无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ

无机盐工业 ›› 2025, Vol. 57 ›› Issue (12): 99-106.doi: 10.19964/j.issn.1006-4990.2024-0561

• 环境·健康·安全 • 上一篇    下一篇

杂质离子对含氟废水氟化钙颗粒结晶沉淀的影响

李军霄1(), 黄鸶云1, 解蕾1, 张雨茜1, 钱玉鹏1,2,3()   

  1. 1.武汉理工大学资源与环境工程学院,湖北 武汉 430070
    2.矿物资源加工与环境湖北省重点实验室,湖北 武汉 430070
    3.关键非金属矿产资源绿色利用教育部重点实验室,湖北 武汉 430070
  • 收稿日期:2024-10-21 出版日期:2025-12-10 发布日期:2025-12-29
  • 通讯作者: 钱玉鹏(1984— ),男,博士,副教授,主要研究方向为非金属矿选矿与深加工、矿物功能材料成型技术;E-mail:qianyupeng@whut.edu.cn
  • 作者简介:李军霄(2001— ),男,硕士研究生,主要研究方向为固废资源化及综合利用的研究;E-mail:lijunxiao2001@163.com
  • 基金资助:
    湖北省自然科学基金项目(2022CFB433)

Effect of impurity ions on crystallization and precipitation of calcium fluoride particles in fluorine-containing wastewater

LI Junxiao1(), HUANG Siyun1, XIE Lei1, ZHANG Yuxi1, QIAN Yupeng1,2,3()   

  1. 1. School of Resources and Environmental Engineering,Wuhan University of Technology,Wuhan 430070,China
    2. Hubei Provincial Key Laboratory of Mineral Resources Processing and Environment,Wuhan 430070,China
    3. Key Laboratory of Green Utilization of Critical Non-metallic Mineral Resources,Ministry of Education,Wuhan 430070,China
  • Received:2024-10-21 Published:2025-12-10 Online:2025-12-29

摘要:

杂质离子是影响含氟废水结晶沉淀的关键因素之一,为探究杂质离子(Al³⁺和Si⁴⁺)对含氟废水钙盐结晶沉淀过程的影响,提高含氟废水的处理效果,利用NaF和CaCl2反应模拟含氟废水沉淀过程,结合Visual MINTEQ软件模拟、XRD表征和SEM-EDS测试,系统研究Al³⁺和Si⁴⁺对沉淀结晶浊度、残余氟离子浓度及沉淀产物特征的影响。研究结果表明,低浓度的Al3+和Si4+对氟化钙结晶沉淀和除氟效果影响较小。当Al3+质量浓度为200.00 mg/L时,碱性条件下反应产生氢氧化铝和冰晶石等杂质沉淀,导致反应浊度升高,残余氟离子浓度随pH升高而降低;当Si4+质量浓度为200.00 mg/L时,结晶沉淀产物中含硅杂质主要为石英和硅酸钙,最佳除氟条件为n(Ca)/n(F)=2.5、pH=9,此时,溶液中残余氟离子质量浓度为5.62 mg/L。SEM-EDS测试表明,沉淀产物呈块状团聚体,氟化钙与杂质产物嵌布关系复杂,分离难度较大。研究结果为实际生产工艺中复杂多离子含氟废水的处理及结晶产物的回收利用提供参考。

关键词: 含氟废水, 氟化钙, 杂质离子, 结晶沉淀, 除氟效果

Abstract:

Impurity ions are one of the key factors affecting the crystallization and precipitation of fluorine-containing wastewater.In order to investigate the influence of impurity ions(Al³⁺ and Si⁴⁺) on the calcium salt crystallization and precipitation process of fluorine-containing wastewater and improve the treatment effect of fluorine-containing wastewater,the reaction of NaF and CaCl2 was used to simulate the sedimentation process of fluorine-containing wastewater.Combined with Visual MINTEQ software simulation,XRD characterization,and SEM-EDS testing,the influence of Al³⁺ and Si⁴+ on the turbidity of precipitation crystallization,residual fluoride ion concentration,and precipitation product characteristics was systematically studied.The research results indicated that low concentrations of Al3+ and Si4+ had little effect on the precipitation and defluorination of calcium fluoride crystals.When the concentration of Al3+ was 200.00 mg/L,impurities such as aluminum hydroxide and cryolite precipitated under alkaline conditions,leading to an increase in reaction turbidity and a decrease in residual fluoride ion concentration with increasing pH.When the concentration of Si4+ was 200.00 mg/L,the silicon impurities in the crystal precipitation product were mainly quartz and calcium silicate,and the optimal defluorination conditions were n(Ca)/n(F)=2.5,pH=9.At this point,the residual fluoride ion concentration in the solution was 5.62 mg/L.SEM-EDS testing showed that the precipitate products were in the form of block aggregates,and the embedding relationship between calcium fluoride and impurity products was complex,making separation difficult.The research results provided reference for the treatment of complex multi ion fluorine-containing wastewater and the recycling of crystallization products in actual production processes.

Key words: fluorinated wastewater, calcium fluoride, impurity ions, crystalline precipitation, fluoride removal effect

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