湿法炼铜浸出液萃取分离硫酸机理

doi:10.16085/j.issn.1000-6613.2023-0756

摘要/Abstract

摘要：

针对湿法炼铜浸出液中游离硫酸含量高的问题，提取铜前需进行中和处理，不仅碱性试剂消耗量大、作业成本高，还会造成金属离子损失的问题。本文提出采用溶剂萃取回收硫酸的工艺，研究了三辛胺（TOA）-正辛醇体系选择性萃取分离硫酸过程的传质机理。结果表明，TOA萃取硫酸的过程中会发生水化作用而产生第三相，加入正辛醇后，因形成疏水性络合体 $(R 3 N H) 2 (A) 0.3 (H 2 O) 1.7 S O 4 ¯$ ，避免了第三相的形成；在有机相构成为45% TOA+10%正辛醇+45% 260^#溶剂油、相比O∶A（有机相与水相之比）为1∶1、温度25℃、震荡速度200r/min、反应时间10min的条件下，硫酸单级萃取率达90.21%，三级逆流萃取率达99%以上，杂质离子Cu²⁺、Fe²⁺、Zn²⁺的萃取率分别小于2.7%、2.2%、2.3%；萃取过程为放热反应，通过计算得萃取反应的∆H为-14.9kJ/mol。

关键词: 萃取, 分离, 综合回收, 湿法炼铜, 三辛胺

Abstract:

In view of the high content of free sulfuric acid in the copper leaching solution in hydrometallurgical process, neutralization treatment is required before copper extraction, which not only consumes large alkaline reagents and high operating cost, but also causes metal ion loss. In this paper, a solvent extraction process for sulfuric acid recovery was proposed and the mass transfer mechanism of the selective extraction process of trioctylamine (TOA) -n-octanol system was studied. The results showed that the third phase would be produced by hydration during TOA extraction of sulfuric acid. After adding n-octanol, the third phase can be avoided due to the formation of hydrophobic complexation $(R 3 N H) 2 (A) 0.3 (H 2 O) 1.7 S O 4 ¯$ . Under the conditions that the organic phase composition was 45% TOA+10% n-octanol +45% 260^# solvent oil, the ratio of O∶A (ratio of organic phase to aqueous phase) was 1∶1, the temperature was 25℃, the oscillation speed was 200r/min and the reaction time was 10min, the single-stage extraction rate of sulfuric acid reached 90.21% and the three-stage countercurrent extraction rate can achieve more than 99%. The extraction rates of Cu²⁺, Fe²⁺ and Zn²⁺were less than 2.7%, 2.2% and 2.3%, respectively. The extraction process was an exothermic reaction and the calculated ∆H of the extraction reaction was -14.9kJ/mol.

Key words: extraction, separation, comprehensive recovery, copper hydrometallurgy, trioctylamine

中图分类号:

TF804.2

马海飞, 廖亚龙, 武敏, 贾小宝, 杨双宇. 湿法炼铜浸出液萃取分离硫酸机理[J]. 化工进展, 2024, 43(6): 3410-3419.

MA Haifei, LIAO Yalong, WU Min, JIA Xiaobao, YANG Shuangyu. Extraction mechanism of sulfuric acid from copper leaching solution of hydrometallurgical process[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3410-3419.

图/表 15

表1 湿法炼铜浸出模拟液成分

成分	含量/g·L^-1
H₂SO₄	80
Cu²⁺	10
Fe²⁺	4
Zn²⁺	2

图1 TOA与硫酸配位机制[27]

图2 萃取剂浓度对硫酸萃取的影响

图3 三辛胺浓度对萃取率的影响

表2 稀释剂及调节剂对硫酸萃取率影响

有机相构成体积分数/%			稀释剂	萃取率/%
三辛胺	正辛醇	正丁醇	稀释剂	萃取率/%
45	55	—	—	86.04
45	10	—	45%甲苯	87.76
45	10	—	45% 260^#溶剂油	90.21
45	—	55	—	85.04
45	—	10	45%甲苯	85.48
45	—	10	45% 260^#溶剂油	86.48

图4 正辛醇浓度对硫酸萃取率的影响

图5 正辛醇加入前后萃取体系静止分层情况

图6 有机相红外光谱sv—伸缩振动；bv—弯曲振动 (R3NH)m(H2O)(4-m)H(2-m)SO4¯+nA= (R3NH)m(A)n(H2O)(4-m-n)H(2-m)SO4¯+nH2O (8)

图7 反应温度对硫酸萃取率影响

图8 硫酸萃取lgD-1000/T关系曲线图

图9 三辛胺-正辛醇萃取硫酸的McCabe-Thiele图

表3 用不同浓度的三辛胺和正辛醇进行斜率分析

斜率分析	三辛胺体积分数/%	260^#溶剂油体积分数/%	正辛醇体积分数/%
三辛胺作用	45	45	10
	35	55	10
	25	65	10
	15	75	10
	5	85	10
正辛醇作用	45	30	25
	45	35	20
	45	40	15
	45	45	10
	45	50	5

图10 三辛胺-正辛醇萃取硫酸时lgD-lg[TOA]、lgD-lg[正辛醇]的关系

图11 红外光谱图sv—伸缩振动；bv—弯曲振动；asv—非对称伸缩振动

图12 三辛胺-正辛醇萃取体系萃取硫酸反应机理示意图

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