铝电解含氟固废处理技术研究进展
收稿日期: 2024-03-27
网络出版日期: 2024-12-12
基金资助
北京市科学技术协会金桥工程项目(Zlhbyjy108202407013);中铝集团第二批青年科技人才培养计划项目(2024)
Research progress on treatment technology for fluorine-containing solid wastes of electrolytic aluminum
Received date: 2024-03-27
Online published: 2024-12-12
综述了湿法和火法技术在处理铝电解炭渣、大修渣及富余电解质等含氟固废方面的应用现状，概括了两种技术的优劣势。湿法处理技术通过选择合适的反应剂，在特定条件下将氟、铝等元素浸出至液相，再经沉淀、煅烧等步骤制备氟化铝产品，但产品质量和性质仍需进一步提升；火法处理技术则侧重于在高温条件下将氟转化为氟化盐产品以实现氟元素回收，不过其高温条件下对设备的腐蚀问题限制了其规模化应用。对铝电解工业含氟固废安全有效、高值化利用技术的持续开发具有重要意义。目前相关工作主要集中在采用化学方法提取和利用含氟固废中的有价元素，未来需探索其他新型处理方式，开发更多种类产品，以实现含氟固废的低成本、规模化利用。
王丹琴 , 练以诚 , 杜心 , 闫飞飞 , 刘万超 , 任武荣 . 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 . DOI: 10.19964/j.issn.1006-4990.2024-0170
The current applications of hydrometallurgical and pyrometallurgical technologies in the treatment of fluorine-containing solid wastes such as carbon slag，spent pot lining and aluminum electrolytes were reviewed.The advantages and disadvantages of these two technologies were outlined.Hydrometallurgical treatment involved selecting appropriate reagents to leach fluorine，aluminum，and other elements into the liquid phase under specific conditions，and then preparing aluminum fluoride products through steps such as precipitation and calcination.However，the quality and properties of the products still needed further improvement.Pyrometallurgical treatment focused on converting fluorine into fluorides under high-temperature conditions to achieve fluorine recovery.However，the corrosion of equipment under high-temperature conditions limited its large-scale application.It was of great significance for the continuous development of safe，effective，and high-value utilization technologies for fluorine-containing solid wastes in China's aluminum electrolysis industry.Current work was mainly concentrated on using chemical methods to extract and utilize valuable elements from fluorine-containing solid wastes.In the future，it was necessary to explore other new treatment methods，develop a wider variety of products，and achieve low-cost and large-scale utilization of fluorine-containing solid wastes.
Key words： aluminum electrolysis; fluorine-containing; solid waste; treatment
| 1 | 林雨琛，刘园，银光，等.基于物质流分析的电解铝氟化物全过程污染防治研究［J］.环境工程技术学报，2023，13（2）：800-807. |
| LIN Yuchen， LIU Yuan， YIN Guang，et al.Research on fluoride whole-process prevention and control in the electrolytic aluminum enterprise based on material flow analysis［J］.Journal of Environmental Engineering Technology，2023，13（2）：800-807. | |
| 2 | 梅向阳，刘群星，卿华，等.电解铝氟化物排放途径及控制措施［J］.轻金属，2023（5）：45-48. |
| MEI Xiangyang， LIU Qunxing， QING Hua，et al.Emission path and control measures for fluorides of electrolytic aluminum［J］.Light Metals，2023（5）：45-48. | |
| 3 | 卢惠民，邱竹贤.铝电解槽炭渣的综合利用研究［J］.矿产综合利用，1997（2）：45-47. |
| LU Huimin， QIU Zhuxian.Comprehensive utilization of carbonaceous slag from aluminium reduction cells［J］.Multipurpose Utilization of Mineral Resources，1997（2）：45-47. | |
| 4 | 张雅琪，陈喜平，孙宁宁.阳极炭渣催化脱碳制备冰晶石工艺研究［J］.无机盐工业，2024，56（3）：91-97. |
| ZHANG Yaqi， CHEN Xiping， SUN Ningning.Study on preparation process of cryolite from anode carbon slag by catalytic decarburization［J］.Inorganic Chemicals Industry，2024，56（3）：91-97. | |
| 5 | NIE Yunfei， GUO Xinyao， GUO Zhaohui，et al.Defluorination of spent pot lining from aluminum electrolysis using acidic iron-containing solution［J］.Hydrometallurgy，2020，194：105319. |
| 6 | LI Nan， XIE Gang， WANG Zuxu，et al.Recycle of spent potlining with low carbon grade by floatation［J］.Advanced Materials Research，2014，881-883：1660-1664. |
| 7 | WANG Jinling， LIU Haiying， LUO Youfa，et al.Study on harmless and resources recovery treatment technology of waste cathode carbon blocks from electrolytic aluminum［J］.Procedia Environmental Sciences，2012，16：769-777. |
| 8 | 赵亮，宋兴宽，路齐英，等.电解铝大修渣中总氟含量分析［J］.环境与可持续发展，2017，42（4）：114-115. |
| ZHAO Liang， SONG Xingkuan， LU Qiying，et al.Analysis of total fluorine in oberhaul waste residues from electrolytic aluminium［J］.Environment and Sustainable Development，2017，42（4）：114- 115. | |
| 9 | 高印，杜婷婷.铝电解过剩电解质产生原因及利用方法探讨［J］.世界有色金属，2020（16）：10-11. |
| GAO Yin， DU Tingting.Discussion on recycle utilization method of excess electrolyte in aluminum electrolysis［J］.World Nonferrous Metals，2020（16）：10-11. | |
| 10 | 易小兵，董春明.过量工业铝电解质产生及循环再利用的技术经济性探讨-值得电解铝厂重视和采用的冰晶石替代方法［C］//中国铝业集团.2007年中国国际铝冶金技术论坛论文汇编.北京：冶金工业出版社，2007：745-749. |
| 11 | ROBSHAW T J， BONSER K， COXHILL G，et al.Development of a combined leaching and ion-exchange system for valorisation of spent potlining waste［J］.Waste and Biomass Valorization，2020，11（10）：5467-5481. |
| 12 | SHI Zhongning， LI Wei， HU Xianwei，et al.Recovery of carbon and cryolite from spent pot lining of aluminium reduction cells by chemical leaching［J］.Transactions of Nonferrous Metals Society of China，2012，22（1）：222-227. |
| 13 | 崔竞波.铝电解中电解质的综合回收利用［D］.沈阳：东北大学，2020. |
| CUI Jingbo.Comprehensive recovery and utilization of electrolyte in aluminum electrolysis［D］.Shenyang：Northeastern University，2020. | |
| 14 | TAO Wenju， YANG Jiaxin， CHEN Liyu，et al.Environmentally friendly and efficient green recovery of fluoride from waste aluminum electrolytic sediment using Al2O3 ［J］.Separation and Purification Technology，2023，317：123934. |
| 15 | DONG Liangmin， JIAO Fen， LIU Wei，et al.A novel approach for extracting lithium from overhaul slag by low temperature roasting-water leaching［J］.Chemical Engineering Journal，2024，481：148571. |
| 16 | DONG Liangmin， JIAO Fen， LIU Wei，et al.Selective preparation of lithium carbonate from overhaul slag by high temperature sulfuric acid roasting-water leaching［J］.Journal of Environmental Management，2024，359：120963. |
| 17 | YUAN Jie， XIAO Jin， TIAN Zhongliang，et al.Optimization of spent cathode carbon purification process under ultrasonic action using taguchi method［J］.Industrial & Engineering Chemistry Research，2018，57（22）：7700-7710. |
| 18 | WANG Hao， FENG Qiming， TANG Xuekun，et al.Preparation of high-purity graphite from a fine microcrystalline graphite concentrate：Effect of alkali roasting pre-treatment and acid leaching process［J］.Separation Science and Technology，2016，51（14）：2465-2472. |
| 19 | 梁诚.利用Na2CO3处理铝电解槽炭渣的研究［D］.沈阳：东北大学，2021. |
| LIANG Cheng.Study on treatment of carbon residue in aluminum reduction cell by Na2CO3 ［D］.Shenyang：Northeastern University，2021. | |
| 20 | XU Rui， LUO Sha， LI Wenzhang，et al.Clean process for selective recovery of lithium carbonate from waste lithium-bearing aluminum electrolyte slag［J］.Industrial & Engineering Chemistry Research，2023，62（36）：14537-14547. |
| 21 | LISBONA D F， SOMERFIELD C， STEEL K M.Treatment of spent pot-lining with aluminum anodizing wastewaters：Selective precipitation of aluminum and fluoride as an aluminum hydroxyfluoride hydrate product［J］.Industrial & Engineering Chemistry Research，2012，51（39）：12712-12722. |
| 22 | MA Lutong， YANG Wanzhang， CUI Yan，et al.Regeneration of raw materials for aluminum electrolysis from spent carbon anodes via a closed-loop environmentally-friendly process based on aluminum-fluorine complexation［J］.Journal of Cleaner Production，2023，402：136787. |
| 23 | WU Shaohua， TAO Wenju， HAN Wang，et al.Hydrometallurgical stepwise separation of alumina and recovery of aluminum fluoride from waste anode cover material of aluminum electrolysis［J］.Minerals Engineering，2022，186：107740. |
| 24 | SCALISE V， SCHOLZ G， KEMNITZ E.Mechanochemical synthesis of low-fluorine doped aluminum hydroxide fluorides［J］.Journal of Solid State Chemistry，2016，243：154-161. |
| 25 | MIGUEL M G， BARRETO R P， PEREIRA S Y.Study of a tropical soil in order to use it to retain aluminum，iron，manganese and fluoride from acid mine drainage［J］.Journal of Environmental Management，2017，204：563-570. |
| 26 | LIU Jinlian， YIN Zhoulan， LIU Wei，et al.Treatment of aluminum and fluoride during hydrochloric acid leaching of lepidolite［J］. Hydrometallurgy，2020，191：105222. |
| 27 | CHEN Yuran， LI Pan， BU Xiangning，et al.Resource utilization strategies for spent pot lining：A review of the current state［J］.Separation and Purification Technology，2022，300：121816. |
| 28 | CUI Li， WANG Weihong， CHAO Xi，et al.Efficient lithium recovery from electrolytic aluminum slag via an environmentally friendly process：Leaching behavior and mechanism［J］.Journal of Cleaner Production，2024，439：140800. |
| 29 | LI Jiaming， YANG Youjian， TAO Wenju，et al.Study on preparation of aluminum fluoride from cryolite［J］.Materials Today Communications，2023，37：107440. |
| 30 | WU Shaohua， TAO Wenju， GE Hui，et al.Extraction and recycling of fluoride-containing phase from spent bottom sedimentation of aluminum smelting cell by leaching in Al3+ solution me- dia［J］.Separation and Purification Technology，2023，306：122797. |
| 31 | LISBONA D F， STEEL K M.Recovery of fluoride values from spent pot-lining：Precipitation of an aluminium hydroxyfluoride hydrate product［J］.Separation and Purification Technology，2008，61（2）：182-192. |
| 32 | LISBONA D F， SOMERFIELD C， STEEL K M.Leaching of spent pot-lining with aluminium nitrate and nitric acid：Effect of reaction conditions and thermodynamic modelling of solution speciation［J］.Hydrometallurgy，2013，134：132-143. |
| 33 | 杨万章，詹勇刚，陈本松，等.铝电解危废渣联合处理和资源综合利用方法：中国，113426807A［P］.2021-09-24. |
| 34 | TANG Yusheng， MA Lutong， QIU Zhesheng，et al.Research on synergistic disposal and high-value utilization of secondary aluminum dross and spent carbon anode［J］.Process Safety and Environmental Protection，2024，184：1094-1105. |
| 35 | 农志藩.氟化铝和冰晶石生产过程中的最佳质量控制［J］.无机盐工业，2015，47（10）：48-53. |
| NONG Zhifan.The best quality control of production process of aluminium-fluoride and synthetic cryolite［J］.Inorganic Chemicals Industry，2015，47（10）：48-53. | |
| 36 | YAN Hengwei， KUANG Ye， YANG Yonghui，et al.Preparation of anhydrous aluminum fluoride［J］.Results in Chemistry，2023，5：100919. |
| 37 | 申士富，刘朋，王金玲，等.高温法处理铝电解废阴极的机理［J］.有色金属（冶炼部分），2023（3）：61-67. |
| SHEN Shifu， LIU Peng， WANG Jinling，et al.Mechanism of high temperature treatment of spent cathode in aluminum electroly-sis［J］.Nonferrous Metals（Extractive Metallurgy），2023（3）： 61-67. | |
| 38 | ZHU Zhi， XU Lei， HAN Zhaohui，et al.Defluorination study of spent carbon cathode by microwave high-temperature roasting［J］.Journal of Environmental Management，2022，302：114028. |
| 39 | 柴登鹏，候光辉，黄海波.真空冶金法处理铝电解碳渣试验研究［J］.轻金属，2016（4）：25-27. |
| CHAI Dengpeng， HOU Guanghui， HUANG Haibo.Experimental study on the treatment of aluminum reduction carbon residue by vacuum metallurgy［J］.Light Metals，2016（4）：25-27. | |
| 40 | 陈喜平，李旺兴，王玉.一种提取铝电解阳极碳渣中电解质的方法：中国，101063215A［P］.2007-10-31. |
| 41 | BROOKS D G， CUTSHALL E R， BANKER D B，et al.Thermal treatment of spent potliner in a rotary kiln［M］.Switzerland Cham：Springer，1992：1044-1048. |
| 42 | HOLYWELL G， BREAULT R.An overview of useful methods to treat，recover，or recycle spent potlining［J］.JOM，2013，65（11）：1441-1451. |
| 43 | WANG Yifei， CHEN Xiping， ZHANG Shaojun，et al.Recycling of spent pot lining first cut from aluminum smelters by utilizing the two-step decomposition characteristics of dolomite［J］.Materials，2020，13（22）：5283. |
| 44 | ZHANG Tao， LIU Fupeng， CHEN Huagen，et al.Cleaner process for the selective extraction of lithium from spent aluminum electrolyte slag［J］.ACS Sustainable Chemistry & Engineering，2024，12（31）：11797-11808. |
| 45 | 刘风琴，赵洪亮，李荣斌，等.一种阳极炭渣和铝电解质回收利用方法：中国，110284157B［P］.2020-06-26. |
| 46 | 高继岩.铝电解危废碳渣制备氟化铝的研究［D］.昆明：昆明理工大学，2023. |
| GAO Jiyan.Study on preparation of aluminum fluoride from hazardous waste carbon slag from aluminum electrolysis［D］.Kunming：Kunming University of Science and Technology，2023. | |
| 47 | 沈祥，陈润冬，陈敏.废铝电解质制备氟化铝工艺的影响因素研究［J］.冶金与材料，2024，16（4）：157-159. |
| SHEN Xiang， CHEN Rundong， CHEN Min.Study on influencing factors of preparation of aluminum fluoride from waste aluminum electrolyte［J］.Metallurgy and Materials，2024，16（4）：157-159. | |
| 48 | LAN Jinghao， GAO Jiyan， YAN Hengwei，et al.Preparation of aluminum fluoride from carbon residue in aluminum electrolysis cell by roasting-leaching method［J］.Journal of Fluorine Chemistry，2024，275：110271. |
| 49 | 赖延清，李帅，杨声海，等.一种从富锂铝电解质废渣中高效提锂和制备无水氟化铝的方法：中国，113718107B ［P］.2022-08-02. |
| 50 | 陈开斌，邱仕麟，杜婷婷，等.一种铝电解含氟废弃物及富余电解质资源利用的方法：中国，111892022A［P］. 2020-11- |
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