摘要
磷石膏是磷肥工业的主要副产物,其废渣在堆存过程中所含氟化物通过淋溶作用释放至环境,引发土壤退化、地下水污染及生态毒性风险。通过优化样品前处理方法、色谱条件、灵敏度与准确性条件,建立了一种准确测定磷石膏废渣中氟化物的全量及浸出液浓度的离子色谱方法。结果表明:氟离子具有良好的线性关系,相关系数为0.9997,浸出液检出限为0.0004 mg/L,定量限为0.0012 mg/L,相对标准偏差(RSD)为0.31%,样品加标回收率在96.4%~98.4%;全量检出限为0.08 mg/kg,定量限为0.24 mg/L,全量相对标准偏差(RSD)为0.68%,样品加标回收率在98.6%~101%。全量消解过程和仪器优化过程具有高度稳定性,浸出液方法稳定,前处理步骤有效减少了干扰物影响,检测条件适配低浓度分析,方法准确、可靠,可应用于实际生产中。
Phosphogypsum is a major by-product of the phosphorus fertilizer industry.During the storage of its waste residue,the fluoride contained therein is released into the environment through leaching,thereby causing soil degradation,groundwater contamination,and ecological toxicity risks.To this end,an ion chromatography method has been established to accurately determine the total fluoride content and leachate concentration in phosphogypsum waste residue.The study compared the test results of three total pretreatment methods-high-temperature semifusion method,mixed acid-microwave digestion method,and ultrasonic-assisted acid leaching method-and optimized the acid system,digestion temperature and time,as well as the elimination of interfering substances in the mixed acid-microwave digestion method.Meanwhile,the leaching agent,oscillation time,and solid-liquid ratio in the leachate pretreatment method were also optimized.In addition,the selection of chromatographic columns,eluents,instrument parameters,sensitivity,and accuracy were finely adjusted.In the experiment,the total digestion solution was diluted tenfold by solid-phase extraction,while the leachate was detected by online enrichment and largevolume injection.The experiment determined that the optimal digestion system was nitric acid:hydrochloric acid=5∶1,and gradient heating was adopted(from 80℃to 160℃,and then to 200℃,maintained for 10 minutes,15 minutes,and 20 minutes respectively).In the total pretreatment using the nitric acid-hydrochloric acidmicrowave digestion method,the addition of 5 g/L H3BO3 and phosphate buffer solution could minimize interference to the greatest extent.For the leachate,acetic acid-sodium acetate buffer solution was determined as the leaching agent,with the optimal oscillation time being 36 hours and the solid-liquid ratio being 1∶30.The experimental results showed that fluoride ions had a good linear relationship,with a correlation coefficient of 0.9997.The detection limit of the leachate was 0.0004 mg/L,the quantification limit was 0.0012 mg/L,the precision RSD was 0.31%,and the spiked sample recovery was between 96.4%and 98.4%.The detection limit of the total amount was 0.08 mg/kg,the quantification limit was 0.24 mg/L,the precision RSD was 0.68%,and the spiked sample recovery rate was between 98.6%and 101%.The total digestion process and instrument optimization process showed high stability.The leachate method,with stable pretreatment steps,effectively reduced the impact of interfering substances,and the detection conditions were suitable for low-concentration analysis.The method is mature and reliable,and is suitable for practical production applications.
作者
贾雷
左修源
彭丽萍
孙兆楠
阿拉木斯
JIA Lei;ZUO Xiuyuan;PENG Liping;SUN Zhaonan;A Lamusi(Hohhot General Survey of Natural Resources Center,China Geological Survey,Hohhot,Inner Mongolia 010010,China;Liaoning Key Laboratory of Chemical Additive Synthesis and Separation,Yingkou Institute of Technology,Yingkou,Liaoning 115014,China)
出处
《中国无机分析化学》
北大核心
2025年第12期1919-1927,共9页
Chinese Journal of Inorganic Analytical Chemistry
基金
2025年国森矿业有限责任公司样品检测技术服务项目
国家重点研发计划项目(2022YFE0196700)
辽宁省教育厅基本科研项目(JYTQN2023016)
营口理工学院2024年产教融合(产业学院)项目(校企共建应用化学专业协同育人平台)。
关键词
磷石膏废渣
浸出液
氟化物
离子色谱
phosphogypsum sludge
leachate
fluoride
ion chromatography
