多价硫化砷渣与铜冶炼烟尘浸出液协同处理过程中沉铜机理研究
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作者单位:

1.广东飞南资源利用股份有限公司,广东 肇庆 526233 ;2.广东省工业固废含铜污泥资源综合利用工程技术研究中心,广东 肇庆 526233

作者简介:

李俊(1986—),男,硕士,高级工程师,主要研究方向为含金属危固废综合利用

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中图分类号:

TF811;X758

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Copper precipitation mechanism of copper smelting dust leaching solution coprocessing with multivalent arsenic sulfide slag
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Affiliation:

1.Guangdong Feinan Resources Recycling Co., Ltd., Zhaoqing 526233 , China ;2.Engineering Technology Research Center for Comprehensive Utilization of Industrial Solid Waste Copper Sludge Resources ofGuangdong, Zhaoqing 526233 , China

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    摘要:

    光和法是处理高砷铜溶液的理想方式之一,现有文献认为硫化砷渣沉铜以As2S3与铜离子的硫化沉淀反应为主,然而现场应用的硫化砷渣中除 As2S3外,还含有大量 As2S5。为厘清多价硫化砷渣的沉铜反应机理,本研究以某企业高铜浸出液和砷滤饼为原料,考察了硫化砷用量、反应温度、反应时间等因素对沉铜浸砷的行为影响规律,并对产物进行了表征分析,得到以下主要结论。硫化砷用量、反应温度及反应时间对铜沉淀率、砷浸出率及渣含砷影响较大,总体上随着硫化砷用量增加、反应温度及反应时间延长,铜沉淀率和砷浸出率呈上升趋势,渣含砷呈下降趋势;在硫化砷渣用量1.3倍、反应温度85℃、 反应时间60 min的条件下,沉铜率大于99%,但渣含砷还能达到14.64%,需要继续延长反应时间浸砷,延长到255 min时,渣含砷4.05%。反应过程可分为沉铜阶段和浸砷阶段,沉铜阶段(15~60 min内)以As2S3 和As2S5的沉铜反应及As2S3耗硫酸沉铜反应为主,反应动力学为零级反应,为化学反应控制步骤;浸砷阶段(75~255 min)以 As2S5向低价硫化砷转化反应和 As2S3、As2S5的硫磺生成反应为主,反应动力学模型符合Boltzmann 模型,后期延长时间,砷浸出率变化幅度极小,渣含砷变化不大。本研究结果对现有的硫化砷渣沉铜机理起到了补充作用,即对于 As(Ⅴ)含量高的多价硫化砷渣,除了 As(Ⅲ)参与沉铜反应外,As(Ⅴ)也参与沉铜反应,且有向低价硫化砷转化继续沉铜的反应。

    Abstract:

    The light sum method is one of the ideal ways to deal with high arsenic copper solution. The existing literature believes that the copper precipitation of arsenic sulfide slag is mainly the sulfide precipitation reaction of As2S3 with copper ions. However, the arsenic sulfide slag used in the field contains a large amount of As2S5 in addition to As2S3. In order to clarify the copper precipitation reaction mechanism of multivalent arsenic sulfide slag, this study used a high arsenic copper leaching solution and arsenic filter cake of an enterprise as raw materials to investigate the effect of factors such as arsenic sulfide dosage, reaction temperature and reaction time on the behavior of copper precipitation and arsenic leaching. The product was characterized and analyzed, and the following main conclusions were obtained. The amount of arsenic sulfide, reaction temperature and reaction time had a great influence on copper precipitation rate, arsenic leaching rate and arsenic content in slag. In general, with the increase of arsenic sulfide dosage, reaction temperature and reaction time, copper precipitation rate and arsenic leaching rate showed an upward trend, and arsenic content in slag showed a downward trend. Under the conditions of arsenic sulfide slag dosage 1. 3 times, reaction temperature 85℃ and reaction time 60 min, the copper deposition rate is more than 99%, and the arsenic content in the slag can reach 14. 64%. It is necessary to continue to extend the reaction time to soak arsenic. When the reaction time is extended to 255 min, the arsenic content in the slag is 4. 05%. The reaction process can be divided into copper precipitation stage and arsenic leaching stage. The copper precipitation stage (15-60 min) is dominated by the copper precipitation reaction of As2S3 and As2S5 and the copper precipitation reaction of As2S3 with sulfuric acid. The reaction kinetics is zero-order reaction, which is the control step of chemical reaction. In the arsenic leaching stage (75-255 min), the conversion reaction of As2S5 to low valence arsenic sulfide and the sulfur generation reaction of As2S3 and As2S5 are the main reactions. The reaction kinetic model conforms to the Boltzmann model. In the later stage, the arsenic leaching rate changes little, and the arsenic content in the slag changes little. The results of this study complement the existing copper deposition mechanism of arsenic sulfide slag, that is, for multivalent arsenic sulfide slag with high As(V) content, in addition to As(III) participating in the copper deposition reaction, As(V) also participates in the copper deposition reaction, and there is a conversion to low valence arsenic sulfide to continue the copper deposition reaction.

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李俊,刘小文,周兆安,等 . 多价硫化砷渣与铜冶炼烟尘浸出液协同处理过程中沉铜机理研究[J]. 中国有色冶金, 2026,55(2):99-107.

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  • 收稿日期:2025-12-02
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  • 在线发布日期: 2026-05-12
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