氰化尾渣矿浆电解液中铁离子的萃取富集

doi:10.16085/j.issn.1000-6613.2022-0580

摘要/Abstract

摘要：

采用二(2-乙基己基)磷酸酯（P204）-磺化煤油萃取体系从高硫酸氰化尾渣矿浆电解液中富集铁离子，重点研究了P204浓度、相比(O/A)、振荡时间、振荡频率及温度等对Fe³⁺萃取率的影响及其萃取过程。研究表明，在P204体积分数为25%、电解液pH为1.5、温度25℃、O/A=1∶1、振荡时间10 min、振荡频率180r/min的条件下，电解液中Fe³⁺的单级萃取率可达97.73%以上，饱和萃取容量可达到21.57g/L。Fe³⁺在有机相中的萃取富集主要归因于其与P204分子结构中羟基的阳离子交换反应以及磷酰基的配位反应，形成的配合物为FeSO₄A(HA)₃与FeA₃(HA)₃。在草酸1mol/L、O/A=1∶1、振荡时间10min、振荡频率190r/min的条件下，负载有机相中Fe³⁺的单级反萃率可达82.64%以上，反萃液中铁主要以[Fe(C₂O₄)₃]^3-、Fe(C₂O₄)⁺、 $F e (C 2 O 4) 2 -$ 、FeSO₄(C₂O₄)^-形式存在，Zn²⁺浓度仅0.628mg/L，未检测到Cu²⁺，反萃后有机相仍具有较好的萃取性能。

关键词: 氰化尾渣, 溶剂萃取, 二(2-乙基己基)磷酸酯, 铁回收

Abstract:

The bis-(2-ethylhexyl) phosphate (P204)-sulfonated kerosene extraction system was used to enrich iron ions from cyanide tailings slurry electrolyte with high sulfuric acid. The effects of P204 concentration, ratio (O/A), oscillation time, oscillation frequency and temperature on the extraction rate of Fe³⁺ and its extraction process were mainly studied. The research showed that under the conditions of P204 concentration of 25%, temperature of 25℃, O/A=1∶1, oscillation time of 10min and oscillation frequency of 180r/min, the single-stage extraction rate of Fe³⁺in the electrolyte can reach 97.73%. The saturated extraction capacity can reach 21.57g/L. The extraction and enrichment of Fe³⁺in the organic phase was mainly attributed to the cation exchange reaction with the hydroxyl group in the molecular structure of P204 and the coordination reaction of the phosphoryl group. The complexes formed were FeSO₄A(HA)₃ and FeA₃(HA)₃. Under the conditions of oxalic acid 1mol/L, O/A=1∶1, oscillation time 10min and oscillation frequency 190r/min, the single-stage stripping rate of Fe³⁺ in the loaded organic phase can reach more than 82.64%. The iron in the stripping solution mainly existed in the form of [Fe(C₂O₄)₃]^3-, Fe(C₂O₄)⁺, Fe(C₂O₄)₂^- and FeSO₄(C₂O₄)^-. The concentration of Zn²⁺ was only 0.628mg/L and no Cu²⁺ was detected. The organic phase still had good extraction performance after stripping.

Key words: cyanide tailings, solvent extraction, bis-(2-ethylhexyl) phosphate, iron recovery

中图分类号:

X758

包进, 宋永辉, 董萍, 李一凡, 朱荣燕, 廖龙. 氰化尾渣矿浆电解液中铁离子的萃取富集[J]. 化工进展, 2023, 42(1): 517-525.

BAO Jin, SONG Yonghui, DONG Ping, LI Yifan, ZHU Rongyan, LIAO Long. Extraction and enrichment of iron ions in cyanide tailings electrolyte[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 517-525.

图/表 16

表1 氰化尾渣矿浆电解液多元素浓度分析结果单位：mg/L

Fe³⁺	Fe²⁺	Cu²⁺	Zn²⁺	Na⁺	$S O 4 2 -$	Cl^-
3348.59	334.21	5.63	32.45	23000	10700	484.3

表1 氰化尾渣矿浆电解液多元素浓度分析结果单位：mg/L

Fe³⁺	Fe²⁺	Cu²⁺	Zn²⁺	Na⁺	$S O 4 2 -$	Cl^-
3348.59	334.21	5.63	32.45	23000	10700	484.3

图1 氰化尾渣中铁的回收工艺流程图1—进料系统；2—矿浆槽；3—矿浆泵；4—电解槽；5—过滤系统；6—电解液储液槽；7—萃取液储液槽；8—萃取塔；9—反萃塔；10—光解槽；11—过滤系统

图2 铁及其他金属离子的萃取率

图3 P204体积分数对萃取率的影响

图4 pH对萃取率的影响

图5 O/A对萃取率的影响

图6 振荡时间及振荡频率对萃取率的影响

图7 温度对萃取的影响

图8 P204饱和萃取容量

表2 P204萃取平行实验

组别	氧化后电解液/mg·L^-1			负载有机相/mg·L^-1			Fe³⁺萃取率/%
组别	Cu²⁺	Zn²⁺	Fe³⁺	Cu²⁺	Zn²⁺	Fe³⁺	Fe³⁺萃取率/%
1	5.63	32.45	3682.80	0.06	3.40	3601.04	97.78
2	5.63	32.45	3682.80	0.07	3.45	3599.20	97.73
3	5.63	32.45	3682.80	0.07	3.65	3594.41	97.60

图9 lgD-lg[H2A2]和lgD-pH的拟合曲线

图10 P204有机相及负载铁有机相的FTIR图

图11 ESI-MS分析

图12 萃取过程的3D模型

图13 草酸浓度对负载有机相反萃的影响

图14 有机相循环次数与Fe3+萃取率的关系

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