Fe3+-C2O42--H2O溶液中Fe(Ⅲ)的形态分布及其在硫酸烧渣和氰化尾渣除铁过程中的应用

doi:10.16085/j.issn.1000-6613.2022-2308

摘要/Abstract

摘要：

针对硫酸烧渣和氰化尾渣选择性除铁过程中存在的问题，提出草酸-草酸铵除铁富集金银等有价金属的技术。计算绘制了Fe³⁺-C₂O $4 2 -$ -H₂O溶液中Fe(Ⅲ)及C₂O $4 2 -$ 的形态分布图，分析了其形态分布与pH、[C₂O $4 2 -$ ]_TOT/[Fe³⁺]_TOT物质的量浓度比以及液固比的关系，揭示赤铁矿浸出效果与浸出液中Fe(Ⅲ)形态分布的关系，并探讨了浸出液资源化利用工艺。结果表明：pH和[C₂O $4 2 -$ ]_TOT/[Fe³⁺]_TOT物质的量浓度比是影响Fe³⁺形态分布的主要因素，而浸出液中Fe(Ⅲ)的形态分布决定赤铁矿的浸出效果与浸出时间。要缩短除铁时间，提高赤铁矿浸出效果，则[C₂O $4 2 -$ ]_TOT/[Fe³⁺]_TOT物质的量浓度比要大于3，且pH宜控制在Fe(C₂O₄) $3 3 -$ 分配分数达到1时的最小pH附近。草酸-草酸铵除铁时间短，除铁效果好，且有利于金、银及金属硫化物的富集以及浸出液的资源化利用。研究结果以期为高效、清洁、资源化利用黄金冶炼工业和合成硫酸工业产出的大宗固废提供理论与技术支持。

关键词: 硫酸烧渣, 氰化尾渣, 选择性, 浸出, 溶解性, 形态分布

Abstract:

Aiming at the problems of selective iron removal from sulfuric acid cinder and cyanide tailings, the technology of iron removal and the valuable metals enrichment such as gold and silver by oxalic acid and ammonium oxalate was proposed. The species distribution diagrams of Fe(Ⅲ) and C₂O $4 2 -$ in Fe³⁺-C₂O $4 2 -$ -H₂O solution were drawn. The relationships between Fe(Ⅲ) species distribution and the pH, the molar concentration ratio of [C₂O $4 2 -$ ]_TOT to [Fe³⁺]_TOTand the liquid to solid ratio were analyzed. The relationship between the leaching effect of hematite and the species distribution of Fe(Ⅲ) in the leaching solution was revealed and the technologies of resource utilization of the leaching solution were also discussed. Results showed that the pH and the molar concentration ratio of [C₂O $4 2 -$ ]_TOT to [Fe³⁺]_TOT were the main factors affecting the species distribution of Fe(Ⅲ), and its species distribution in the leaching solution determined the leaching effect and the leaching time of hematite. In order to shorten the iron removal time and improve leaching effect, the molar ratio of [C₂O $4 2 -$ ]_TOT to [Fe³⁺]_TOT should be higher than 3, and the pH should be controlled near the minimum pH when the Fe(C₂O₄) $3 3 -$ distribution fraction reached 1. The iron removal technology of oxalate and ammonium oxalate had a short time and a good iron removal effect, and it was beneficial to concentrate gold, silver and metal sulfide as well as the resource utilization of the leaching solution. The research results would provide the theoretical and technical support for efficient, clean and resource utilization of these industrial solid wastes containing gold and hematite, which were produced in gold smelting industry and synthetic sulfuric acid industry.

Key words: sulphuric acid cinder, cyanide tailings, selectivity, leach, solubility, species distribution

中图分类号:

TF04

党晓娥, 张婷. Fe³⁺-C₂O $4 2 -$ -H₂O溶液中Fe(Ⅲ)的形态分布及其在硫酸烧渣和氰化尾渣除铁过程中的应用[J]. 化工进展, 2023, 42(11): 6005-6014.

DANG Xiao’e, ZHANG Ting. Species distribution of Fe(Ⅲ) in Fe³⁺-C₂O $4 2 -$ -H₂O solution and application in the process of iron removal from sulphuric acid cinder and syanide tailings[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 6005-6014.

图/表 12

图1 Fe3+-C2O42--H2O溶液中C2O42-形态分布图

图2 Fe3+-C2O42--H2O溶液中Fe(Ⅲ)的形态分布图

图3 Fe3+-C2O42--H2O溶液中C2O42-的形态分布图

图4 Fe3+-C2O42--H2O溶液中Fe(Ⅲ)的形态分布图

图5 Fe3+-C2O42--H2O体系中C2O42-的形态分布图

图6 Fe3+-C2O42--H2O体系中Fe(Ⅲ)形态分布图

表1 草酸-草酸铵浸出赤铁矿结果

液固比	草酸与草酸铵摩尔比
	2.5︰0.5		2︰1		1.5︰1.5		1︰2
	pH	铁浸出率 /%	pH	铁浸出率 /%	pH	铁浸出率 /%	pH	铁浸出率 /%
4︰1	0.28	61.76	1.13	78.75	2.67	91.38	4.37	69.43
6︰1	0.36	66.03	1.25	78.25	2.76	89.73	4.66	67.40
8︰1	0.44	64.02	1.44	77.86	2.88	89.69	4.79	67.06

表2 氰化尾渣除铁效果对除铁渣中金浸出率的影响

C₂O $4 2 -$ _TOT与Fe³⁺_TOT摩尔比	浸出pH	除铁渣重/g	渣含铁/%	铁浸出率/%	氰化前渣含金/g·t^-1	氰化后渣含金/g·t^-1	金浸出率/%
0		200.00	30.10		13.03	9.53	26.86
1.8	—	152.41	16.50	58.09	14.23	9.83	30.92
2.4	—	141.25	11.43	73.09	16.55	9.69	41.45
3.0	2.77	125.02	6.30	86.87	19.66	9.48	51.78
3.6	1.94	105.62	3.70	93.49	23.54	9.56	59.39
4.2	1.92	101.37	1.90	96.79	24.83	9.66	61.10

表2 氰化尾渣除铁效果对除铁渣中金浸出率的影响

C₂O $4 2 -$ _TOT与Fe³⁺_TOT摩尔比	浸出pH	除铁渣重/g	渣含铁/%	铁浸出率/%	氰化前渣含金/g·t^-1	氰化后渣含金/g·t^-1	金浸出率/%
0		200.00	30.10		13.03	9.53	26.86
1.8	—	152.41	16.50	58.09	14.23	9.83	30.92
2.4	—	141.25	11.43	73.09	16.55	9.69	41.45
3.0	2.77	125.02	6.30	86.87	19.66	9.48	51.78
3.6	1.94	105.62	3.70	93.49	23.54	9.56	59.39
4.2	1.92	101.37	1.90	96.79	24.83	9.66	61.10

图7 氰化尾渣除铁前后的X衍射图谱

表3 草酸-草酸铵浸出不同渣中赤铁矿的结果 (%)

矿物种类

陕西两段焙烧

氰化尾渣

湖南郴州

硫酸烧渣

陕西某固废处理

中心氰化尾渣

山东两段焙烧

氰化尾渣

表4 除铁前后主要金属含量

渣类型	元素	金含量/g·t^-1	铁质量分数/%	铜质量分数/%	锌质量分数/%	铅质量分数/%
陕西两段焙烧氰化尾渣	除铁前	13.03	30.10	0.28	0.38	0.99
陕西两段焙烧氰化尾渣	除铁后	25.39	2.20	0.51	0.34	1.91
湖南郴州硫酸烧渣	除铁前	4.00	38.00	0.6	1.00	2.20
湖南郴州硫酸烧渣	除铁后	11.23	1.45	1.59	2.67	5.02
陕西某固废中心氰化渣	除铁前	2.19	35.66	0.02	0.04	0.29
陕西某固废中心氰化渣	除铁后	5.71	6.59	0.21	0.38	2.26
山东两段焙烧氰化尾渣	除铁前	7.18	32.60	0.01	1.26	2.73
山东两段焙烧氰化尾渣	除铁后	15.71	3.26	0.03	3.41	4.59

表5 陕西某两段焙烧氰化尾渣除铁前后主要矿相组成及质量分数 (%)

矿物名称	除铁前	除铁后	矿物名称	除铁前	除铁后
铁氧化物相	62.06	1.43	石英	17.46	43.34
闪锌矿	0.05	0.12	碳酸盐矿物	0.74	10.38
黄铜矿	0.15	0.79	方铅矿	0.23	0.43
斑铜矿	0.06	0.15	白云母	10.58	21.11

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Fe³⁺-C₂O $4 2 -$ -H₂O溶液中Fe(Ⅲ)的形态分布及其在硫酸烧渣和氰化尾渣除铁过程中的应用

Species distribution of Fe(Ⅲ) in Fe³⁺-C₂O $4 2 -$ -H₂O solution and application in the process of iron removal from sulphuric acid cinder and syanide tailings

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