纳滤膜对高镁锂比盐湖卤水镁锂分离性能研究

doi:10.11949/0438-1157.20201594

化工学报 ›› 2021, Vol. 72 ›› Issue (6): 3130-3139.DOI: 10.11949/0438-1157.20201594

• 青海盐湖资源综合利用专栏 • 上一篇下一篇

纳滤膜对高镁锂比盐湖卤水镁锂分离性能研究

李燕^1,^2,³(),王敏^1,²(),赵有璟^1,²,王怀有^1,²,杨红军^1,²,祝增虎^1,²

^1.中国科学院青海盐湖研究所，中国科学院盐湖资源综合高效利用重点实验室，青海西宁 810008
^2.青海省盐湖资源化学重点实验室，青海西宁 810008
^3.中国科学院大学，北京 101408

收稿日期:2020-11-03 修回日期:2020-12-18 出版日期:2021-06-05 发布日期:2021-06-05
通讯作者: 王敏
作者简介:李燕(1992—)，女，博士研究生，liyan615@mails.ucas.edu.cn
基金资助:
青海省重大科技专项(2019-GX-A7);国家重点研发计划项目(2018YFC0604804)

Study on separation of magnesium and lithium from salt lake brine with high magnesium-to-lithium mass ratio by nanofiltration membrane

LI Yan^1,^2,³(),WANG Min^1,²(),ZHAO Youjing^1,²,WANG Huaiyou^1,²,YANG Hongjun^1,²,ZHU Zenghu^1,²

^1.Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, Qinghai, China
^2.Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province, Xining 810008, Qinghai, China
^3.University of Chinese Academy of Sciences, Beijing 101408, China

Received:2020-11-03 Revised:2020-12-18 Online:2021-06-05 Published:2021-06-05
Contact: WANG Min

摘要/Abstract

摘要：

纳滤作为一种新兴的膜分离技术，在高镁锂比盐湖卤水镁、锂分离领域具有非常好的应用前景。研究了不同镁锂比、原料液循环流量对镁锂分离过程的影响，并对膜分离过程中的分离机理进行分析。结果表明原料液镁锂比对膜通量影响较小，镁、锂离子截留率及镁锂分离效果均随原料液镁锂比的增加而降低。当原料液循环流量为225 L/h时，镁离子截留率为95%，锂离子截留率为-66%，透过液镁锂比降低至1.2。膜分离传质机理研究表明，镁离子在分离过程中受到较强的介电排斥效应与尺寸筛分效应。纳滤技术能够有效降低高镁锂比盐湖卤水的镁锂比，为后续高纯锂盐的制备提供基础。

关键词: 膜, 纳滤, 盐湖卤水, 分离, 镁锂比, 循环流量

Abstract:

As an emerging membrane separation technology, nanofiltration has a potential application in separating magnesium and lithium from salt lake brine with a high magnesium-to-lithium mass ratio (Mg/Li). The separation of magnesium and lithium at different Mg/Li and cross-flow rates was evaluated and analysis on the mechanism in separation process was performed. The results showed that the membrane flux remained almost constant at different Mg/Li, the retention rates of magnesium and lithium and the separation efficiency decreased with increasing Mg/Li. When the cross-flow rate was 225 L/h, the retention rates of magnesium and lithium were 95% and -66%, respectively. In addition the Mg/Li in the permeate was reduced to 1.2. Study on the mechanism of mass transport for membrane process showed that magnesium was greatly influenced by dielectric exclusion, and steric hindrance. Nanofiltration shows considerable promise as a means to separate magnesium and lithium from salt lake brine with high magnesium-to-lithium mass ratios, which provides the basis for the subsequent preparation of high-purity lithium salt.

Key words: membrane, nanofiltration, salt lake brine, separation, Mg/Li, cross-flow rate

中图分类号:

O 611.65

李燕, 王敏, 赵有璟, 王怀有, 杨红军, 祝增虎. 纳滤膜对高镁锂比盐湖卤水镁锂分离性能研究[J]. 化工学报, 2021, 72(6): 3130-3139.

LI Yan, WANG Min, ZHAO Youjing, WANG Huaiyou, YANG Hongjun, ZHU Zenghu. Study on separation of magnesium and lithium from salt lake brine with high magnesium-to-lithium mass ratio by nanofiltration membrane[J]. CIESC Journal, 2021, 72(6): 3130-3139.

图/表 15

表1 溶质的水合半径和扩散系数

Table 1 Hydrated radius and diffusion coefficient of solutes

离子	水合半径/nm	扩散系数/(m²/S)
Mg²⁺	0.428	0.72×10⁴
Li⁺	0.382	1.03×10⁴
Cl^-	0.332	2.03×10⁴

图1 卷式纳滤膜分离装置1—循环罐；2—管道过滤器；3—柱塞隔膜泵；4—变频器；5—透过液；6—卷式膜组件；7—调压阀；8—浓缩液流量计；9—溢流液；10—浓缩液；11—原料液；12—冷却水；13—加热水

Fig.1 Schematic diagram of the spiral-wound membrane apparatus

表2 DK纳滤膜主要操作参数

Table 2 Main operating parameters of DK nanofiltration membrane

膜元件	最高操作压力/MPa	pH操作范围	工作温度/ K
DK-1812	3.5	2~11	283~323

图2 纳滤膜表面微观形貌

Fig.2 Surface morphology of nanofiltration membrane

图3 DK纳滤膜接触角图像

Fig.3 Contact angle image of DK nanofiltration membrane

表3 不同溶液条件下DK纳滤膜表面荷电性

Table 3 The surface electric charge of DK nanofiltration membrane in different solutions

膜	溶液环境	zeta电位/mV
DK新膜	1 mol/L KCl	-0.013
运行一年后回收DK膜	1 mol/L KCl	-45
DK新膜	模拟卤水	-11

图4 纳滤膜通量随原料液镁锂比的变化

Fig.4 Effect of Mg/Li on the membrane flux

图5 镁锂比对纳滤膜分离因子及镁、锂截留率的影响

Fig.5 Effect of Mg/Li on SF and retention rates of the membrane

表4 透过液镁锂比及锂离子回收率随原料液镁锂比的变化

Table 4 Variations of Mg/Li in the permeate and the yield of lithium with increasing Mg/Li of feed

原料液镁锂比	透过液镁锂比	锂离子回收率/%
17	0.5	10.4
30	1.0	11.0
40	1.7	11.1
53	2.4	11.4
63	3.2	11.5
75	4.3	11.6

图6 纳滤膜膜面荷电作用示意图

Fig.6 Charged surface of nanofiltration membrane

图7 溶质离子在不同介电常数介质间传质过程示意图

Fig.7 Schematic diagram of solute transfer in mediums with different dielectric constants

图8 循环流量对膜通量的影响

Fig.8 Effect of cross-flow rates on the membrane flux

图9 循环流量对镁、锂截留率的影响

Fig.9 Effect of cross-flow rate on the retention rates for magnesium and lithium

图10 循环流量对透过液镁锂比及膜分离因子的影响

Fig.10 Effect of cross-flow rate on the Mg/Li in the permeate and the SF of the membrane

图11 循环流量对锂离子回收率的影响

Fig.11 Effect of cross-flow rate on the yield of lithium

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纳滤膜对高镁锂比盐湖卤水镁锂分离性能研究

Study on separation of magnesium and lithium from salt lake brine with high magnesium-to-lithium mass ratio by nanofiltration membrane

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