针对粉末状锂铝水滑石(LiAl-LDH)水洗脱附锂时,结构不稳定、易流失的问题,采用共沉淀和一步热聚合法制备了铁掺杂锂铝水滑石/石墨烯/海藻酸钠复合水凝胶材料(LiAlFe-LDH/GBs),采用各种物理化学方法表征了材料的形貌、组成和吸附性能。结果表明:LiAlFe-LDH/GBs对Li+具有良好的选择性吸附性能,吸附过程符合准二阶动力学模型和Langmuir等温吸附模型。在pH=7.0,45℃下,吸附12h,最大理论吸附容量为8.674mg/g;在Na+、K+、Ca2+、Mg2+存在下,对Li+具有较强的选择性,且循环5次后吸附量依然可达到5.5mg/g,具有良好的循环稳定性。
The iron-doped lithium aluminum layered double hydroxide/graphene/sodium alginate composite hydrogel material (LiAlFe-LDH/GBs) was prepared by coprecipitation and one-step thermal polymerization to deal with the problems of easy loss and long desorbing time when the powder LiAl-LDH was desorbed by water.The morphology,composition and adsorption properties of the materials were characterized by various physical and chemical technologies.The results shown that LiAlFe-LDH/GBs had good selective adsorption performance for Li+.The adsorption process conformed to the pseudo-second order kinetic model and Langmuir isotherm adsorption model.The maximum theoretical adsorption capacity was 8.674mg/g at pH 7.0 and 45℃ for 12h.LiAlFe-LDH/GBs had strong selectivity to Li+ in the presence of Na+,K+,Ca2+,and Mg2+.The adsorption capacity of LiAlFe-LDH/GBs can still reach 5.5mg/g after five cycles,which had good cycle stability.
[1] Liu X H,Zhong M L,Chen X Y,et al.Separating lithium and magnesium in brine by aluminum-based materials[J].Hydrometallurgy,2018,176:73-77.
[2] Kotsupalo N P,Ryabtsev A D,Poroshina I A,et al.Effect of structure on the sorption properties of chlorine-containing form of double aluminum lithium hydroxide[J].Russian Journal of Applied Chemistry,2013,86(4):482-487.
[3] 陈程,李亦然,孙占学,等.磁性铝盐吸附剂的制备及高镁锂比盐湖卤水中提锂性能研究[J].有色金属:冶炼部分,2018(1):29-33.
[4] Kotsupalo N P,Ryabtsev A D,Poroshina I A,et al.Effect of structure on the sorption properties of chlorine-containing form of double aluminum lithium hydroxide[J].Russian Journal of Applied Chemistry,2013,86(4):482-487.
[5] Zhong J,Lin S,Yu J G,et al.Lithium recovery from ultrahigh Mg2+/Li+ ratio brine using a novel granulated Li/Al-LDHs adsorbent[J].Separation and Purification Technology,2021,256:117780.
[6] Ma L W,Chen B Z,Chen Y,et al.Preparation,characterization and adsorptive properties of foam-type lithium adsorbent[J].Microporous & Mesoporous Materials,2011,142(1):147-153.
[7] Chung K S,Lee J C,Kim W K,et al.Inorganic adsorbent containing polymeric membrane reservoir for the recovery of lithium from seawater[J].Journal of Membrane Science,2008,325(2):503-508.
[8] Muris K,Tyler M D.Removable colored coatings based on calcium alginate hydrogels[J].Biomacromolecules,2006,7:2357-2361.
[9] 单凤君,张婷婷,王双红.氧化石墨烯/海藻酸钠复合材料对Ni2+的吸附特性研究[J].化工新型材料,2020,48(10):212-216.
[10] 刘浩怀,何芝洲,刘鹏,等.氧化石墨烯/羧甲基纤维素钠/海藻酸钠复合材料的制备与性能研究[J].化工新型材料,2017,45(1):109-111.
[11] Marcano D C,Kosynkin D V,Berlin J M,et al.Improved synthesis of graphene oxide[J].ACS Nano,2010,4(8):4806-4814.
[12] Wu L L,Evans S F,Cheng Y Q,et al.Neutron spectroscopic and thermochemical characterization of lithium-aluminum-layered double hydroxide chloride:implications for lithium recovery[J].The Journal of Physical Chemistry C,2019,123(34):20723-20729.
[13] Sun Y R,Zhou T,Li W Y,et al.Amino-functionalized alginate/graphene double-network hydrogel beads for emerging contaminant removal from aqueous solution[J].Chemosphere,2020,241:125-110.
[14] Jin T,Christopher D E,Tang Y C,et al.Nitrogen-doped graphene oxide monoliths crosslinked by short chain aliphatic amines[J].Journal of Hazardous Materials,2018,357:100-108.
[15] Zhang F R,Hou W G.Mechano-hydrothermal preparation of Li-Al-OH layered double hydroxides[J].Solid State Sciences,2018,79:93-98.
[16] Wu L L,Li L,Samuel F E,et al.Lithium aluminum-layered double hydroxide chlorides(LDH):formation enthalpies and energetics for lithium ion capture[J].Journal of the American Ceramic Society,2019,102:2398-2404.
[17] Li J H,Li J Y,Meng H,et al.Ultra-light,compressible and fire-resistant graphene aerogel as a highly efficient and recyclable absorbent for organic liquids[J].Journal of Materials Chemistry A,2014,2:2934-2941.
[18] Jiang H X,Yang Y,Sun S Y,et al.Adsorption of lithium ions on lithium-aluminum hydroxides:equilibrium and kinetics[J].The Canadian Journal of Chemical Engineering,2020,98(2):544.
[19] Hong H J,Park I S,Ryu J,et al.Immobilization of hydrogen manganese oxide (HMO) on alpha-alumina bead (AAB) to effective recovery of Li+ from seawater[J].Chemical Engineering Journal,2015,271:71-78.
[20] 于潇,孙淑英,于建国.层状吸附剂提锂过程研究[J].无机盐工业,2017,49(12):23-26.
[21] Chowdhury S,Rahul M,Papita S,et al.Adsorption thermodynamics,kinetics and isosteric heat of adsorption of malachite green onto chemically modified rice husk[J].Desalination,2011,265:159-168.
[22] 许惠,宋应华,张杰.H2TiO3的制备及锂吸附性能研究[J].化工新型材料,2019,47(10):163-166.
[23] 董茜,李燕杰,朴香兰,等.铝盐吸附剂从盐湖卤水中吸附锂的研究[J].稀有金属,2007,31(3):357-361.
[24] Fan J C,Shi Z X,Lian M,et al.Mechanically strong graphene oxide/sodium alginate/polyacrylamide nanocomposite hydrogel with improved dye adsorption capacity[J].Journal of Materials Chemistry A,2013,1(25):7433-7443.
基金资助
科技部“科技助力经济2020”重点专项(SQ2020YFF0412719);安徽省科技攻关计划项目(JZ2018AKKG0332)
PDF
