SA膜状锂离子筛的制备及其锂吸附性能

doi:10.11949/0438-1157.20230061

摘要/Abstract

摘要：

采用亲水的SA为成膜材料，PEG为致孔剂，制备了掺杂自制锆氧化物包覆的锂离子筛前体LMZO的膜状锂离子筛，研究其对锂的吸附性能以及循环稳定性能等，并对其进行了吸附动力学及吸附等温模型分析。结果表明：SA浓度为30 mg·ml^-1，PEG含量为1%，LMZO含量为55%时，制得的膜状锂离子筛对Li⁺的吸附性能最好，为1202.17 mg·m^-2。用0.1 mol·L^-1HCl溶液解吸，平衡时锂解吸率可达66.55%，锰溶损率仅为0.345%。在卤水中进行了10次循环吸附解吸后，吸附量降至1116.64 mg·m^-2，吸附量仅损失了7.0%。在含有多种复杂离子如Na⁺、K⁺、Mg²⁺和Ca²⁺的卤水中，SA膜状锂离子筛对Li⁺有很高的选择性，其吸附过程更符合伪二级动力学方程及Langmuir吸附等温模型。膜状锂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。

关键词: 锂离子筛, 海藻酸钠, 盐湖卤水, 吸附, 膜, 分离

Abstract:

SA lithium ion sieve membrane was prepared by blend of the zirconium-coated lithium ion sieve precursor LMZO with sodium alginate (SA) and polyethylene glycol (PEG). A series of experiments for examining its adsorption and cycle stability were carried out, and the adsorption isotherm model and the adsorption kinetics were analyzed. The results showed that the adsorption capacity of SA lithium ion sieve membrane was 1202.17 mg·m^-2 when the concentration of SA was 30 mg·ml^-1, the content of PEG was 1%, and the amount of loading of LMZO was 55%. After treated with 0.1 mol·L^-1 HCl, the extraction of Li⁺ reached 66.55% and the dissolution loss rate of Mn²⁺ was only 0.345% in equilibrium. After 10 cycles of adsorption and desorption in brine, the Li⁺ adsorption capacity was lost only 7.0% (from 1198.40 mg·m^-2 to 1116.64 mg·m^-2). In brine containing a variety of complex ions such as Na⁺, K⁺, Mg²⁺ and Ca²⁺, the SA film-like lithium ion sieve has a high selectivity to Li⁺, and its adsorption process is more in line with the pseudo-second-order kinetic equation and the Langmuir adsorption isotherm model. It is potential to be used in enrichment and recovery of lithium from salt lake brine and other liquid lithium sources.

Key words: lithium ion sieve, sodium alginate, brine, absorption, membrane, separation

中图分类号:

TQ 131.11

王蕾, 王磊, 白云龙, 何柳柳. SA膜状锂离子筛的制备及其锂吸附性能[J]. 化工学报, 2023, 74(5): 2046-2056.

Lei WANG, Lei WANG, Yunlong BAI, Liuliu HE. Preparation of SA lithium ion sieve membrane and its adsorptive properties[J]. CIESC Journal, 2023, 74(5): 2046-2056.

图/表 16

表1 青海昆特依盐湖卤水水质成分

Table 1 The components of the Qinghai Kunty salt lake brine

金属离子	初始浓度/(g·L^-1)
Li⁺	0.11
Mg²⁺	10.98
Ca²⁺	0.063
K⁺	4.04
Na⁺	4.98
Mn²⁺	—

图1 SA浓度对膜的拉伸强度和断裂伸长率的影响

Fig.1 Effects of SA concentration on tensile strength and elongation at break of the membranes

图2 Gl添加量对膜的拉伸强度和断裂伸长率的影响

Fig.2 Effects of glycerol contents on tensile force and elongation at break of the membranes

表2 不同Gl添加量的SA膜状锂离子筛的膜通量参数

Table 2 Membrane flux performance of SA lithium ion sieve membrane with different glycerol contents

Gl添加量/%	卤水通量/(L·m²·h^-1)
0	334.51
1	361.98
2	383.85
3	402.37
4	414.73
5	429.63

图3 CaCl2浓度对膜的拉伸强度和吸附量的影响

Fig.3 Effects of CaCl2 concentration on tensile force and Li+ adsorption capacity of the membranes

图4 不同LMZO含量的SA膜状锂离子筛的SEM图

Fig.4 SEM images of SA lithium ion sieve membranes of different LMZO contents

图5 LMZO的添加量对SA膜状锂离子筛吸附量的影响

Fig.5 Relation between content of LMZO and Li+ adsorption capacity of SA lithium ion sieve membranes

图6 不同PEG含量SA膜状锂离子筛的SEM图

Fig.6 SEM images of SA lithium ion sieve membranes of different PEG contents

图7 PEG的添加量对SA膜状锂离子筛吸附量的影响

Fig.7 Relation between content of PEG and Li+ adsorption capacity of SA lithium ion sieve membranes

表3 不同PEG添加量的SA膜状锂离子筛的膜通量参数及比表面积

Table 3 Membrane flux performance and BET surface area of SA lithium ion sieve membrane with different PEG contents

PEG含量/%	卤水通量/ (L·m²·h^-1)	比表面积/ (m²·g^-1)	孔隙体积/ (cm³·g^-1)
0	378.15	11.608	0.0206
0.5	501.98	14.815	0.0293
1	668.37	17.095	0.0379
2	796.02	19.362	0.0404
4	959.33	21.298	0.0495

图8 SA膜状锂离子筛的吸附容量

Fig.8 Adsorption capacity of SA lithium ion sieve membrane

图9 SA膜状锂离子筛锂解吸率及锰溶损率

Fig.9 Extraction of Li+ and dissolution loss rate of Mn2+ from SA lithium ion sieve membrane

图10 SA膜状锂离子筛循环过程的锰溶损率及锂吸附量

Fig.10 Dissolution loss rate of Mn2+ and lithium adsorption capacity of SA lithium ion sieve membrane in the cycling process

表4 膜状锂离子筛从卤水中分离锂离子的性能

Table 4 Performance of SA lithium ion sieve membrane in the separation of Li+ from other cations in brine

阳离子	C₀/(mg·L^-1)	C_e/(mg·L^-1)	Q/(mg·m^-2)	Q/(mmol·m^-2)	K_d/(L·m^-2)	$a M L i$	CF/(L·m^-2)
Li⁺	112.701	76.922	1202.17	173.22	15.628	1.00	10.667
Mg²⁺	10983.090	10867.487	3884.26	159.81	0.357	43.78	0.354
K⁺	4043.177	4031.080	406.46	10.42	0.101	154.73	0.101
Na⁺	4985.966	4979.104	902.56	39.24	0.182	85.87	0.181

表4 膜状锂离子筛从卤水中分离锂离子的性能

Table 4 Performance of SA lithium ion sieve membrane in the separation of Li+ from other cations in brine

阳离子	C₀/(mg·L^-1)	C_e/(mg·L^-1)	Q/(mg·m^-2)	Q/(mmol·m^-2)	K_d/(L·m^-2)	$a M L i$	CF/(L·m^-2)
Li⁺	112.701	76.922	1202.17	173.22	15.628	1.00	10.667
Mg²⁺	10983.090	10867.487	3884.26	159.81	0.357	43.78	0.354
K⁺	4043.177	4031.080	406.46	10.42	0.101	154.73	0.101
Na⁺	4985.966	4979.104	902.56	39.24	0.182	85.87	0.181

图11 SA膜状锂离子筛吸附锂的动力学曲线

Fig.11 Kinetics of Li+ adsorption by SA lithium ion sieve membrane

图12 SA膜状锂离子筛吸附等温拟合曲线

Fig.12 Adsorption isotherm of Li+ adsorption by SA lithium ion sieve membrane

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