离子筛型锂吸附剂吸附法从盐湖卤水/海水中提锂的研究进展

doi:10.16085/j.issn.1000-6613.2017.03.005

摘要/Abstract

摘要：

金属锂及其化合物广泛应用于各个领域，其需求与日俱增，是一种重要的战略资源。传统的从矿石中提锂步骤繁琐、能耗大，且资源量日益减少，因此，从液态锂源如盐湖卤水、海水中提取锂资源具有十分重要的意义。相关研究者对液态提锂的方法也进行了积极的探索研究，而离子筛型锂吸附剂以其绿色而高效的优势，引起了众多学者的关注，成为目前最有发展潜力的液态提锂方法之一。本文对离子筛型锂吸附剂进行了分类，综述了锰系氧化物、钛系氧化物以及掺杂型离子筛这3种典型锂离子筛型吸附剂的吸附机理、制备方法、吸附性能等方面的研究进展，分析比较了各自的优缺点，并指出离子筛型吸附剂目前存在的问题，最后对离子筛型锂吸附剂的改进及应用进行了展望。

关键词: 盐湖卤水, 离子筛, 吸附, 锂

Abstract:

Due to the growing demand and as an important strategic resource, lithium and its compounds play an important role in various fields. Traditional methods of extracting lithium from ore consumed a large amount of energy and the process was complicated. Therefore,it is of great significance to extract lithium from liquid lithium resources,such as brines and seawater. Active exploration of lithium extraction methods has been conducted by researchers,and the lithium ion sieve with its green and efficient advantages draws attention of scholars. It has become one of the most potential methods of extracting lithium from liquid lithium resources. In this paper,lithium ion-sieves were classified;the adsorption mechanism, preparation methods,and adsorption properties of manganese-based,titanium-based and doped lithium ion-sieves were summarized. Their advantages and disadvantages were compared and analyzed. The problems existed in lithium ion-sieves at present was pointed out. Finally,the improvement and prospect were suggested.

Key words: brine, ion-sieve, absorption, lithium

中图分类号:

TQ131.11

柏春, 郭敏, 张慧芳, 吴志坚, 李权. 离子筛型锂吸附剂吸附法从盐湖卤水/海水中提锂的研究进展[J]. 化工进展, 2017, 36(03): 802-809.

BAI Chun, GUO Min, ZHANG Huifang, WU Zhijian, LI Quan. The research progress of extracting lithium from brine by lithium ion sieve[J]. Chemical Industry and Engineering Progress, 2017, 36(03): 802-809.

参考文献

[1] 高峰,郑绵平,乜贞,等. 盐湖卤水锂资源及其开发进展[J]. 地球学报,2011,32(4):483-492. GAO F,ZHEN M P,YE Z,et al. Brine lithium resource in the salt lake and advances in its exploitation[J]. Acta Geoscientica Sinica, 2011,32(4):483-492.
[2] 雪晶,胡山鹰. 我国锂工业现状及前景分析[J]. 化工进展,2011, 30(4):782-787,801. XUE J,HU S Y. Review on lithium industry in China[J]. Chemical Industry and Engineering Progress,2011,30(4):782-787,801.
[3] 任世中,曾英,李陇岗,等. 盐湖卤水提锂方法研究进展[J]. 广州化工,2013,41(1):35-37,50. REN S Z,ZENG Y,LI L G,et al. Development progress on the extraction of lithium from salt lake brines[J]. Guangzhou Chemical Industry,2013,41(1):35-37,50.
[4] 李权,庞全世,高洁. 金属锂生产工艺优化[J]. 盐湖研究,2009, 17(1):63-67. LI Q,PANG Q S,GAO J. Optimization of production process of lithium[J]. Journal of Salt Lake Research,2009,17(1):63-67.
[5] 陈婷,康自华. 我国锂资源及其开发技术进展[J]. 广东微量元素科学,2007,14(3):6-8. CHEN T,KANG Z H. Lithium resources status and its progress of development technology in China[J]. Guangdong Trace Elements Science,2007,14(3):6-8.
[6] 余疆江,郑绵平,伍倩. 富锂盐湖提锂工艺研究进展[J]. 化工进展,2013,32(1):13-21. YU J J,ZHEN M P,WU Q. Research progress of lithium extraction process in lithium-containing salt lake[J]. Chemical Industry and Engineering Progress,2013,32(1):13-21.
[7] 周燕芳,钟辉. 尖晶石LiMn₂O₄正极材料的研究进展[J]. 化工进展,2003,22(2):140-145. ZHOU Y F,ZHONG H. Research progress of spinel LiMn₂O₄ cathode materials[J]. Chemical Industry and Engineering Progress, 2003,22(2):140-145.
[8] 余疆江,郑绵平,唐力君,等. 碳酸盐型卤水实验室模拟提锂和太阳池提锂的对比[J]. 化工进展,2013,32(6):1248-1252,1260. YU J J,ZHEN M P,TANG L J,et al. Comparative study of lithium extraction from the carbonate brine between solar pond and laboratory simulation experiment[J]. Chemical Industry and Engineering Progress, 2013,32(6):1248-1252,1260.
[9] 刘卓,周云峰,柴登鹏,等. 从盐湖卤水中提取锂的技术研究进展与展望[J]. 材料导报,2015,29(26):133-137. LIU Z,ZHOU Y F,CHAI D P,et al. Progress and prospects of lithium extraction technology from salt lake brine[J]. Materials Review,2015,29(26):133-137.
[10] 刘元会,邓天龙. 国内外从盐湖卤水中提锂工艺技术研究进展[J]. 世界科技研究与开发,2006,28(5):69-75. LIU Y H,DENG T L. Progresses on the process and technique of lithium recovery from salt lake brines around the world[J]. World Sci-Tech R&D,2006,28(5):69-75.
[11] 杨建元,夏康明. 一种生产高纯镁盐、碳酸锂、盐酸和氯化铵的方法:1724373[P]. 2006-01-25. YANG J Y,XIA K M. A method for producing high purity magnesium,lithium carbonate,ammonium chloride and hydrochloric acid:1724373[P]. 2006-01-25.
[12] 郑绵平,郭珍旭,张永生,等. 从碳酸锂盐型卤水中提取锂盐的方法:1270927[P]. 2000-10-25. ZHEN M P,GUO Z X,ZHANG Y S,et al. The method of extracting lithium from brine with lithium carbonate:1270927[P]. 2000-10-25.
[13] 肖小玲,戴志锋,祝增虎,等. 吸附法盐湖卤水提锂的研究进展[J]. 盐湖研究,2005,13(2):66-69. XIAO X L,DAI Z F,ZHU Z F,et al. Progress of adsorption methods on the extraction of lithium from the salt lake brine[J]. Journal of Salt Lake Research,2005,13(2):66-69.
[14] 董茜,朴香兰,朱慎林. 从盐湖卤水中提取锂的吸附技术及研究进展[J]. 盐业与化工,2007,36(3):31-34. DONG Q,PU X L,ZHU S L. Adsorption techniques and progress on the extraction of lithium from salt lake brines[J]. Journal of Salt and Chemical Industry,2007,36(3):31-34.
[15] 杨兆娟,向兰. 从盐湖卤水中提锂的研究进展[J]. 海湖盐与化工, 2005,34(6):27-29. YANG Z J,XIANG L. Progress on the extraction of lithium from the salt lake brine[J]. Sea-Lake Salt and Chemical Industry,2005,34(6):27-29.
[16] 王卫东,曹茜. 国内盐湖卤水提取碳酸锂生产工艺及现状[J]. 盐湖研究,2010,18(4):52-61. WANG W D,CAO Q. Process and status of extracting lithium carbonate from brine in China[J]. Journal of Salt Lake Research, 2010,18(4):52-61.
[17] 贾旭宏,李丽娟,曾忠明,等. 盐湖锂资源分离提取方法研究进展[J]. 广州化工,2010,38(10):10-13. JIA X H, LI L J, ZENG Z M, et al. Progress of the method-development of separating and extracting lithium from brine lakes[J]. Guangzhou Chemical Industry,2010,38(10):10-13.
[18] KENTA O,MIYAI Y,KATOH S. Lithium-ion insertion/extraction reaction with λ-MnO₂ in the aqueous phase[J]. Chemistry Letters, 1988,6:989-992.
[19] MOLENDAA M,DZIEMBAJ R,MAJDA D,et al. Synthesis and characterisation of sulphided lithium manganese spinels LiMn₂O_4-yS_y prepared by sol-gel method[J]. Solid State Ionics,2005,176(19-22):1705-1709.
[20] CHITRAKAR R,KANOH H,MIYAI Y. A new type of manganese oxide(MnO₂·0.5H₂O)derived from li_1.6Mn_1.6O₄ and its lithium ion-sieve properties[J]. Chem. Mate,2000,12(10):3151-3157.
[21] 雷家珩,杨顺林,郭丽萍,等. 水热法制备尖晶石型锂锰氧化物锂离子筛分材料:1702043[P]. 2005-11-30. LEI J Y,YANG S L,GUO L P,et al. Preparation of spinel type lithium-manganese oxide lithium ion sieve material by hydrothermal method:1702043[P]. 2005-11-30.
[22] 董殿权. 锂离子筛的制备及离子交换性能[D]. 天津:天津大学, 2006. DONG D Q. Preparation and ion-exchange of lithium ion-sieve[D]. Tianjing:Tianjin University,2006.
[23] MIYAI Y,UMENO A,CHITORAKAA R,et al. Method for producing porous granular lithium adsorbent:JP2002282684[P]. 2002-10-02.
[24] 纪志永,许长春,袁俊生,等. 尖晶石型锰离子筛研究进展[J]. 化工进展,2005,24(12):1336-1340. JI Z Y,XU C C,YUAN J S,et al. Progress of study on spinel lithium ion-sieve[J]. Chemical Industry and Engineering Progress,2005,24(12):1336-1340.
[25] 竺柏康,王东光,任益枰,等. 新型磁性纳米锂离子筛的合成[J]. 化工学报,2011,62(7):2067-2074. ZHU B K,WANG D G,REN Y P,et al. Synthesis of a new-style nano magnetic lithium ion sieves[J]. CIESC Journal,2011,62(7):2067-2074.
[26] 申辉,钟辉,黄溢民. 离子筛型锂吸附剂的研究现状[J]. 四川化工, 2012,15(3):19-22. SHEN H,ZHONG H,HUANG Y M. Research status of lithium ion sieve adsorbent[J]. Sichuan Chemical Industry,2012,15(3):19-22.
[27] 陈白珍,马立文,石西昌,等. 锂离子筛前驱体制备方法的研究进展[J]. 无机盐工业,2009,41(7):1-4. CHEN B Z,MA L W,SHI X C,et al. Research progress on preparation methods for precursors of lithium ion-sieve[J]. Inorganic Chemicals Industry,2009,41(7):1-4.
[28] 汤卫平. 尖晶石锰酸锂在水溶液中的锂嵌/脱机理和应用[C]//第16届全国固态离子学学术会议暨下一代能源材料与技术国际研讨会论文摘要集. 成都:中国硅酸盐学会固态离子学分会,2012:A18. TANG W P. Lithiation/deintercalation reactions of spinel lithium manganese oxides in aqueous and its applications[C]//The Abstracts of the 16th National Academic Conference about Solid-State Ionics and Next Generation Technology Energy Materials International Symposium,Chengdu:CSSI,2012:A18.
[29] 徐占武,岳德宇,张蕾,等. 锂离子筛吸附剂及成型的研究进展[J]. 无机盐工业,2014,46(6):12-16. XU Z W,YUE D Y,ZHANG L,et al. Research progress of preparation and formation of lithium ion sieve[J]. Inorganic Chemicals Industry, 2014,46(6):12-16.
[30] 李少鹏,张钦辉,孙淑英,等. TiO₂离子筛的制备及表征[J]. 天津大学学报,2007,40(4):453-456. LI S P,ZHANG Q H,SUN S Y,et al. Preparation and characterization of titania ion-sieves[J]. Journal of Tianjin University,2007,40(4):453-456.
[31] 杨珊珊,阮慧敏,沈江南,等. 尖晶石型锂锰氧化物离子筛的制备方法及构效性能分析[J]. 化工进展,2015,34(6):1690-1698, 1736. YANG S S,RUAN H M,SHEN J N,et al. Preparation methods and analyses of structural performance of spinel-type lithium manganese oxide ion sieves[J]. Chemical Industry and Engineering Progress, 2015,34(6):1690-1698,1736.
[32] 李超,肖伽励,孙淑英,等. 球形离子筛吸附剂的制备及其锂吸附性能评价[J]. 化工学报,2014,65(1):220-226. LI C,XIAO J L,SUN S Y,et al. Preparation and lithium adsorption evaluation for spherical ion-sieve granulated by agarose[J]. CIESC Journal,2014,65(1):220-226.
[33] 尹世豪. 锰系锂离子筛钛掺杂改性工艺及其性能研究[D]. 长沙:中南大学,2014. YI S H. Research on the process and properties of titanium doped manganate lithium ion-sieve[D]. Changsha:Central South University, 2014.
[34] HUNTER J C. Preparation of a new crystal form of manganese dioxide:λ-MnO₂[J]. Journal of Solid State Chemistry,1981,39(2):142-147.
[35] CLEARFIELD A. Inorganic ion exchange,past,present,future[J]. Solvent Extraction and Ion Exchange,2000,18(4):656-678.
[36] SATO K,POOJARY D,CLEARFIELD A. The surface structure of the proton-exchanged lithium manganese oxide spinels and their lithium-ion sieve properties[J]. Journal of solid State Chemistry, 1997,131(1):84-93.
[37] FENG Q,MIYAI Y,KANOH H,et al. Li⁺ extraction/insertion with spinel-type lithium manganese oxides characterization of redox-type and ion-exchange-type sites[J]. Langmuir,1992,8(7):1861-1867.
[38] 马立文. 锂锰氧化物及其锂离子筛的制备、性能及应用[D]. 长沙:中南大学,2011. MA L W. Preparation, properties and applications of lithium manganese oxides and their lithium ion-sieve[D]. Changsha:Central South University,2011.
[39] 张绍成,董丽春,戈桦,等. 负载二氧化锰球形吸附剂的制备及锂吸附性质的研究[J]. 离子交换与吸附,1993,9(1):54-58. ZHANG S C,DONG L C,GE H,et al. Preparation of load spherical manganese dioxide adsorbent and properties of lithium adsorption[J]. Ion Exchange and Adsorption,1993,9(1):54-58.
[40] 王禄,马伟,韩梅,等. 高效锂离子筛吸附剂MnO₂·0.5H₂O的软化学合成及吸附性能研究[J]. 化学学报,2007,65(12):1135-1139. WANG L,MA W,HAN M,et al. Soft chemical synthesis and adsorption properties of MnO₂·0.5H₂O,a high performance ion sieve for lithium[J]. Acta Chimica Sinica,2007,65(12):1135-1139.
[41] 孙淑英,张钦辉,于建国. 低维纳米立方相Li₄Mn₅O₁₂的制备及锂吸附性能[J]. 无机化学学报,2010,25(6):626-630. SUN S Y,ZHANG Q H,YU J G. Preparation and lithium adsorption properties of low-dimensional cubic Li₄Mn₅O₁₂ nanostructure[J]. Journal of Inorganic Materials,2010,25(6):626-630.
[42] 石西昌,余亮良,陈白珍,等. 尖晶石型锂离子筛的制备及其吸附性能[J]. 中南大学学报(自然科学版),2011,42(8):2198-2203. SHI X C,YU L L,CHEN B Z,et al. Preparation and adsorption property of spinel-type lithium ion-sieve[J]. Journal of Central South University(Science and Technology),2011,42(8):2198-2203.
[43] 石西昌,张志兵,周定方,等. Li_1.6Mn_1.6O₄酸洗后离子筛在盐湖卤水中的吸附性能[J]. 中南大学学报(自然科学版),2013,44(3):892-900. SHI X C,ZHANG Z B,ZHOU D F,et al. Adsorption performance of ion-sieve obtained after Li_1.6Mn_1.6O₄ pickled in brine[J]. Journal of Central South University(Science and Technology),2013,44(3):892-900.
[44] 解利昕,陈小棉. Li_1.6Mn_1.6O₄/PVDF多孔膜的制备及提锂性能[J]. 化工学报,2014,65(1):237-243. XIE L X,CHEN X M. Preparation of Li_1.6Mn_1.6O₄/PVDF membrane and its lithium uptaking[J]. CIESC Journal,2014,65(1):237-243.
[45] 大井健太,蒋修治. 海水中稀有金属的提取[J]. 国外稀有金属, 1992,2:21-26. KENTA O,JIANG X Z. Extraction of rare metals in seawater[J]. Foreign Rare Metals,1992,2:21-26.
[46] KENTA O,MIYAI Y,KATOH S. Recovery of lithium from seawater by manganese oxide adsorbent[J]. Separation Science and Technology,1986,21(8):755-766.
[47] HONG H,PARK I,RYU T. Granulation of Li_1.33Mn_1.67O₄(LMO) through the use of cross-linked chitosan for the effective recovery of Li+ from seawater[J]. Chemical Engineering Journal,2013,234:16-22.
[48] ZANDEVAKILI S, RANJBAR M, EHTESHAMZADEH M. Recovery of lithium from Urmia Lake by a nanostructure MnO₂ ion sieve[J]. Hydrometallurgy,2014,149:148-152.
[49] KIM S,LEE J,KANG J S. Lithium recovery from brine using a k-MnO₂/activated carbon hybrid supercapacitor system[J]. Chemosphere,2015,125:50-56.
[50] KAUWAZU K,YASUDA S. 分离科学及其在稀有全属的应用(译文集)[J]. 稀有金属与硬质合金1989(s1):19. KAUWAZU K,YASUDA S. Separation science and its application in rare metals(translated collections)[J]. Rare Metals and Cemented Carbides,1989(s1):19.
[51] 闫树旺,钟辉,周永兴. 二氧化钛吸附剂的研制及从卤水中提锂[J]. 离子交换与吸附,1992,8(3):222-225. YAN S W,ZHONG H,ZHOU Y X. Preparation of titanium dioxide adsorbent and lithium extraction from brine[J]. Ion Exchangeand Adsorption,1992,8(3):222-225.
[52] 钟辉. 偏钛酸型锂交换体制备机理及其从液态锂矿提锂研究[D]. 成都:成都理工大学,2004. ZHONG H. Research on the preparation and mechanism of the H₂TiO₃-type lithium exchanger and its application to the extraction of Li+ from the brine[D]. Chengdu:Chengdu University of Technology, 2004.
[53] 董殿权,张凤宝,张国亮,等. Li₄Ti₅O_l2的合成及对Li+的离子交换动力学[J]. 物理化学学报,2007,23(6):950-954. DONG D Q,ZHANG F B,ZHANG G L,et al. Synthesis of Li₄Ti₅O_l2 and its exchange kinetics with Li+[J]. Acta Physico-Chimica Sinica, 2007,23(6):950-954.
[54] 张丽芬. 偏钛酸型锂吸附剂的制备及性能研究[D]. 长沙:中南大学,2010. ZHANG L F. Research on the preparation and mechanism of the H2Ti03-type lithium absorbent[D]. Changsha:Central South University,2010.
[55] 张丽芬,陈白珍,石西昌,等. 偏钛酸型锂吸附剂的合成及吸附性能[J]. 中国有色金属学报,2010,20(9):1850-1854. ZHANG L F,CHEN B Z,SHI X C,et al. Synthesis and adsorption
[56] 董殿权,张凤宝,张国亮,等. LiAlTiO₄的合成及对Li+的离子交换选择性[J]. 应用化学,2005,22(7):754-758. DONG D Q,ZHANG F B,ZHANG G L,et al. Synthesis of LiAlTiO₄ and its ion-exchange thermodynamics for Li+[J]. Chinese Journal of Applied Chemistry,2005,22(7):754-758.
[57] 董殿权,刘维娜,刘亦凡. LiNi_0.05Mn_1.95O₄的合成及其对Li+的离子交换热力学[J]. 物理化学学报,2009,25(7):1279-1284. DONG D Q,LIU W N,LIU Y F. Synthesis of LiNi_0.05Mn_1.95O₄ and its ion-exchange thermodynamics for Li⁺[J]. Acta Physico-Chimica Sinica,2009,25(7):1279-1284.
[58] THIRUNAKARAN R,SIVASHANMUGAM A,GOPUKUMAR S. Electrochemical behaviour of nano-sized spinel LiMn₂O₄ and LiAl_xMn_2xO₄(x=Al:0.00-0.40)synthesized via fumaric acid-assisted sol-gel synthesis for use in lithium rechargeable batteries[J]. Journal of Physics and Chemistry of Solids,2008,69(8):2082-2090.
[59] SON J T,KIM H G. New investigation of fluorine-substituted spinelLiMn₂O_4-xF_x by using sol-gel process[J]. Journal of Power Sources,2005,147(1-2):220-226.
[60] KANG Y J,KIM J H,SUN Y K. Structural and electrochemical study of Li-Al-Mn-O-F spinel material for lithium secondary batteries[J]. Journal of Power Sources,2005,146(1-2):237-240.
[61] SUN Y K,BOOKEUN,LEE H J. Synthesis and electrochemical characterization of oxysulfide spinel LiAl_0.15Mn_1.85O_3.97S_0.03 cathode materials for rechargeable batteries[J]. Electrochimica Acta,2000, 46(4):541-546.
[62] 陈猛,杨闯,肖斌. 尖晶石型LiNi_0.1Mn_1.9O₄材料的合成及性能研究[J]. 化学工程师,2006,125(2):11-13. CHEN M,YANG C,XIAO B. Synthesis and investigation of the property of spinel LiNi_0.1Mn_1.9O₄[J]. Chemical Engineer,2006,125(2):11-13.
[63] NI J,ZHOU H,CHEN J. Improved electrochemical performance of layered LiNi_0.4Co_0.2Mn_0.4O₂ via Li₂ZrO₃ coating[J]. Electrochimica Acta,2008,53(7):3075-3083.
[64] NITHYA C, THIRUNAKARAN R, SIVASHANMUGAM A. Correction to high performing LiMg_xCu_yCo_1-x-yO₂ cathode materialfor lithium rechargeable batteries[J]. ACS Appl. Mater. Interfaces,2012, 4(8):4040-4046.
[65] KAN W,HUQ A,MANTHIRAM A,et al. Exploration of a metastable normal spinel phase diagram for the quaternary Li-Ni-Mn-C-O system[J]. Chem. Mater.,2016,28(6):1832-1837.
[66] HE H,ZAN L,ZHANG Y. Effects of amorphous V₂O₅ coating on the electrochemical properties of Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ as cathode material for Li-ion batteries[J]. Journal of Alloys and Compounds, 2016,680:95-104. property of H₂TiO₃ type adsorbent[J]. The Chinese Journal of Nonferrous Metals,2010,20(9):1850-1854.