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过程工程学报 ›› 2022, Vol. 22 ›› Issue (2): 268-275.DOI: 10.12034/j.issn.1009-606X.221043

• 研究论文 • 上一篇    下一篇

高温煅烧脱除磷酸铁中硫的研究

娄文博1,2， 张盈2,3， 张洋2,3， 王晓健2,3， 李建中1， 乔珊2,3， 郑诗礼2,3*， 张懿2,3   

  1. 1. 东北大学冶金学院，辽宁 沈阳 110819 2. 中国科学院过程工程研究所绿色过程与工程重点实验室，湿法冶金清洁生产技术国家工程实验室，北京 100190 3. 中国科学院绿色过程制造创新研究院，北京 100190
  • 收稿日期:2021-02-04 修回日期:2021-04-06 出版日期:2022-02-28 发布日期:2022-02-28
  • 通讯作者: 郑诗礼 slzheng@ipe.ac.cn
  • 作者简介:娄文博(1992-)，男，黑龙江省海伦市人，博士研究生，冶金物理化学专业，E-mail: 1510753205@qq.com；郑诗礼，通讯联系人，E-mail: slzheng@ipe.ac.cn.
  • 基金资助:
    中国科学院重点部署项目;中国科学院绿色过程制造创新研究院自主部署项目

Study on sulfur removal from ferric phosphate by high-temperature calcination

Wenbo LOU1,2,  Ying ZHANG2,3,  Yang ZHANG2,3,  Xiaojian WANG2,3,  Jianzhong LI1,  Shan QIAO2,3,  Shili ZHENG2,3*,  Yi ZHANG2,3   

  1. 1. School of Metallurgy, Northeastern University, Shenyang, Liaoning 110819, China 2. CAS Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 3. Innovation Academy for Green Manufacture, Chinese Academy of Sciences, Beijing 100190, China
  • Received:2021-02-04 Revised:2021-04-06 Online:2022-02-28 Published:2022-02-28
  • Contact: ZHENG Shi-li slzheng@ipe.ac.cn

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摘要： 磷酸铁是合成磷酸铁锂电池正极材料的主要原料，目前多采用硫酸亚铁和磷酸盐共沉淀方法制备。硫酸体系内共沉淀获得的磷酸铁中硫杂质含量较高，目前采用水洗方式脱除，吨磷酸铁洗水用量需60~100吨，硫酸盐废水处理成本高。为从源头削减磷酸铁脱硫过程产生的大量废水，根据硫酸盐高温分解的性质，提出磷酸铁高温煅烧脱硫新方法，开展了热力学可行性计算与高温煅烧脱硫动力学研究。结果表明，磷酸铁中硫元素主要以硫酸根形式存在，高温煅烧可有效促进含硫杂质分解，温度越高，脱硫效果越好。高温煅烧脱硫过程反应动力学级数为2，活化能为88.075 kJ/mol，属于化学反应控制。在温度1173 K、煅烧时间10 min的条件下，磷酸铁中硫杂质含量可降至0.01wt%以下。

关键词: 磷酸铁, 高温煅烧, 脱硫, 热力学, 动力学

Abstract: Iron phosphate is the main material for the synthesis of lithium iron phosphate battery cathode material, which is mainly produced by co-precipitation method of using ferrous sulfate and phosphate salt. The sulfur content in the iron phosphate prepared by the co-precipitation process in the sulfate system is high, which has to be removed by washing with large amount of water of around 60~100 tons per ton of iron phosphate, bringing a huge burden of sulfate-bearing wastewater treatment. To reduce the amount of wastewater from the source, this research proposed an alternative way for desulfurization by high-temperature calcination based on the feature of sulfate decomposition at high temperatures. The thermodynamic feasibility and kinetics of the desulfurization were studied. The results showed that the sulfur in ferric phosphate existed in the form of sulfate, which can be effectively removed by high-temperature calcination. A higher temperature was preferred for a more satisfactory desulfurization efficiency. Kinetic study uncovered that the desulfurization reaction order was 2, and the activation energy was 88.075 kJ/mol, indicating a chemical reaction control mode. The sulfur content in iron phosphate can be reduced to less than 0.01wt% by calcining at 1173 K for 10 min.

Key words: iron phosphate, high-temperature calcination, desulfurization, thermodynamics, kinetics