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聚氯乙烯锂离子筛膜的制备及其在卤水中的锂吸附性能

王蕾 王磊

王蕾, 王磊. 聚氯乙烯锂离子筛膜的制备及其在卤水中的锂吸附性能[J]. 复合材料学报, 2023, 40(9): 5107-5123. doi: 10.13801/j.cnki.fhclxb.20221124.002
引用本文: 王蕾, 王磊. 聚氯乙烯锂离子筛膜的制备及其在卤水中的锂吸附性能[J]. 复合材料学报, 2023, 40(9): 5107-5123. doi: 10.13801/j.cnki.fhclxb.20221124.002
WANG Lei, WANG Lei. Preparation of polyvinyl chloride lithium ion sieve membrane and its lithium adsorption properties in brine[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5107-5123. doi: 10.13801/j.cnki.fhclxb.20221124.002
Citation: WANG Lei, WANG Lei. Preparation of polyvinyl chloride lithium ion sieve membrane and its lithium adsorption properties in brine[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5107-5123. doi: 10.13801/j.cnki.fhclxb.20221124.002

聚氯乙烯锂离子筛膜的制备及其在卤水中的锂吸附性能

doi: 10.13801/j.cnki.fhclxb.20221124.002
基金项目: 陕西省自然科学基础研究专项基金(2019 JM-596);陕西省技术创新引导计划基金(S2019-YD-CGXNX-0049);陕西省科技成果转移与推广计划(2018 SJRG-X-02)
详细信息
    通讯作者:

    王磊,博士,教授,博士生导师,研究方向为膜分离技术 E-mail: wl0178@126.com

  • 中图分类号: TQ131.11;TQ028.8;TB331

Preparation of polyvinyl chloride lithium ion sieve membrane and its lithium adsorption properties in brine

Funds: Project Supported by Natural Science Basic Research Plan in Shaanxi Province of China (2019 JM-596); Technology Innovation Leading Program of Shaanxi (S2019-YD-CGXNX-0049); Guidance Fund for Transformation of Scientific and Technological Achievements (2018 SJRG-X-02)
  • 摘要: 锂离子筛的成型技术对于其在卤水中的工业化生产应用具有重要意义。以聚氯乙烯(PVC)为成膜材料,聚甲基丙烯酸甲酯(PMMA)和聚乙烯吡咯烷酮(PVPk30)为改性剂,制备了负载Li1.6Mn1.6O4的PVC锂离子筛前驱体膜,研究了膜经稀盐酸抽锂后得到的PVC锂离子筛膜对锂的吸附性能及循环吸附解吸性能等,并对离子筛膜进行了吸附动力学及吸附等温模型分析。结果表明:PVC浓度为10wt%,PMMA的添加量为6wt%,PVPk30的添加量为2wt%,Li1.6Mn1.6O4含量为20wt%联用时,制得的离子筛膜吸附量为1336.30 mg/m2。经0.1 mol·L−1 HCl溶液解吸,约2 h时解吸达到平衡,锰的溶损率为0.56%左右。在卤水中进行了10次循环吸附解吸过程,吸附量降至1294.16 mg/m2,吸附量仅损失了3%。在含有多种复杂离子如Na+、K+、Mg2+和Ca2+的卤水中,锂离子筛膜对Li+有很高的选择性。说明该PVC锂离子筛膜结构稳定,循环利用性能优异,有利于其工业化应用。PVC锂离子筛膜的吸附过程更符合伪二级动力学方程及Langmuir吸附等温模型,说明该吸附过程的吸附类型为单分子层化学吸附。膜状的离子筛对于从盐湖卤水等液态锂资源中提取锂具有很大的开发潜力。

     

  • 图  1  聚氯乙烯(PVC)浓度对膜拉力和断裂伸长率的影响

    Figure  1.  Effects of polyvinyl chloride (PVC) concentration on tensile force and elongation at break of membranes

    图  2  PVC浓度对锂离子筛膜吸附量的影响

    Figure  2.  Relation between Li+ adsorptive capacity and concentration of PVC

    图  3  不同PVC浓度条件下制备的锂离子筛膜的SEM图像

    Figure  3.  SEM images of PVC lithium ion sieve membranes of different PVC concentration

    图  4  Li1.6Mn1.6O4的添加量对锂离子筛膜吸附量的影响

    Figure  4.  Relation between Li+ adsorptive capacity and the content of Li1.6Mn1.6O4

    图  5  不同Li1.6Mn1.6O4含量的PVC锂离子筛膜的SEM图像

    Figure  5.  SEM images of PVC lithium ion sieve membranes of different Li1.6Mn1.6O4 contents

    图  6  聚甲基丙烯酸甲酯(PMMA)添加量对PVC锂离子筛膜吸附性能的影响

    Figure  6.  Relation between Li+ adsorptive capacity and the content of polymethyl methacrylate (PMMA)

    图  7  PMMA含量对膜拉力和断裂伸长率的影响

    Figure  7.  Tensile force and elongation at break of membranes with different PMMA contents

    图  8  不同PMMA添加量的PVC锂离子筛膜接触角θ测试

    Figure  8.  Contact angle θ measurement of PVC lithium ion sieve membranes with different PMMA contents

    图  9  不同PMMA含量的PVC锂离子筛膜的SEM图像

    Figure  9.  SEM images of PVC lithium ion sieve membranes of different PMMA contents

    图  10  聚乙烯吡咯烷酮(PVPk30)添加量对 PVC 锂离子筛膜吸附性能的影响

    Figure  10.  Relation between Li+ adsorptive capacity and the content of polyvinylpyrrolidone (PVPk30)

    图  11  PVPk30含量对膜拉力和断裂伸长率的影响

    Figure  11.  Tensile force and elongation at break of membranes with different PVPk30 contents

    图  12  不同PVPk30含量PVC锂离子筛膜的SEM表面 ((a1)~(d1)) 和断面 ((a2)~(d2)) 图像

    Figure  12.  SEM images of the surface ((a1)-(d1)) and section ((a2)-(d2)) in PVC lithium ion sieve membranes of different PVPk30 contents

    图  13  PVC锂离子筛膜的FTIR图谱

    Figure  13.  FTIR spectra of PVC lithium ion sieve membrane

    图  14  不同Li1.6Mn1.6O4添加量的PVC锂离子筛膜的XRD图谱

    Figure  14.  XRD patterns of PVC lithium ion sieve membrane with different Li1.6Mn1.6O4 contents

    图  15  PVC锂离子筛膜吸附量

    Figure  15.  Adsorption capacity of PVC lithium ion sieve membrane

    图  16  PVC锂离子筛膜锂解吸率及锰溶损率

    Figure  16.  Extraction of Li+ and dissolution loss rate of Mn2+ from PVC lithium ion sieve membrane

    图  17  PVC锂离子筛膜循环过程的锰溶损率及锂吸附量

    Figure  17.  Dissolution loss rate of Mn2+ and lithium adsorption capacity of PVC lithium ion sieve membrane in the cycling process

    图  18  锂离子筛膜吸附锂的动力学曲线

    Figure  18.  Kinetics of Li+ adsorption by PVC lithium ion sieve membrane

    Qt—Li+ adsorption capacity at time t

    图  19  PVC锂离子筛膜的等温吸附拟合曲线

    Figure  19.  Adsorption isotherm of Li+ adsorption by PVC lithium ion sieve membrane

    表  1  青海昆特依盐湖卤水水质成分

    Table  1.   Components of the Qinghai Kunty salt lake brine

    Metal ionLi+Mg2+Ca2+K+Na+Mn2+Cd2+Cr3+Cu2+Fe2+Mg2+/Li+
    Initial concentration/(g·L−1)0.1510.520.0723.635.390.00340.00690.00240.0170
    下载: 导出CSV

    表  2  不同致孔剂聚乙烯吡咯烷酮PVPk30添加量的PVC锂离子筛膜的膜通量参数

    Table  2.   Membrane flux performance of PVC lithium ion sieve membrane with different pore-causing agent polyvinylpyrrolidone PVPk30 contents

    PVPk30 content/wt% Brine flux
    /(L·m2·h−1)
    0 228.06
    1 311.20
    2 488.83
    3 593.78
    4 669.69
    下载: 导出CSV

    表  3  锂离子筛膜从卤水中分离锂离子的性能

    Table  3.   Performance of PVC lithium ion sieve membrane the separation of Li+ from other cations in brine

    CationsC0/(mg·L−1)Ce/(mg·L−1)Q/(mg·m−2)Q/(mmol·m−2)Kd/(L·m−2)$\alpha_{\rm{M}}^{{\rm{L i}}} $CF/(L·m−2)
    Li+ 128.98 89.22 1335.78 192.45 14.972 1.00 10.356
    Mg2+ 10155.32 10054.91 3373.78 138.81 0.335 44.69 0.332
    K+ 3820.16 3804.65 521.14 13.33 0.137 109.28 0.136
    Na+ 4370.87 4336.58 1152.14 50.09 0.266 56.29 0.264
    Ca2+ 72 71
    Notes: C0 and Ce—Initial and equilibrium Li+ concentrations in brine, respectively; Q—Li+ adsorption capacity; Kd—Distribution coefficient; α—Separation factor; CF—Concentration factor; M—Li, Na, K, Mg and Ca.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-09-30
  • 修回日期:  2022-11-06
  • 录用日期:  2022-11-12
  • 网络出版日期:  2022-11-25
  • 刊出日期:  2023-09-15

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