铝基锂吸附剂分离高钠型地下卤水锂资源过程研究

doi:10.11949/0438-1157.20230375

摘要/Abstract

摘要：

铝基锂吸附剂由于其解吸条件温和，不发生溶损，是目前唯一一种成功实现工业化生产的盐湖卤水提锂吸附剂，然而其在高钠型地下卤水中的应用可行性还有待考察。使用实验室自制的H-LDHs颗粒吸附剂，系统研究了吸附液进料流速、解吸温度及解吸液中离子浓度对固定床吸附和解吸过程的影响，实验结果表明，在高钠卤水中，当进料流速从1 BV/h（1 BV/h = 0.170 L/h）增加到4 BV/h时，穿透时间缩短了79%，而穿透吸附容量仅降低了17.8%。升高解吸温度可显著提高固定床的Li⁺解吸量，而增大解吸液中的Na⁺浓度会抑制Li⁺的解吸。此外，开发了分段循环解吸工艺，并将其用于四川某地实际地下卤水提锂过程，该工艺能够有效实现解吸工段固定床出料液中Li⁺的富集。

关键词: 铝基锂吸附剂, 地下卤水, 固定床, 吸附提锂, 分段循环解吸

Abstract:

Aluminum-based lithium adsorbent is the only adsorbent which has achieved industrial application of lithium recovery from salt lakes due to its moderate desorption conditions without dissolution loss. However, its application feasibility in high-sodium underground brine remains to be investigated. The effects of the flow rate of brine, desorption temperature and the initial concentration of ions in eluent on adsorption and desorption processes in the fixed bed were systematically investigated with granular H-LDHs adsorbents homemade in the laboratory. The results showed that the breakthrough time decreased by 79% while the breakthrough adsorption capacity only decreased by 17.8% when the flow rate rose from 1 BV/h (1 BV/h = 0.170 L/h) to 4 BV/h in high Na⁺ brine. Increasing desorption temperature could significantly enhance the Li⁺ desorption amount, however, the Li⁺ desorption amount was suppressed with the increasing concentration of Na⁺ in eluent. In addition, a stage-by-stage cyclic desorption technology was designed and applied on the real underground brine somewhere in Sichuan, which could effectively achieve the enrichment of Li⁺ in the eluent during the desorption process.

Key words: aluminum-based lithium adsorbent, underground brine, fixed bed, lithium adsorption, stage-by-stage cyclic desorption

中图分类号:

TQ 131.1

盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.

Bingchun SHENG, Jianguo YU, Sen LIN. Study on lithium resource separation from underground brine with high concentration of sodium by aluminum-based lithium adsorbent[J]. CIESC Journal, 2023, 74(8): 3375-3385.

图/表 15

表1 四川某地实际地下卤水中主要离子浓度

Table 1 Concentrations of the main existing ions in the real underground brine somewhere in Sichuan

离子	浓度/(g/L)
Li⁺	0.135
Na⁺	91.905
K⁺	5.145
Ca²⁺	18.100
Mg²⁺	1.970
B³⁺	0.500
Sr²⁺	0.955
Rb⁺	0.008
$C l -$	195.300
$S 2 -$	0.068
$N H 4 +$	0.265
$S O 4 2 -$	0.140

表1 四川某地实际地下卤水中主要离子浓度

Table 1 Concentrations of the main existing ions in the real underground brine somewhere in Sichuan

离子	浓度/(g/L)
Li⁺	0.135
Na⁺	91.905
K⁺	5.145
Ca²⁺	18.100
Mg²⁺	1.970
B³⁺	0.500
Sr²⁺	0.955
Rb⁺	0.008
$C l -$	195.300
$S 2 -$	0.068
$N H 4 +$	0.265
$S O 4 2 -$	0.140

图1 固定床实验装置

Fig.1 The fixed bed experimental setup

图2 固定床Li+提取率随吸附时间的变化

Fig.2 Li+ extraction yield over adsorption time in the fixed bed

图3 进料流速对固定床吸附性能的影响

Fig.3 Effect of flow rate on fixed bed adsorption performance

表2 进料流速对固定床吸附穿透性能的影响

Table 2 Effect of flow rate on the fixed bed adsorption breakthrough performance

$Q$ /(BV/h)	$t b$ /h	$q b$ /(mg/g)	$V b$ /BV
1	9.64	3.396	9.64
2	4.74	3.249	9.48
4	2.06	2.791	8.24

表2 进料流速对固定床吸附穿透性能的影响

Table 2 Effect of flow rate on the fixed bed adsorption breakthrough performance

$Q$ /(BV/h)	$t b$ /h	$q b$ /(mg/g)	$V b$ /BV
1	9.64	3.396	9.64
2	4.74	3.249	9.48
4	2.06	2.791	8.24

图4 解吸温度对固定床解吸性能的影响

Fig.4 Effect of desorption temperature on fixed bed desorption performance

图5 在40℃下解吸时解吸液中Na+浓度对固定床解吸性能的影响

Fig.5 Effect of concentration of Na+ in eluent on fixed bed desorption performance at 40℃

图6 解吸后吸附剂的XRD谱图

Fig.6 XRD patterns of adsorbents after desorption

图7 固定床出口处Li+浓度随解吸液量的变化

Fig.7 Outlet concentration curves of Li+ over eluent dosage in the fixed bed during the desorption process

图8 在地下卤水中吸附时固定床的吸附性能

Fig.8 Fixed bed adsorption performance in the underground brine

表3 在地下卤水中吸附Li+的穿透曲线经验模型拟合参数

Table 3 Fitting parameters for breakthrough curve empirical models of Li+ adsorption from the underground brine

模型	A	r/h^-1	$q 0, T$ /(mg/g)	$k T$ /(L/(h·mg))	$q 0, M$ /(mg/g)	$a N$	相关系数	残差平方和
Clark	0.00004	0.45881	—	—	—	—	0.9695	0.06927
Thomas	—	—	3.728	0.00483	—	—	0.9416	0.14037
M-D-R	—	—	—	—	3.136	1.73474	0.9976	0.00356

表3 在地下卤水中吸附Li+的穿透曲线经验模型拟合参数

Table 3 Fitting parameters for breakthrough curve empirical models of Li+ adsorption from the underground brine

模型	A	r/h^-1	$q 0, T$ /(mg/g)	$k T$ /(L/(h·mg))	$q 0, M$ /(mg/g)	$a N$	相关系数	残差平方和
Clark	0.00004	0.45881	—	—	—	—	0.9695	0.06927
Thomas	—	—	3.728	0.00483	—	—	0.9416	0.14037
M-D-R	—	—	—	—	3.136	1.73474	0.9976	0.00356

图9 固定床分段解吸流程

Fig.9 Flowchart of stage-by-stage desorption in the fixed bed

图10 固定床吸附穿透曲线、Li+吸附容量及固定床出口处Li+浓度随解吸液量的变化

Fig.10 Adsorption breakthrough curves over time and adsorption capacities of Li+, as well as outlet concentration curves of Li+ over eluent dosage in the fixed bed

表4 四次解吸过程中各段收集液中的Li+浓度

Table 4 The concentration of Li+ in each stage of eluent during four desorption processes

项目		Li⁺浓度/(mg/L)
项目		第一段	第二段	第三段	总收集液
模拟高钠卤水	0.1 mol/L Na⁺	786.5	371.4	119.1	284.4
	No.1	785.0	331.6	108.1	—
	No.2	840.8	367.2	134.4	—
	No.3	865.6	408.4	137.7	336.7
实际地下卤水	0.1 mol/L Na⁺	729.3	343.1	113.7	254.6
	No.1	734.9	362.3	120.2	—
	No.2	755.0	391.1	149.0	—
	No.3	756.2	381.4	146.5	309.8

图11 分段解吸循环后吸附剂的XRD谱图

Fig.11 XRD patterns of adsorbents after stage-by-stage desorption cycles

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