显下降。有机相中TBP浓度为0.1mol/L, LIX84浓度为40%,水相铜离子浓度为25 g/L,总氨浓度为3 mol/L,相比为1:1,pH为9.1,萃取时间为30 min时,铜萃取率约为81%,与未添加TBP相比,铜萃取率基本保持不变,而负载有机相中的共萃氨量由未添加TBP时的260mg/L降至添加TBP后的85 mg/L。
Tangdan copper ore, located near Dongchuan City in Yunnan Province, having copper reserve of 1.16×106 tons, is a refractory oxidized ore with high-alkaline gangues. Its average copper content is 0.46%, this oxidized copper mineral has 40% content of alkaline gangue. If acid-leaching method is adopted, it has high production cost because of huge acid consumption of alkaline gangue. In the "ammonia leaching-solvent extraction-electrowinning" process, there was a problem of ammonia extraction in the loaded organic phase when the two phase were contacted. The ammonia presented in the loaded organic phase should be removed before attempting copper stripping with the spent electrolyte. Otherwise, ammonia in the loaded organic phase is transferred to the pregnant electrolyte after copper stripping, which may result in the accumulation and the precipitation of (NH4)2SO4 in the pregnant electrolyte. The extraction of ammonia may bring many problems to the whole process and may be a waste of ammonia.
In this paper, two different extractants were used to decrease the ammonia extraction in the loaded organic phase by deploying simple factor experiments. (1) A laboratory synthesized sterically hinderedβ-diketone was applied as a kind of extractant; (2) The other kind of extractant was LIX84 (a commercial extractant) adding TBP. The effects of the concentration of copper ion, the total ammonia concentration and initial pH in the aqueous phase, the concentration of extractant in organic phase, and the phase ratio on copper extraction ratio and ammonia extraction in loaded organic phase were studied.
The experimental results show as follows:(1) When the laboratory synthesized sterically hinderedβ-diketone was applied, the copper extraction ratio was up to 95% at proper conditions, and the ammonia extraction content was no more than 40 mg/L. (2) Compared with absence of TBP, the high copper extraction ratio was almost unchanged while the ammonia extraction content was decreased manifestly. When the copper concentration in the aqueous phase and total ammonia concentration were 25 g/L and 3 mol/L, respectively, the pH of aqueous phase was 9.1. The organic phase was LIX84 concentration of 40% adding TBP of 0.1 mol/L. The phase ratio was 1:1. The contact time was 30 min. The result showed that the copper extraction ratio was 81% and the ammonia extraction in the loaded organic phase was 85 mg/L. While the copper extraction ratio and ammonia extraction in the loaded organic phase in the absence of TBP were 81% and 260 mg/L.
引文
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