球形锂离子筛的制备及其吸附性能
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摘要
采用了悬浮聚合造粒法,以聚苯乙烯和Li_(1.6)Mn_(1.6)O_4粉体为原料制备球形锂离子筛前驱体,经0.5mol/L的HCl解析脱锂,得到球形锂离子筛。并利用X射线衍射、扫描电子显微镜、原子吸收分光光度计等测试手段对样品的晶体结构、形貌、吸附性能等进行表征。吸附-解析实验结果表明,球形离子筛前驱体在HCl中处理2 h后解析基本完成。球形锂离子筛对Li~+的吸附速率比较快,在含锂溶液中吸附3 h基本达到平衡。升高温度有利于离子筛对Li~+的吸附,在pH 12.57、温度70℃下,离子筛的平衡吸附量为24 mg/g。吸附过程符合Langmuir吸附等温方程和动力学二级模型,是单分子层化学吸附。球形锂离子筛对盐湖卤水中的锂具有良好的吸附和选择性以及良好的循环吸附性能,在卤水中经过10次循环吸附后,吸附量仍有9.2 mg/g,Mn的总溶损率只有1.92%。
A spherical lithium ion sieve precursor was synthesized by suspension polymerization using polystyrene resin and LLi_(1.6)Mn_(1.6)O_4 powder, and converted into a lithium ion sieve by leaching in 0.5 mol/L HCl solution. The crystal structure, morphology and adsorption capacity of the products were investigated by X-ray diffractometry, scanning electron microscopy and atomic absorption spectrophotometry. The desorption process was basically completed at 2 h.The adsorption rate of Li~+ by the spherical lithium ion sieve is fast. The adsorption capacity of the ion sieve reaches to equilibrium value after adsorption for 3 h. Increasing temperature is beneficial to the adsorption of Li~+ on the lithium ion sieve. The equilibrium adsorption capacity of the lithium ion sieve is 24 mg/g at p H 12.57 and 70 ℃. The adsorption process conforms to Langmuir adsorption isotherm equation and pseudo-second-order adsorption kinetics model, which is the monolayer chemical adsorption. After 10 cycles of adsorption in brine, the adsorption capacity is 9.2 mg/g, and the total loss rate of dissolved Mn is only 1.92%.
A spherical lithium ion sieve precursor was synthesized by suspension polymerization using polystyrene resin and LLi_(1.6)Mn_(1.6)O_4 powder, and converted into a lithium ion sieve by leaching in 0.5 mol/L HCl solution. The crystal structure, morphology and adsorption capacity of the products were investigated by X-ray diffractometry, scanning electron microscopy and atomic absorption spectrophotometry. The desorption process was basically completed at 2 h.The adsorption rate of Li~+ by the spherical lithium ion sieve is fast. The adsorption capacity of the ion sieve reaches to equilibrium value after adsorption for 3 h. Increasing temperature is beneficial to the adsorption of Li~+ on the lithium ion sieve. The equilibrium adsorption capacity of the lithium ion sieve is 24 mg/g at p H 12.57 and 70 ℃. The adsorption process conforms to Langmuir adsorption isotherm equation and pseudo-second-order adsorption kinetics model, which is the monolayer chemical adsorption. After 10 cycles of adsorption in brine, the adsorption capacity is 9.2 mg/g, and the total loss rate of dissolved Mn is only 1.92%.
引文
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[19]侯昭升,张浩,纪晨旭,张冬梅,曲文强,孙斌.悬浮聚合法制备热膨胀聚(偏氯乙烯-丙烯腈-苯乙烯)微球及其性能[J].高分子材料科学与工程,2015,31(9):49-52,57.HOU Zhao-sheng,ZHANG Hao,JI Chen-xu,ZHANGDong-mei,QU Wen-qiang,SUN Bin.Preparation and properties of thermal-expandable microspheres with P(VDC-AN-St)shell by suspension polymerization[J].Polymeric Materials Science and Engineering,2015,31(9):49-52,57.
[20]XU Xin,ZHOU You,FAN Mao-hong,LüZi-jian,TANGYang,SUN Yan-zhi,CHEN Yong-mei,WAN Ping-yu.Lithium adsorption performance of a three-dimensional porous H2Ti O3-type lithium ion-sieve in strong alkaline Bayer liquor[J].RSC Advances,2017,7(31):18883-18891
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[24]WANG Lu,MENG Chang-gong,HAN Mei,MA Wei.Lithium uptake in fixed-pH solution by ion sieves[J].Journal of Colloid and Interface Science,2008,325(1):31-40.
[2]GUNTHER M,LARS R,MICHAEL H,MARTIN B.Lithium market researchglobal supply,future demand and price development[J].Energy Storage Materials,2017,6:171-179.
[3]NARINS T P.The battery business:Lithium availability and the growth of the global electric car industry[J].The Extractive Industries and Society,2017,4(2):321-328.
[4]宋彭生,李武,孙柏,乜贞,卜令忠,王云生.盐湖资源开发利用进展[J].无机化学学报,2011,27(5):801-815.SONG Peng-sheng,LI Wu,SUN Bai,NIE Zhen,BULing-zhong,WANG Yun-sheng.Recent development on comprehensive utilization of salt lake resources[J].Chinese Journal of Inorganic Chemistry,2011,27(5):801-815.
[5]刘东帆,孙淑英,于建国.盐湖卤水提锂技术研究与发展[J].化工学报,2018,69(1):141-155.LIU Dong-fan,SUN Shu-ying,YU Jian-guo.Research and development on technique of lithium recovery from salt lake brine[J].Journal of Chemical Industry and Engineering,2018,69(1):141-155.
[6]陈自正,沈卫华,陈立芳,成洪业,漆志文.纳米H2Ti O3锂吸附剂的水热合成及其吸附性能[J].中国有色金属学报,2017,27(3):547-554.CHEN Zi-zheng,SHEN Wei-hua,CHEN Li-fang,CHENGHong-ye,QI Zhi-wen.Hydrothermal synthesis and adsorption properties of nano scale H2Ti O3adsorbent[J].The Chinese Journal of Nonferrous Metals,2017,27(3):547-554.
[7]CHITRAKAR R,KANOH H,MIYAI Y,OOI K.Recovery of lithium from seawater using manganese oxide adsorbent(H1.6Mn1.6O4)derived from Li1.6Mn1.6O4[J].Industrial Engineering Chemical Research,2001,40(9):2054-2058.
[8]SHI Xi-chang,ZHOU Ding-fang,ZHANG Zhi-bing,YULiang-liang,XU Hui,CHEN Bai-zhen,YANG Xi-yun.Synthesis and properties of Li1.6Mn1.6O4 and its adsorption application[J].Hydrometallurgy,2011,110(1/4):99-106.
[9]SOROUR M H,EL-RAFEI A M,HANI H A.Synthesis and characterization of electrospun aluminum doped Li1.6Mn1.6O4spinel[J].Ceramics International,2016,42(4):4911-4917.
[10]石西昌,张志兵,周定方,周喜诚,唐天罡,尹世豪.Li1.6Mn1.6O4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 Xi-chang,ZHANG Zhi-bing,ZHOU Ding-fang,ZHOUXi-cheng,TANG Tian-gang,YIN Shi-hao.Adsorption performance of ion-sieve obtained after Li1.6Mn1.6O4 pickled in brine[J].Journal of Central South University(Science and Technology),2013,44(3):892-900.
[11]XIAO Guo-ping,TONG Ke-feng,ZHOU Long-sheng,XIAO Jia-li,SUN Shu-ying,LI Ping,and YU Jian-guo.Adsorption and desorption behavior of lithium ion in spherical PVC-MnO2 ion sieve[J].Industrialand Engineering Chemistry Research,2012,51(33):10921-10929.
[12]XU Xin,CHEN Yong-mei,WAN Ping-yu,KHALED G,WANG Kai-ying,HE Ting,HERTANTO A,FAN Mao-hong.Extraction of lithium with functionalized lithium ion-sieves[J].Progress in Materials Science,2016,84:276-313.
[13]MIYAI Y,OOI K,NISHIMURA T,KUMAMOTO J.Lithium adsorptive properties of a new selective adsorbent derived from Li1.33Mn1.67O4[J].Bulletin of the Society of Sea Water Science Japan,1994,48:411-415.
[14]ZHU Gui-ru,WANG Pan,QI Peng-fei,GAO Cong-jie.Adsorption and desorption properties of Li+on PVC-H1.6Mn1.6O4 lithium ion-sieve membrane[J].Chemical Engineering Journal,2013,235:340-348.
[15]XIAO Guo-ping,TONG Ke-fen,SUN Shu-ying,YUJian-guo.Preparation of spherical PVC-MnO2 ion-sieve and its lithium adsorption property[J].Chinese Journal of Inorganic Chemistry,2012,28(11):2385-2394.
[16]YOSEP H,KIM H,PARK J.Millimeter-sized spherical ion-sieve foams with hierarchical pore structure for recovery of lithium from seawater[J].Chemical Engineering Journal,2012,210:482-489.
[17]HONG H,PARK I,RYU T,KIM B,CHUNG K.Granulation of Li1.33Mn1.67O4(LMO)through the use of cross-linked chitosan for the effective recovery of Li+from seawater[J].Chemical Engineering Journal,2013,234:16-22.
[18]XIAO Jia-Li,SUN Shu-Ying,SONG Xing-fu,LI Ping,YUJian-guo.Lithium ion recovery from brine using granulated polyacrylamide-Mn O2ion-sieve[J].Chemical Engineering Journal,2015,279(1):659-666.
[19]侯昭升,张浩,纪晨旭,张冬梅,曲文强,孙斌.悬浮聚合法制备热膨胀聚(偏氯乙烯-丙烯腈-苯乙烯)微球及其性能[J].高分子材料科学与工程,2015,31(9):49-52,57.HOU Zhao-sheng,ZHANG Hao,JI Chen-xu,ZHANGDong-mei,QU Wen-qiang,SUN Bin.Preparation and properties of thermal-expandable microspheres with P(VDC-AN-St)shell by suspension polymerization[J].Polymeric Materials Science and Engineering,2015,31(9):49-52,57.
[20]XU Xin,ZHOU You,FAN Mao-hong,LüZi-jian,TANGYang,SUN Yan-zhi,CHEN Yong-mei,WAN Ping-yu.Lithium adsorption performance of a three-dimensional porous H2Ti O3-type lithium ion-sieve in strong alkaline Bayer liquor[J].RSC Advances,2017,7(31):18883-18891
[21]BARKAT M,NIBOU D,CHEGROUCHE S,MELLAH A.Kinetics and thermodynamics studies of chromium(VI)ions adsorption onto activated carbon from aqueous solutions[J].Chemical Engineering and Processing,2009,48(1):38-47.
[22]BENHAMMOU A,YAACOUBI A,NIBOU L,TANOUTI B.Adsorption of metal ions onto Moroccan stevensite:Kinetic and isotherm studies[J].Journal of Colloid and Interface Science,2005,282(2):320-326.
[23]NAIYA T K,BHATTACHARYA A K,DAS S K.Removal of Cd(II)from aqueous solutions using clarified sludge[J].Colloid and Interface Science,2008,325(1):48-56.
[24]WANG Lu,MENG Chang-gong,HAN Mei,MA Wei.Lithium uptake in fixed-pH solution by ion sieves[J].Journal of Colloid and Interface Science,2008,325(1):31-40.