Fe(II)-Fe(III)-Cu(II)-H2SO4-H2O 溶液的热力学模型及其在铜电解精炼过程中测定氧化还原电位的应用（最高 70 °C）,Industrial & Engineering Chemistry Research

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Fe(II)-Fe(III)-Cu(II)-H2SO4-H2O 溶液的热力学模型及其在铜电解精炼过程中测定氧化还原电位的应用（最高 70 °C）
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2021-11-01 , DOI: 10.1021/acs.iecr.1c02000
Yongteng Dong ₁ , Jiahao Xu ₁ , Bradford Wesstrom ₂ , Blanca R. Olave ₂ , Juan Sanchez ₂ , John P. Quinn ₂ , Guikuan Yue ₁

Affiliation

开发了 Fe(II)-Fe(III)-Cu(II)-H ₂ SO ₄ -H ₂ O 系统的热力学模型，并证明其能够可靠地模拟 25 到 70° 工业铜电解精炼电解液中的物质分布C。先前开发的 Fe(II)-Fe(III)-H ₂ SO ₄ -H ₂ O 系统在浸出条件下的模型首先被评估，并证明其适用性可以扩展到更高的酸浓度（185 g /L)。然后确定了 Cu(II) 物种，并收集并评估了它们的热力学数据以进行建模计算。结果表明，添加大量铜（40-50 g/L）后，Fe(II) 仍以游离 Fe ^{2+ 的形式}分布、FeHSO ₄⁺和 FeSO ₄ °；Fe(III) 以游离 Fe ³⁺、FeSO ₄⁺、FeHSO ₄²⁺和 Fe(SO ₄ ) ₂^{– 的形式分布}。Cu(II) 溶解为 Cu ²⁺、CuSO ₄ ° 和 CuHSO ₄⁺. 通过在所有溶液条件下对测得的氧化还原电位进行可靠和准确的预测，验证了所提出的模型。之前开发的用于预测氧化还原电位的表达式仍然可以应用于这项工作。形态分析结果强烈支持具有如此高酸和铜浓度的酸性硫酸铁溶液的氧化还原电位仍然可以完全由 Fe ³⁺ /Fe ²⁺对决定。还获得并讨论了 pH 值和有效离子强度。这些发现有助于进一步研究铜生产过程中其他溶液的形态。

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Thermodynamic Modeling of the Fe(II)–Fe(III)–Cu(II)–H2SO4–H2O Solution and Its Application to Determination of Redox Potential during Copper Electrorefining up to 70 °C

A thermodynamic model of the Fe(II)–Fe(III)–Cu(II)–H₂SO₄–H₂O system is developed and shown to reliably simulate the species distribution in the industrial copper electrorefining electrolyte from 25 to 70 °C. The previously developed model of the Fe(II)–Fe(III)–H₂SO₄–H₂O system under leaching conditions was first evaluated, and it proved that its applicability can be extended to a much higher acid concentration (185 g/L). Cu(II) species were then identified, and their thermodynamic data were collected and assessed for modeling calculations. Results reveal that after addition of a high amount of copper (40–50 g/L), Fe(II) is still distributed as free Fe²⁺, FeHSO₄⁺, and FeSO₄°; Fe(III) is distributed as free Fe³⁺, FeSO₄⁺, FeHSO₄²⁺, and Fe(SO₄)₂^–. Cu(II) is dissolved as Cu²⁺, CuSO₄°, and CuHSO₄⁺. The proposed model was validated by reliable and accurate prediction of the measured redox potential throughout all solution conditions. An expression developed previously to predict the redox potential can still be applied in this work. Analysis of speciation results strongly supports that the redox potential of acidic iron sulfate solutions with such a high acid and copper concentration can still be solely determined by the Fe³⁺/Fe²⁺ couple. The pH and effective ionic strength were also obtained and discussed. These findings contribute to further investigation on speciation of other solutions during copper production.

更新日期：2021-11-10

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