碱浸体系中氧化剂对砷黄铁矿的选择性溶解及机理研究

金凯; 袁文彬; 王小龙; 覃文庆; 张雁生

doi:10.3969/j.issn.1000-6532.2025.02.014

碱浸体系中氧化剂对砷黄铁矿的选择性溶解及机理研究

中南大学　资源加工与生物工程学院，湖南　长沙　410083

基金项目: 国家自然科学基金的支持（51974363）

详细信息

作者简介: 金凯（1996-），男，硕士研究生，主要从事浮选电化学和浮选药剂研发

通讯作者: 张雁生(1980-)，男，博士，副教授，从事矿物加工和生物冶金研究

中图分类号: TD953

收稿日期: 2022-04-18

刊出日期: 2025-04-25

Selective Dissolution and Mechanism of Arsenopyrite by the Oxidizing Agent in Alkaline Leaching System

School of Resource Processing and Bioengineering, Central South University, Changsha 410083, Hunan, China

More Information

Corresponding author: ZHANG Yansheng, Zhangyansheng405@126.com

Received Date: 18 April 2022

Publish Date: 25 April 2025

摘要

摘要:
砷黄铁矿是一种常见的载金矿物，砷的存在导致金回收困难。本文研究了砷黄铁矿常压碱浸脱砷过程中，浸出时间、NaOH浓度、温度和高锰酸钾浓度对砷浸出率的影响，并结合电化学、动力学分析，阐明了高锰酸钾的助浸氧化机制。结果表明，当使用0.25 mol/L高锰酸钾作为氧化剂，NaOH浓度为3.5 mol/L时，砷浸出率最高，为63.72%。电化学与动力学分析表明，控制砷黄铁矿常压碱浸反应速率的决定性步骤是化学反应步骤，表观活化能为40.19 kJ/mol，高锰酸钾等氧化剂促进了砷黄铁矿碱浸初期铁的氧化溶解。
- 砷迁移 /
- 砷黄铁矿 /
- 浸出 /
- 预氧化
Abstract:
Arsenopyrite is a common gold-bearing mineral, and the presence of arsenic leads to difficulties in gold recovery. In this paper, the effects of leaching time, NaOH concentration, temperature and potassium permanganate concentration on the arsenic leaching rate in the process of arsenopyrite arsenic removal by atmospheric pressure alkaline leaching were investigated, and the leaching mechanism of potassium permanganate was elucidated by combining electrochemical and kinetic analysis. The results showed that the highest arsenic leaching rate of 63.72% was achieved when 0.25 mol/L potassium permanganate was used as the oxidant and the NaOH concentration was 3.5 mol/L. Electrochemical and kinetic analyses showed that the decisive step controlling the rate of arsenopyrite atmospheric pressure alkali leaching reaction was the chemical reaction step. The apparent activation energy of the reaction is 40.19 kJ/mol. Oxidizing agents such as potassium permanganate promote the oxidative dissolution of iron at the beginning of the alkaline leaching of arsenopyrite.
- Arsenic removal /
- Arsenopyrite /
- Dissolution /
- Pre-oxidation

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图 1 砷黄铁矿XRD分析

Figure 1.

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图 2 FeAsS-H₂O体系Eh-pH（电位vs SHE）

Figure 2.

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图 3 各因素对砷浸出率的影响（a）时间；（b）KMnO₄浓度；（c）NaOH浓度；（d）温度

Figure 3.

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图 4 表面拉曼光谱（a）原矿；（b）浸出渣

Figure 4.

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图 5 浸出前后砷黄铁矿表面XPS

Figure 5.

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图 6 浸出前砷黄铁矿XPS高分辨图谱（a）Fe 2p；（b）As 3d；（c）S 2p

Figure 6.

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图 7 浸出后XPS高分辨图谱（a）Fe 2p；（b）As 3d；（c）S 2p

Figure 7.

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图 8 浸出渣表面SEM（a）0.25 mol/L KMnO₄、3.0 mol/L NaOH、45 ℃、24 h；（b）3.0 mol/L NaOH、45 ℃、24 h

Figure 8.

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图 9 砷黄铁矿循环伏安曲线（a）pH=7；（b）pH=14

Figure 9.

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图 10 砷黄铁矿循环伏安曲线（a）pH=7；（b）pH=14

Figure 10.

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图 11 不同反应温度下砷黄铁矿的动力学模型拟合

Figure 11.

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图 12 砷黄铁矿的阿伦尼乌斯曲线

Figure 12.

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表 1 砷黄铁矿的主要化学成分分析/%

Table 1. Main chemical composition analysis of arsenopyrite

	Fe	As	S	其他	合计
理论	34.30	46.01	19.69	0.00	97.30
实际	33.14	44.78	19.38	2.70	97.30

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表 2 25 ℃下砷黄铁矿碱浸反应的Eh-pH关系式

Table 2. Eh-pH equations for the alkaline leaching reaction of arsenopyrite at 25 ℃

序号	反应式	Eh-pH关系式
a	O₂+4H⁺+4e^-=2H₂O	Eh=1.22-0.059pH
b	H₂=2H⁺+2e^-	Eh=-0.059pH
1	FeAsS+5OH^-+3.5O₂=Fe(OH)₃+AsO₄^3-+SO₄^2-+H₂O	Eh=1.34-0.021pH
2	14MnO₄^-+FeAsS+19OH^-=14MnO₄^2-+8H₂O+AsO₄^3-+Fe(OH)₃+SO₄^2-	Eh=2.31-0.080pH
3	FeAsS+1.5O₂+3H₂O=Fe(OH)₃+H₂AsO₃^-+S⁰+H⁺	Eh=1.18-0.015pH
4	S⁰+2OH^-+1.5O₂=SO₄^2-+H₂O	Eh=1.39-0.020pH
5	H₂AsO₃^-+2OH^-+0.5O₂=AsO₄^3-+2H₂O	Eh=1.98-0.059pH
6	4MnO₄^-+4OH^-=4MnO₄^2-+2H₂O+O₂	Eh=0.98-0.059pH
7	6MnO₄^-+8OH^-+S⁰=SO₄^2-+4H₂O+6MnO₄^2-	Eh=2.37-0.079pH
8	2MnO₄^-+4OH^-+H₂AsO₃^-=2MnO₄^2-+3H₂O+AsO₄^3-	Eh=2.84-0.118pH

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表 3 25 ℃时砷黄铁矿碱浸反应的反应平衡常数与吉布斯自由能

Table 3. Equilibrium constants and Gibbs free energy for the alkaline leaching reaction of arsenopyrite at 25 ℃

序号	反应平衡常数	吉布斯自由能 /(kJ/mol)	序号	反应平衡常数	吉布斯自由能 /(kJ/mol)
1	243.664	-1 483.982	5	35.578	-218.387
2	283.445	-1 726.259	6	11.366	-69.222
3	85.933	-523.353	7	125.804	-766.179
4	108.755	-662.347	8	41.261	-251.294

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表 4 不同温度和高锰酸钾与氢氧化钠的不同浓度下砷的浸出率/%

Table 4. Recovery of As at different temperatures and different concentrations of NaOH and KMnO₄

药剂种类	用量/(mol/L)	30 ℃	45 ℃	60 ℃
KMnO₄ （NaOH 2.5 mol/L，24 h）	0.05	13.09	18.03	27.25
	0.10	18.39	25.57	34.32
	0.15	24.97	33.65	38.19
	0.20	32.73	39.31	43.27
	0.25	39.31	44.03	54.14
NaOH （KMnO₄ 0.25 mol/L，24 h）	2.00	37.99	40.65	50.76
	2.50	39.31	44.03	54.14
	3.00	39.70	44.23	62.65
	3.50	41.17	47.01	63.72

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表 5 不同矿物的拉曼峰峰位

Table 5. Raman band positions of different minerals

矿物种类	化学式	主要拉曼峰 /cm⁻¹	次要拉曼峰 /cm⁻¹
砷黄铁矿	FeAsS	217，280，392	127，231，333， 427，453
赤铁矿	ɑ-Fe₂O₃	222，290	230，408，490，607
针铁矿	ɑ-FeO(OH)	297，384	477，545，655
水合氧化铁	5Fe₂O₃·9H₂O	707	361, 508, 1045
雌黄	As₂S₃	379	152, 289, 200,308

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表 6 未反应收缩核模型

Table 6. Shrinking core model equations

#	控制步骤	方程式
1	液相传质	1-3(1-x)^2/3+2(1-x)=kt
2	表面化学反应	1-(1-x)^1/3=kt

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