铝工业危废中氟元素分析方法研究

doi:10.19964/j.issn.1006-4990.2025-0039

摘要/Abstract

摘要：

当前，针对溶液中氟离子质量浓度的主流测定手段是氟离子计法，此法因操作简便、快捷、准确性高等优点而被普遍采用；但将其直接应用于测定铝工业危废处理过程中产生的成分复杂的含氟溶液时，准确度会大幅降低。为提高测量精度，以配制的标准含氟溶液为研究对象，研究总离子强度调节缓冲液（TISAB）对分析结果的影响。研究发现，适宜的TISAB添加量受溶液中氟和铝离子浓度的影响。溶液中不含与氟络合的离子时，可按取样溶液与TISAB体积比为1∶0.5进行初测，根据初测结果再参考不同氟离子浓度与TISAB最佳体积比的规律调整正式测定的比例。溶液中含铝等能与氟络合的离子时，需在测定前分析铝离子浓度并确定TISAB添加量。对铝离子质量浓度高于120.0 mg/L的溶液，可将铝离子质量浓度稀释至120.0 mg/L，并选择取样溶液与TISAB体积比为1∶1进行测量。若铝离子质量浓度较高而氟离子质量浓度较低，不适合过度稀释，则可稀释铝离子质量浓度至240.0 mg/L，并将取样溶液与TISAB的体积比设定为1：2进行测量，此时需在测试结果上加4.50%的正偏差。此方法能在复杂含氟溶液的测量中，将误差控制在2.00%以内，这可为其他复杂成分含氟溶液的准确测量提供参考。

关键词: 铝工业含氟危废, 氟元素分析, 总离子强度调节缓冲液

Abstract:

At present，the mainstream method for determining the mass concentration of fluoride ions in solutions is the fluoride ion selective electrode method，which is widely recognized for its advantages of simple operation，rapidity and high accuracy.However，when it is directly applied to the fluorine-containing solution with complex components produced during the treatment of hazardous waste in the aluminum industry，the accuracy will be greatly reduced.In order to improve the measurement accuracy，the prepared standard fluorine-containing solution was used as the research object to study the influence of the total ionic strength adjustment buffer（TISAB） on the analysis results. It was found that the appropriate dosage of TISAB was influenced by the concentrations of fluoride and aluminum ions in the solution.For solutions free of ions that could complex with fluoride，the volume ratio of the sample solution to TISAB could be set at 1∶0.5 for the preliminary test.Based on the preliminary test results，the ratio for the formal measurement could be adjusted by referring to the rule of the optimal volume ratio of different fluoride ion concentrations to TISAB.For solutions containing ions such as aluminum that could form complexes with fluoride，it was necessary to analyze the aluminum ion concentration and determine the dosage of TISAB to be added prior to the measurement.For solutions with an aluminum ion mass concentration higher than 120.0 mg/L，the aluminum ion mass concentration could be diluted to 120.0 mg/L，and the measurement could be performed with the volume ratio of the sample solution to TISAB of 1∶1.If the aluminum ion concentration was high while the fluoride ion concentration was too low，making excessive dilution inappropriate，the aluminum ion mass concentration could be diluted to 240.0 mg/L and the volume ratio of the sample solution to TISAB could be set to 1∶2，with a positive deviation of 4.50% added to the measured results.This method could control the error within 2.00% in the measurement of complex fluorine-containing solutions，and it provided a reference for the accurate determination of other fluorine-containing solutions with complex components.

Key words: fluoride-containing hazardous waste in aluminum industry, fluorine element analysis, total ionic strength adjustment buffer

中图分类号:

X705

刘应谆, 杨昇, 范阳阳, 梁学民. 铝工业危废中氟元素分析方法研究[J]. 无机盐工业, 2026, 58(2): 100-107.

LIU Yingzhun, YANG Sheng, FAN Yangyang, LIANG Xuemin. Study on analytical method of fluorine element in hazardous waste of aluminum industry[J]. Inorganic Chemicals Industry, 2026, 58(2): 100-107.

图/表 8

图1

图2

图3

图4

图5

表1

表2

表3

参考文献 28

[1]	ZHU He， LI Jingfei.Advancements in corrosion protection for aerospace aluminum alloys through surface treatment［J］.International Journal of Electrochemical Science，2024，19（2）：100487.
[2]	石志平，姜澜，杨洪亮，等.铝灰的回收处理及资源化利用研究现状［J］.无机盐工业，2020，52（9）：21-25.
	SHI Zhiping， JIANG Lan， YANG Hongliang，et al.Research status of recycling and resource utilization of aluminum dross［J］.Inorganic Chemicals Industry，2020，52（9）：21-25.
[3]	许国栋，敖宏，佘元冠.可持续发展背景下世界铝工业发展现状、趋势及我国的对策［J］.中国有色金属学报，2012，22（7）：2040-2051.
	XU Guodong， AO Hong， SHE Yuanguan.Current status and development trend of aluminum industry in world and strategy suggestions in China under background of sustainable development［J］.The Chinese Journal of Nonferrous Metals，2012，22（7）：2040-2051.
[4]	LI Shuangshuang， YUE Xin， LI Qingyuan，et al.Development and applications of aluminum alloys for aerospace industry［J］.Journal of Materials Research and Technology，2023，27：944-983.
[5]	CHANDEL R， SHARMA N， BANSAL S A.A review on recent developments of aluminum-based hybrid composites for automotive applications［J］.Emergent Materials，2021，4（5）：1243-1257.
[6]	刘宏博，郝雅琼，吴昊，等.铝冶炼行业危险废物产生和利用处置现状与管理对策建议［J］.环境工程技术学报，2021，11（6）：1273-1280.
	LIU Hongbo， HAO Yaqiong， WU Hao，et al.Present situation of production，utilization and disposal of hazardous waste in aluminium smelting industry and management countermeasures［J］.Journal of Environmental Engineering Technology，2021，11（6）：1273-1280.
[7]	王丹琴，练以诚，杜心，等.铝电解含氟固废处理技术研究进展［J］.无机盐工业，2025，57（6）：9-17.
	WANG Danqin， LIAN Yicheng， DU Xin，et al.Research progress on treatment technology for fluorine-containing solid wastes of electrolytic aluminum［J］.Inorganic Chemicals Industry，2025，57（6）：9-17.
[8]	AL-FAKIH A， MOHAMED NOR Z， INAYATH BASHA S，et al.Characterization and applications of red mud，an aluminum industry waste material，in the construction and building industries，as well as catalysis［J］.The Chemical Record，2023，23（5）：e202300039.
[9]	OLEJARCZYK M， RYKOWSKA I， URBANIAK W.Management of solid waste containing fluoride：A review［J］.Materials，2022，15（10）：3461.
[10]	LI Xueke， LIU Yan， ZHANG Ting′an.A comprehensive review of aluminium electrolysis and the waste generated by it［J］.Waste Management & Research，2023，41（10）：1498-1511.
[11]	李红英，王海宝，何晓波.离子选择电极法测定磷石膏中全氟含量［J］.无机盐工业，2009，41（3）：59-61.
	LI Hongying， WANG Haibao， HE Xiaobo.Determination on total fluorine content in phosphogypsum by ion selection electrode method［J］.Inorganic Chemicals Industry，2009，41（3）：59-61.
[12]	MAROCCO P， SUNDSETH K， AARHAUG T，et al.Online measurements of fluoride ions in proton exchange membrane water electrolysis through ion chromatography［J］.Journal of Power Sources，2021，483：229179.
[13]	SOLANKI Y S， AGARWAL M， GUPTA A B，et al.Fluoride occurrences，health problems，detection，and remediation methods for drinking water：A comprehensive review［J］.Science of the Total Environment，2022，807：150601.
[14]	焦阳，段小红.氟离子检验方法研究进展［J］.药物生物技术，2014，21（2）：180-184.
	JIAO Yang， DUAN Xiaohong.Recent research progress in the detection of fluoride ion［J］.Pharmaceutical Biotechnology，2014，21（2）：180-184.
[15]	ZACHARIOUDAKI D E， FITILIS I， KOTTI M.Review of fluorescence spectroscopy in environmental quality applications［J］.Molecules，2022，27（15）：4801.
[16]	DURODOLA S S， TOVIDE O O， OYEBODE B A，et al.Dye-assisted analysis of fluoride in water using UV-visible spectrophotometry：A preliminary study［J］.Water Practice & Technology，2024，19（5）：1615-1623.
[17]	徐华，田松，唐碧玉，等.混合碱熔-离子选择电极法测定钨尾矿的氟含量［J］.矿产与地质，2023，37（2）：414-419.
	XU Hua， TIAN Song， TANG Biyu，et al.Determination of fluorine content in tungsten tailings by mixed alkali fusion-ion selective el-ectrode method［J］.Mineral Resources and Geology，2023，37（2）：414-419.
[18]	蔡漫霞，刘福平，刘宏江，等.离子选择电极法测定氟离子的影响因素分析［J］.铜业工程，2017（1）：68-70.
	CAI Manxia， LIU Fuping， LIU Hongjiang，et al.Analysis of influencing factors on the determination of fluoride by ion selective electrode method［J］.Copper Engineering，2017（1）：68-70.
[19]	刘文春.氟离子电极法测定磷酸中氟含量需注意的问题［J］.化工设计通讯，2018，44（12）：142.
	LIU Wenchun.Problems needing attention in fluorine ion electrode method for determination of fluorine content in phosphoric acid［J］.Chemical Engineering Design Communications，2018，44（12）：142.
[20]	郝一莼，孙小单，徐桐，等.氟离子检测分析方法研究进展［J］.中国地方病防治杂志，2010，25（6）：412-415.
	HAO Yichun， SUN Xiaodan， XU Tong，et al.The study advance on examine method of fluorion［J］.Chinese Journal of Control of Endemic Diseases，2010，25（6）：412-415.
[21]	周洲，王红梅，张晗，等.微量血清氟电极法测定过程中总离子强度调节缓冲液的对比与优化［J］.卫生研究，2016，45（2）：194-199.
	ZHOU Zhou， WANG Hongmei， ZHANG Han，et al.Comparison and optimization of total ionic strength adjustment buffer during detecting fluoride in trace serum sample by fluoride ion selective electrode method［J］.Journal of Hygiene Research，2016，45（2）：194-199.
[22]	ZHAO Hang， ZHANG Xiaoguang， ZHANG Qijun，et al.Mechanochemical removal and recovery of fluorine from hazardous fluorine-containing solid waste：Experiments and mechanisms［J］.Journal of Environmental Chemical Engineering，2024，12（6）：114280.
[23]	唐伟月，邓全富，张环.缓冲液对碳酸钙含氟牙膏可溶氟稳定性的影响［J］.口腔护理用品工业，2023，33（1）：29-31.
	TANG Weiyue， DENG Quanfu， ZHANG Huan.Effect of buffer solution on soluble fluoride stability of calcium carbonate-based fluo-ride-containing toothpaste［J］.Oral Care Industry，2023，33（1）：29-31.
[24]	蔡德花，曾德文.离子缓冲剂对选择性电极法测定湿法炼锌体系中氟的影响［J］.冶金分析，2018，38（5）：41-46.
	CAI Dehua， ZENG Dewen.Influence of total ionic strength adjustment buffer on the determination of fluorine in zinc hydrometallurgy system by selective electrode method［J］.Metallurgical Analysis，2018，38（5）：41-46.
[25]	徐荣，孙娟，叶瑾.钙、镁、铁、铝离子对土壤中总氟化物检测干扰的消除［J］.化学分析计量，2018，27（4）：16-20.
	XU Rong， SUN Juan， YE Jin.Elimination of interference from calcium magnesium iron and aluminum ions in the detection of the total fluoride in soil［J］.Chemical Analysis and Meterage，2018，27（4）：16-20.
[26]	韩泽勋，罗丽琼，吴勇聪，等.废铝电解质浸出液的冰晶石诱导结晶除氟工艺研究［J］.中南大学学报（自然科学版），2023，54（2）：595-606.
	HAN Zexun， LUO Liqiong， WU Yongcong，et al.Cryolite-induced crystallization defluorination process of spent aluminium electrolyte leaching solution［J］.Journal of Central South University （Science and Technology），2023，54（2）：595-606.
[27]	谢堂锋，陈若葵，王明，等.氟离子选择电极法测定废旧锂电池回收浸出液中氟含量［J］.矿冶工程，2020，40（6）：126-129.
	XIE Tangfeng， CHEN Ruokui， WANG Ming，et al.Determination of fluoride concentration in the leachate of spent lithium batteries by using fluoride ion selective electrode［J］.Mining and Metallurgical Engineering，2020，40（6）：126-129.
[28]	康茂约，时君.不同TISAB在检测氟离子时消除Fe³⁺、Al³⁺干扰能力的研究［J］.现代食品，2016，22（6）：98-99.
	KANG Maoyue， SHI Jun.Study on eliminating the interference ability of Fe³⁺ and Al³⁺ in the detection of fluoride ions by different TISAB［J］.Modern Food，2016，22（6）：98-99.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会