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研究了采用高温固相法制备Fe/F共掺杂锰系离子筛HMFeO-F,通过XRD、SEM、FT-IR、BET等手段考察了煅烧温度、煅烧时间和掺杂配比对离子筛结构的影响，并探讨了其对锂的吸附性能。结果表明：在煅烧温度800℃、煅烧时间10 h、锂锰物质的量比1/2、Fe、F掺杂摩尔分数分别为5%、10%条件下，HMFeO-F对锂的吸附容量为31.57 mg/g,吸附过程中锰溶损率仅为4.52%,相较于未掺杂时降低61%,同时磁性Fe3O4的引入使材料磁回收率达90.2%;经过5次循环试验后，HMFeO-F的平衡吸附容量仍可达25.87 mg/g,锰溶损率保持在5%以内；针对锂质量浓度为12.98 mg/L的某煤矸石酸浸液，用HMFeO-F吸附锂，锂吸附率可达99%。采用该离子筛提取煤矸石中的锂不仅为提锂提供了一种新的途径，而且有望实现煤矸石的高值化利用。
Abstract：Iron and fluorine co-doped manganese ion sieve HMFeO-F was prepared by high temperature solid phase method.The effects of calcination temperature, calcination time and doping ratio on the structure of the ion sieve were investigated by XRD,SEM,FT-IR and BET,and its adsorption performance was studied.The results show that the adsorption capacity for lithium of HMFeO-F is 31.57 mg/g under the conditions of calcination temperature of 800 ℃,calcination time of 10 h, molar ratio of lithium to manganese of 1/2,and doping mole fractions of Fe and F of 5% and 10%,respectively.The Mn dissolution loss rate during the adsorption process is only 4.52%,which is 61% lower than that of the undoped.At the same time, the introduction of magnetic Fe3O4 makes the magnetic recovery rate of the material can reach 90.2%. After five cycles of tests, the equilibrium adsorption capacity for lithium of HMFeO-F can still reach 25.87 mg/g, and the manganese dissolution loss rate remains within 5%.For a coal gangue acid leaching solution with a lithium mass concentration of 12.98 mg/L,lithium is adsorbed by HMFeO-F,and the lithium adsorption rate can reach 99%.The use of ion sieve to extract lithium from coal gangue can not only develop a new way to extract lithium, but also is expected to achieve the high-value utilization of coal gangue.
[1] 王雅茹，解玉龙.盐湖卤水提锂吸附材料研究进展[J].盐湖研究，2025,33(1):113-122.WANG Yaru,XIE Yulong.Research progress on extracting lithium adsorption materials from salt lake brine[J].Journal of Salt Lake Research,2025,33(1):113-122.
[2] 李成伟，柴文帅.全球锂资源供需现状分析[J].中国资源综合利用，2024,42(7):167-170.LI Chengwei,CHAI Wenshuai.Analysis of global lithium resource supply and demand status[J].China Resources Comprehensive Utilization,2024,42(7):167-170.
[3] 陈欣怡，夏开胜，高强，等.锂离子选择性吸附材料的制备与提取应用[J].化学进展，2023,35(10):1519-1533.CHEN Xinyi,XIA Kaisheng,GAO Qiang,et al.Preparation and extraction application of lithium ion selective adsorption materials[J].Progress in Chemistry,2023,35(10):1519-1533.
[4] LIU B J,WANG J Y,HE H T,et al.Geochemistry of carboniferous coals from the Laoyaogou mine,Ningwu coalfield,Shanxi province,Northern China:emphasis on the enrichment of valuable elements[J].Fuel,2020,279.DOI:10.1016/j.fuel.2020.118414.
[5] 王沙，秦伟，韩雪，等.粉煤灰中锂元素的浸出及动力学研究[J].湿法冶金，2024,43(6):646-651.WANG Sha,QIN Wei,HAN Xue,et al.Leaching and kinetic of lithium element from waste coal fly ash[J].Hydrometallurgy of China,2024,43(6):646-651.
[6] 罗清龙，董明哲，李军，等.吸附法分离盐湖卤水中锂的研究进展[J].盐湖研究，2023,31(1):106-115.LUO Qinglong,DONG Mingzhe,LI Jun,et al.Research progress of lithium separation from salt lake brine by adsorption method[J].Journal of Salt Lake Research,2023,31(1):106-115.
[7] WENG D,DUAN H Y,HOU Y C,et al.Introduction of manganese based lithium-ion sieve:a review[J].Progress in Natural Science:Materials International,2020,30(2):139-152.
[8] 段曼华，程丹，高倩，等.锂离子筛吸附材料的研究进展[J].功能材料，2023,54(2):2072-2081.DUAN Manhua,CHENG Dan,GAO Qian,et al.Research progress of lithium ion sieve adsorption materials[J].Journal of Functional Materials,2023,54(2):2072-2081.
[9] 侯永茹，李彦恒，代红，等.用吸附法从粉煤灰碱性溶液里提取锂[J].粉煤灰综合利用，2015(3):10-11.HOU Yongru,LI Yanheng,DAI Hong,et al.Experimental study on lithium extraction from fly ash alkaline solution by absorption method[J].Fly Ash Comprehensive Utilization,2015(3):10-11.
[10] 成俊伟，任卫国，王建成，等.吸附法提取煤矸石中锂的工艺[J].化工进展，2019,38(8):3589-3595.CHENG Junwei,REN Weiguo,WANG Jiancheng,et al.Extraction of lithium from coal gangue by manganese ion sieve adsorption[J].Chemical Industry and Engineering Progress,2019,38(8):3589-3595.
[11] CHUNG Y K,SHU D,KIM K B.Determination of the potential range responsible for the replacement of surface film on LiMn2O4[J].Electrochimica Acta,2003,49(6):887-898.
[12] 李珍，高建明，赵茜，等.铬铁复合掺杂锂离子筛的制备及其吸附性能研究[J].功能材料，2024,55(4):4094-4101.LI Zhen,GAO Jianming,ZHAO Qian,et al.Study on preparation and adsorption performance of chromium-iron composite doped lithium-ion sieve[J].Journal of Functional Materials,2024,55(4):4094-4101.
[13] 储迎宇，夏开胜，高强，等.宏观大尺寸锂离子筛的制备与吸附应用研究进展[J].矿产保护与利用，2023,43(4):130-144.CHU Yingyu,XIA Kaisheng,GAO Qiang,et al.Research progress on preparation and adsorption application of macroscopical large size lithium-ion sieves[J].Conservation and Utilization of Mineral Resources,2023,43(4):130-144.
[14] 朱晓峰，吕龙，李天玉，等.用H2TiO3型锂离子筛从盐湖卤水中提锂试验研究[J].湿法冶金，2024,43(3):275-283.ZHU Xiaofeng,LYU Long,LI Tianyu,et al.Extraction of lithium from salt lake brine by H2TiO3 lithium ion sieves[J].Hydrometallurgy of China,2024,43(3):275-283.
[15] SHEN X M,CLEARFIELD A.Phase transitions and ion exchange behavior of electrolytically prepared manganese dioxide[J].Journal of Solid State Chemistry,1986,64(3):270-282.
[16] YE S H,BO J K,LI C Z,et al.Improvement of the high-rate discharge capability of phosphate-doped spinel LiMn2O4 by a hydrothermal method[J].Electrochimica Acta,2010,55(8):2972-2977.
[17] ZHU L,LIU Y,WU W Y,et al.Surface fluorinated LiNi0.8Co0.15Al0.05O2 as a positive electrode material for lithium ion batteries[J].Journal of Materials Chemistry:A,2015,3(29):15156-15162.
[18] ZHANG G T,ZHANG J Z,ZHOU Y,et al.Synthesis of aluminum-doped ion-sieve manganese oxides powders with enhanced adsorption performance[J].Colloids and Surfaces:A,2019,583.DOI:10.1016/j.colsurfa.2019.123950.
[19] QIAN F R,ZHAO B,GUO M,et al.Trace doping by fluoride and sulfur to enhance adsorption capacity of manganese oxides for lithium recovery[J].Materials & Design,2020,194:DOI:10.1016/j.matdes.2020.108867.
[20] 钱方仁，郭敏，赵炳，等.Mg2+掺杂对H1.6Mn1.6O4锂离子筛吸附性能的影响[J].盐湖研究，2020,28(2):1-14.QIAN Fangren,GUO Min,ZHAO Bing,et al.Effect of Mg doping on adsorption property of H1.6Mn1.6O4 lithium ion sieve[J].Journal of Salt Lake Research,2020,28(2):1-14.
[21] GAO J M,DU Z Y,ZHAO Q,et al.Enhanced Li+ adsorption by magnetically recyclable iron-doped lithium manganese oxide ion-sieve:synthesis,characterization,adsorption kinetics and isotherm[J].Journal of Materials Research and Technology,2021,13:228-240.
[22] HAN H J,QU W,ZHANG Y L,et al.Enhanced performance of Li+ adsorption for H1.6MneO4 ion-sieves modified by Co doping and micro array morphology[J].Ceramics International,2021,47(15):21777-21784.
[23] 牛越，薛峰，周鑫，等.HGa0.1Mn1.9O4锂离子筛的制备与性能评价[J].应用化工，2022,51(5):1242-1247.NIU Yue,XUE Feng,ZHOU Xin,et al.Preparation and performance measurement of HGa0.1Mn1.9O4 lithium manganese ion sieve[J].Applied Chemical Industry,2022,51(5):1242-1247.
[24] ZHANG G T,HAI C X,ZHOU Y,et al.Al and F ions co-modified Li1.6Mn1.6O4 with obviously enhanced Li+ adsorption performances[J].Chemical Engineering Journal,2022,450.DOI:10.1016/j.cej.2022.137912.
[25] GAO Y W,WANG S G,GAO F,et al.Al and Cr ions co-doped spinel manganese lithium ion-sieve with enhanced Li+ adsorption performance and structural stability[J].Microporous and Mesoporous Materials,2023,351.DOI:10.1016/j.micromeso.2023.112492.
[26] GAO J M,DU Z Y,ZHAO Q,et al.Enhanced Li+ adsorption by magnetically recyclable iron-doped lithium manganese oxide ion-sieve:synthesis,characterization,adsorption kinetics and isotherm[J].Journal of Materials Research and Technology,2021,13:228-240.
基本信息:
DOI：10.13355/j.cnki.sfyj.2025.05.007
中图分类号:TD849.5;TF826;O647.3
引用信息:
[1]解文鹏,姚素玲,付元鹏等.铁氟共掺杂锰系离子筛的制备及其对锂的吸附性能研究[J].湿法冶金,2025,44(05):626-634.DOI:10.13355/j.cnki.sfyj.2025.05.007.
基金信息:
国家自然科学基金青年基金项目(52504303); 山西省重点研发计划项目(202202090301009); 山西省基础研究计划项目(202103021223045)