锂铝层状吸附剂超低品位卤水提锂冲洗和解吸过程

doi:10.16085/j.issn.1000-6613.2020-1985

摘要/Abstract

摘要：

锂铝层状氢氧化物对Li⁺具有高吸附选择性，能够有效地从高镁锂比（质量比）盐湖卤水中进行锂资源提取，具有工艺简单、经济环保等特点。本文使用球形锂铝层状吸附剂GLDH作为吸附柱填充物，系统研究了流速、温度和Li⁺初始浓度对铝盐锂吸附剂盐湖提锂工艺中冲洗、解吸的影响。试验结果表明，低温快速冲洗能有效降低冲洗过程中的Li⁺损失率。当冲洗液中Li⁺的浓度为200mg/L，冲洗液以12.0BV/h的速度在0℃下通入吸附柱时，Li⁺损失率可降低到17.8%。在解吸过程中，高温、低速和低初始Li⁺浓度的条件有利于Li⁺从吸附剂中脱出。但鉴于吸附剂的循环稳定性，采用初始Li⁺浓度为300mg/L的解吸液以2BV/h的流速在40℃下对吸附柱进行解吸，3BV时停止解吸，此时锂解吸量可达3.76mg/g，解吸液中Li⁺的平均浓度为590.83mg/L，Mg/Li比仅为0.13，可有效实现镁锂分离和锂元素集浓。循环30个周期后吸附剂的吸附容量没有明显下降，表明锂铝层状吸附剂GLDH具有良好的循环稳定性。

关键词: 吸附剂, 盐湖卤水, 提锂, 解吸, 冲洗, 高镁锂比

Abstract:

Lithium/aluminum layered double hydroxides (Li/Al-LDHs) was an effective adsorbent with high lithium selectivity for lithium extraction from old brine with ultrahigh Mg²⁺/Li⁺ ratio and low Li⁺ grade. The effects of flow rate, temperature, and initial lithium concentration on the washing and desorption processes of lithium recovery with granulated lithium aluminum layered double hydroxides (GLDH) had been investigated in this study. A lower temperature, higher flow rate, and initial lithium concentration could increase the Li⁺ deintercalation resistance during washing, but be negative to the Li⁺ unloading from GLDH during desorption. The Li⁺ loss rate could be reduced to 17.8% when the initial Li⁺ concentration of 200mg/L had been applied with the flow rate of 12.0BV/h at 0℃. The Li⁺ desorption amount could reach to 3.76mg/g when the initial lithium concentration of 300mg/L went through the column at a flow rate of 2BV/h at 40℃ for 3BV. The average lithium concentration in collected strip solution was 590.83mg/L with an Mg/Li ratio of 0.13, which could perfectly achieve the separation of magnesium and lithium and the lithium concentration. The Li⁺ adsorption capacity of GLDH was immobile in 30 adsorption-washing-desorption cycles, proving the good adsorption performance stability.

Key words: adsorbent, salt lake brine, lithium recovery, desorption, washing, high Mg/Li ratio

中图分类号:

TQ425

钟静, 陆旗玮, 林森, 于建国. 锂铝层状吸附剂超低品位卤水提锂冲洗和解吸过程[J]. 化工进展, 2021, 40(8): 4638-4646.

ZHONG Jing, LU Qiwei, LIN Sen, YU Jianguo. Washing and desorption procedures research on granulated lithium aluminum layered double hydroxides for lithium recovery from low-grade brine[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4638-4646.

图/表 18

图1 吸附柱吸附提锂试验装置

表1 吸附剂GLDH的物理性质

比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm	表观密度/g·mL^-1	粒度/mm
61.11	0.19	8.75	1.45	1-1.6

表2 察尔汗盐湖老卤阳离子组成

Li⁺/g·L^-1	Na⁺/g·L^-1	K⁺/g·L^-1	Ca²⁺/g·L^-1	Mg²⁺/g·L^-1
0.399	1.394	0.478	0.046	120.330

图2 不同温度下锂离子、镁离子浓度随冲洗体积的变化曲线

表3 不同温度下冲洗收集液中的镁锂比和锂损失率

编号

温度

/℃

流速

/BV·h^-1

初始锂浓度

/mg·L^-1

锂损失率

图3 不同锂初始浓度下锂离子、镁离子浓度随冲洗体积的变化曲线

图4 不同锂初始浓度下镁锂比随冲洗体积的变化曲线

表4 不同初始浓度下冲洗收集液中的镁锂比和锂损失率

编号	流速 /BV·h^-1	初始锂浓度 /mg·L^-1	镁锂比	锂损失率 /%
1	8.0	0	133.3	21.0
2	8.0	50	145.3	20.3
3	8.0	100	156.7	19.4
4	8.0	200	185.8	17.8

图5 不同流速下锂离子、镁离子浓度随冲洗体积的变化曲线

图6 不同流速下镁锂比随冲洗体积的变化曲线

表5 不同流速下冲洗收集液中的镁锂比和锂损失率

编号	流速 /BV·h^-1	镁锂比	锂损失率 /%
1	3.7	83.9	26.7
2	6.0	122.7	22.3
3	8.0	133.3	21.0
4	12.0	133.7	20.3

图7 流速对脱附曲线的影响

图8 流速对锂离子解吸量的影响

图9 温度对脱附曲线的影响

图10 温度对锂离子解吸量的影响

图11 锂初始浓度对脱附曲线的影响

图12 浓度对锂离子解吸量的影响

图13 GLDH长周期吸附/解吸循环稳定性

参考文献 34

1	DEETMAN S, PAULIUK S, VUUREN D P VAN, et al. Scenarios for demand growth of metals in electricity generation technologies, cars, and electronic appliances[J]. Environmental Science & Technology, 2018, 52(8): 4950-4959.
2	VIKSTRÖM H, DAVIDSSON S, HÖÖK M. Lithium availability and future production outlooks[J]. Applied Energy, 2013, 110: 252-266.
3	SPEIRS J, CONTESTABILE M, HOUARI Y, et al. The future of lithium availability for electric vehicle batteries[J]. Renewable and Sustainable Energy Reviews, 2014, 35: 183-193.
4	SWAIN B. Recovery and recycling of lithium: a review[J]. Separation and Purification Technology, 2017, 172: 388-403.
5	宁占玉, 杨春梅, 曹兆江, 等. 青海省锂资源开发利用现状及前景分析[J]. 化工设计通讯, 2019, 45(4): 219-220.
	NING Zhanyu, YANG Chunmei, CAO Zhaojiang, et al. Present situation and prospect of lithium resources development and utilization in Qinghai Province[J]. Chemical Engineering Design Communications, 2019, 45(4): 219-220.
6	SONG J F, NGHIEM L D, LI X M, et al. Lithium extraction from Chinese salt-lake brines: opportunities, challenges, and future outlook[J]. Environmental Science: Water Research & Technology, 2017, 3(4): 593-597.
7	JI Z Y, CHEN Q B, YUAN J S, et al. Preliminary study on recovering lithium from high Mg²⁺/Li⁺ ratio brines by electrodialysis[J]. Separation and Purification Technology, 2017, 172: 168-177.
8	付烨, 钟辉. 沉淀法分离高镁锂比盐湖卤水的研究现状[J]. 矿产综合利用, 2010(2): 30-33.
	FU Ye, ZHONG Hui. Research situation of separating magnesium and lithium from high Mg/Li ratio salt lake brine[J]. Multipurpose Utilization of Mineral Resources, 2010(2): 30-33.
9	ISUPOV V P, MITROFANOVA R P, CHUPAKHINA L É, et al. Mechanism of formation of nanosized copper particles in a nanoreactor based on the [LiAl₂(OH)₆]₂[Cuedta]·nH₂O supramolecular system[J]. Journal of Structural Chemistry, 2007, 48(2): 350-357.
10	MENZHERES L T, KOTSUPALO N P, MAMYLOVA E V. Solid-state interaction of aluminium hydroxide with lithium salts[J]. Journal of Materials Synthesis and Processing, 1999, 7(4): 239-244.
11	LEE J M, BAUMAN W C. Recovery of lithium from brines: US 4221767[P]. 1980-09-09.
12	BURBA III J L. Crystalline 2-layer lithium-hydroxy aluminates: US 4477367[P]. 1984-10-16.
13	PARANTHAMAN M P, LI L, LUO J Q, et al. Recovery of lithium from geothermal brine with lithium-aluminum layered double hydroxide chloride sorbents[J]. Environmental Science & Technology, 2017, 51(22): 13481-13486.
14	NAYAK M, KUTTY T R N, JAYARAMAN V, et al. Preparation of the layered double hydroxide (LDH) LiAl₂(OH)₇·2H₂O, by gel to crystallite conversion and a hydrothermal method, and its conversion to lithium aluminates[J]. Journal of Materials Chemistry, 1997, 7(10): 2131-2137.
15	YU Miao, LI Haiping, DU Na, et al. Understanding Li-Al-CO₃ layered double hydroxides (Ⅰ). Urea-supported hydrothermal synthesis[J]. Journal of Colloid and Interface Science, 2019, 547: 183-189.
16	RYABTSEV A D, MENZHERES L T, TEN A V. Sorption of lithium from brine onto granular LiCl·2Al(OH)₃·mH₂O sorbent under dynamic conditions[J]. Russian Journal of Applied Chemistry, 2002, 75(7): 1069-1074.
17	MENZHERES L T, RYABTSEV A D, MAMYLOVA E V. Synthesis of selective sorbent LiCl⋅2Al(OH)₃⋅nH₂O[J]. Theoretical Foundations of Chemical Engineering, 2019, 53(5): 821-826.
18	KOZLOVA S G, GABUDA S P, ISUPOV V P, et al. Using NMR in structural studies of aluminum hydroxide intercalation compounds with lithium salts[J]. Journal of Structural Chemistry, 2003, 44(2): 198-205.
19	SISSOKO I, IYAGBA E T, SAHAI R, et al. Anion intercalation and exchange in Al(OH)₃-derived compounds[J]. Journal of Solid State Chemistry, 1985, 60(3): 283-288.
20	ISUPOV V P, CHUPAKHINA L E, MITROFANOVA R P, et al. Synthesis and thermolysis of lithium aluminum double hydroxide containing [Fe(OH)Edta]^2-[J]. Russian Journal of Inorganic Chemistry, 2009, 54(2): 204-210.
21	HOU X J, LI H Q, HE P, et al. Structural and electronic analysis of Li/Al layered double hydroxides and their adsorption for CO₂[J]. Applied Surface Science, 2017, 416: 411-423.
22	LIU Yuting, WANG Mingkuang, CHEN Tsan Yao, et al. Arsenate sorption on lithium/aluminum layered double hydroxide intercalated by chloride and on gibbsite: sorption isotherms, envelopes, and spectroscopic studies[J]. Environmental Science & Technology, 2006, 40(24): 7784-7789.
23	NAGENDRAN S, KAMATH P V. Structure of the chloride- and bromide-intercalated layered double hydroxides of Li and Al - interplay of coulombic and hydrogen-bonding interactions in the interlayer gallery[J]. European Journal of Inorganic Chemistry, 2013, 2013(26): 4686-4693.
24	ZHONG Jing, LIN Sen, YU Jianguo. Effects of excessive lithium deintercalation on Li⁺ adsorption performance and structural stability of lithium/aluminum layered double hydroxides[J]. Journal of Colloid and Interface Science, 2020, 572: 107-113.
25	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.
26	RYABTSEV A D. Benefication technology for lithium-containing hydrogenic mineral products[J]. Journal of Mining Science, 2005, 41(6): 573-582.
27	BAUMAN W C, BURBA III J L. Recovery of lithium values from brines: US 5599516[P]. 1997-02-04.
28	JIANG H X, YANG Y, YU J G. Application of concentration-dependent HSDM to the lithium adsorption from brine in fixed bed columns[J]. Separation and Purification Technology, 2020, 241: 116682.
29	JIANG H X, ZHANG S Y, YANG Y, et al. Synergic and competitive adsorption of Li-Na-MgCl₂ onto lithium-aluminum hydroxides[J]. Adsorption, 2020, 26(7): 1039-1049.
30	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.
	CHEN Cheng, LI Yiran, SUN Zhanxue, et al. Preparation of magnetic aluminum salt adsorbent and extraction performance of lithium from saline lake brine with high magnesium lithium ratio[J]. Nonferrous Metals (Extractive Metallurgy), 2018(1): 29-33.
31	CHEN Jun, LIN Sen, YU Jianguo. Quantitative effects of Fe₃O₄ nanoparticle content on Li⁺ adsorption and magnetic recovery performances of magnetic lithium-aluminum layered double hydroxides in ultrahigh Mg/Li ratio brines[J]. Journal of Hazardous Materials, 2020, 388: 122101.
32	张黎辉, 杨志平, 李存增, 等. 吸附法提锂快洗除镁工艺技术研究[J]. 无机盐工业, 2016, 48(12): 52-54.
	ZHANG Lihui, YANG Zhiping, LI Cunzeng, et al. Research on lithium extraction with adsorption method and fast leaching for magnesium removal technology[J]. Inorganic Chemicals Industry, 2016, 48(12): 52-54.
33	李良彬, 郭敏, 吴志坚, 等. 一种铝盐锂吸附剂性能恢复的再生方法: CN106140121A[P]. 2016-11-23.
	LI Liangbin, GUO Min, WU Zhijian, et al. Regeneration method for aluminum salt lithium adsorbent performance recovery: CN106140121A[P]. 2016-11-23.
34	ZHONG J, LIN S, YU J G. Lithium recovery from ultrahigh Mg²⁺/Li⁺ ratio brine using a novel granulated Li/Al-LDHs adsorbent[J]. Separation and Purification Technology, 2021, 256: 117780.

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