Performance evaluation and comparison of aluminum-based granulated lithium adsorbent

doi:10.11949/0438-1157.20201717

Abstract

Abstract:

Lithium resources are abundant in Qarhan Salt Lake in China. However, the overall grade is low, with the characteristics of low lithium concentration and high magnesium-lithium ratio, which makes development difficult. It has been proved that the adsorption method is effective for extracting lithium from brines with an ultrahigh Mg/Li ratio, especially, the lithium aluminum double layered hydroxides is the only adsorbent for industrial application relying on the advantage of elution without dissolution. In this work, the laboratory-made granulated adsorbent (C) and other adsorbents (A, B) that have been industrialized are evaluated to compare the adsorption performances. Through the characterization analysis of these adsorbents, the adsorbent C displays a good mechanical strength without dissolution or powder lose, declaring a great granulation process. The adsorption capacities of adsorbent A, B and C are 2.23 mg·g^-1, 0.45 mg·g^-1 and 4.90 mg·g^-1, respectively. All adsorption courses are in accordance with the pseudo-second-order kinetic equation. The fitting results of adsorption isotherms at different temperatures show that the Sips three-parameter model can describe the adsorption of the three adsorbents accurately.

Key words: ultrahigh Mg/Li ratio brine, lithium aluminum double layered hydroxide, lithium adsorption, granulation

摘要：

我国察尔汗盐湖卤水中蕴含丰富的锂资源，但总体品位较低，具有锂浓度低、镁锂比高的特点，导致开发难度很大。吸附法是针对高镁锂比卤水进行提锂的有效方法，其中铝系锂吸附剂具有洗脱无溶损的优势，目前已在盐湖提锂工业中应用。分别对两种工业化铝系锂吸附剂A、B以及实验室自制吸附剂C进行了系统化表征与吸附性能评价。实验结果显示三种成型吸附剂的有效成分均是锂铝层状氢氧化物，在静态吸附条件下，25℃时吸附剂A、B、C对察尔汗老卤中锂的吸附量分别为2.23、0.45、4.90 mg·g^-1，吸附动力学均符合拟二级动力学方程，不同温度下吸附等温线拟合结果表明Sips三参数模型能够准确描述三种吸附剂的吸附过程。

关键词: 高镁锂比卤水, 锂铝层状氢氧化物, 吸附提锂, 吸附剂成型

CLC Number:

TQ 133.1

ZHANG Rui, LU Qiwei, LIN Sen, YU Jianguo. Performance evaluation and comparison of aluminum-based granulated lithium adsorbent[J]. CIESC Journal, 2021, 72(6): 3053-3062.

张瑞, 陆旗玮, 林森, 于建国. 铝系成型锂吸附剂性能测试评价与对比[J]. 化工学报, 2021, 72(6): 3053-3062.

Figures/Tables 16

References 30

1	胡兴军. 锂: 市场前景极为广阔[J]. 中国金属通报, 2011(9): 26-28.
	Hu X J. Lithium: the market prospect is broad [J]. China Metal Bulletin, 2011, (9): 26-28.
2	周园园. 中国锂资源供需形势及对外依存度分析[J]. 资源与产业, 2019, 21(3): 46-50.
	Zhou Y Y. Supply-demand situation and external dependence of China's lithium resource[J]. Resources & Industries, 2019, 21(3): 46-50.
3	Bernhardt D, Reilly Ⅱ J F. Minerals Commodity Summaries 2019[R]. Reston:
	Geological Survey U. S., 2019.
4	苏彤, 郭敏, 刘忠, 等. 全球锂资源综合评述[J]. 盐湖研究, 2019, 27(3): 104-111.
	Su T, Guo M, Liu Z, et al. Comprehensive review of global lithium resources[J]. Journal of Salt Lake Research, 2019, 27(3): 104-111.
5	杨卉芃, 柳林, 丁国峰. 全球锂矿资源现状及发展趋势[J]. 矿产保护与利用, 2019, 39(5): 26-40.
	Yang H P, Liu L, Ding G F. Present situation and development trend of lithium resources in the world[J]. Conservation and Utilization of Mineral Resources, 2019, 39(5): 26-40.
6	曹兆江, 高敏, 宁占玉, 等. 青海盐湖锂资源及提锂技术概述[J]. 化工设计通讯, 2019, 45(6): 190,207.
	Cao Z J, Gao M, Ning Z Y, et al. Lithium resources and lithium extraction technology in Qinghai salt lake[J]. Chemical Engineering Design Communications, 2019, 45(6): 190,207.
7	陈念, 钟辉, 颜辉. 国内外卤水提锂工艺技术现状[J]. 盐业与化工, 2014, 43(3): 1-4.
	Chen N, Zhong H, Yan H. Present situation of the process and technique of lithium recovery from brine around the world[J]. Journal of Salt and Chemical Industry, 2014, 43(3): 1-4.
8	张绍成, 冉广芬. 吸附法盐湖卤水提锂工艺试验[J]. 盐湖研究, 1997, 5(1): 59-68.
	Zhang S C, Ran G F. Technological experiment on lithium extraction from bittern of salt lake by adsorption method[J]. Journal of Salt Lake Research, 1997, 5(1): 59-68.
9	刘东帆, 孙淑英, 于建国. 盐湖卤水提锂技术研究与发展[J]. 化工学报, 2018, 69(1): 141-155.
	Liu D F, Sun S Y, Yu J G. Research and development on technique of lithium recovery from salt lake brine[J]. CIESC Journal, 2018, 69(1): 141-155.
10	孙淑英, 张钦辉, 于建国. 尖晶石型LiMn₂O₄的水热合成及其锂吸附性能[J]. 过程工程学报, 2010, 10(1): 185-189.
	Sun S Y, Zhang Q H, Yu J G. Hydrothermal synthesis and lithium adsorption properties of LiMn₂O₄ spinel[J]. The Chinese Journal of Process Engineering, 2010, 10(1): 185-189.
11	席晓丽, 王凯丰, 马立文, 等. 一种尖晶石型锂离子筛的制备方法: 106622116A[P]. 2017-05-10.
	Xi X L, Wang K F, Ma L W. A method for preparing spinel lithium ion sieve: 106622116A[P]. 2017-05-10.
12	闫树旺, 钟辉, 周永兴. 二氧化钛吸附剂的研制及从卤水中提锂[J]. 离子交换与吸附, 1992, 8(3): 222-228.
	Yan S W, Zhong H, Zhou Y X. Study on ionic seive of titanium oxide and lithium recovery from brines[J]. Ion Exchange and Adsorption, 1992, 8(3): 222-228.
13	董殿权, 张凤宝, 张国亮, 等. Li₄Ti₅O₁₂的合成及对Li⁺的离子交换动力学[J]. 物理化学学报, 2007, 23(6): 950-954.
	Dong D Q, Zhang F B, Zhang G L, et al. Synthesis of Li₄Ti₅O₁₂ and its exchange kinetics with Li⁺[J]. Acta Physico-Chimica Sinica, 2007, 23(6): 950-954.
14	Isupov V P, Kotsupalo N P, Nemudry A P, et al. Aluminium hydroxide as selective sorbent of lithium salts from brines and technical solutions[J]. Studies in Surface Science and Catalysis, 1999, 120: 621-652.
15	吴志坚, 郭敏, 李权, 等. 氢氧化铝基锂吸附剂从卤水中吸附锂的机理[J]. 盐湖研究, 2018, 26(3): 1-6.
	Wu Z J, Guo M, Li Q, et al. Adsorption mechanisms for the recovery of lithium from brines using aluminum hydroxide based adsorbent[J]. Journal of Salt Lake Research, 2018, 26(3): 1-6.
16	张绍成, 马培华, 邓小川. 吸附法从盐湖卤水中提取锂的方法: 1511964A[P]. 2004-07-14.
	Zhang S C, Ma P H, Deng X C. Methods for lithium recovery from salt lake brine: 1511964A[P]. 2004-07-14.
17	李杰. 铝盐锂吸附剂制备工艺及吸附性能研究[D]. 成都: 成都理工大学, 2011.
	Li J. Studies on the synthesis of aluminum salt lithium-adsorbent and its adsorptive property[D]. Chengdu: ChengduUniversity of Technology, 2011.
18	Qu J, He X M, Wang B T, et al. Synthesis of Li-Al layered double hydroxides via a mechanochemical route[J]. Applied Clay Science, 2016, 120: 24-27.
19	Fogg A M, Freij A J, Parkinson G M. Synthesis and anion exchange chemistry of rhombohedral Li/Al layered double hydroxides[J]. Chemistry of Materials, 2002, 14(1): 232-234.
20	郭敏, 刘忠, 李权, 等. 铝基锂吸附剂从卤水中吸附提锂的研究及进展[J]. 青海科技, 2019, 26(3): 16-20.
	Guo M, Liu Z, Li Q, et al. Research and development of aluminum-based lithium adsorbent for lithium recovery from brine [J]. Qinghai Science and Technology, 2019, 26(3): 16-20.
21	Bauman W C, Burba Iii J L. Composition for the recovery of lithium values from brine and process of making/using said composition: US6280693[P]. 2001-08-28.
22	Lee J M, Bauman W C. Recovery of lithium from brines: US4116856(A)[P]. 1978-09-26.
23	Lee J M, Bauman W C. Recovery of lithium from brines: US4221767(A)[P]. 1982-08-31.
24	Lee J M, Bauman W C. Alumina compounds in ion exchange resins: US4381349[P]. 1983-04-26.
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	张升书, 李法强, 祝增虎, 等. Ca(ALG)₂-LiCl·2Al(OH)₃·nH₂O的合成研究[J]. 洛阳理工学院学报(自然科学版), 2016, 26(2): 6-9.
	Zhang S S, Li F Q, Zhu Z H, et al. Study on synthesis of Ca(ALG)₂-LiCl·2Al(OH)₃·nH₂O[J]. Journal of Luoyang Institute of Science and Technology (Natural Science Edition), 2016, 26(2): 6-9.
27	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 C, Li Y R, Sun Z X, 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.
28	Chen J, Lin S, Yu J G. 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.
29	寇晓康, 王刚, 刘金华. 一种吸附法从盐湖卤水中提取锂的方法: 101928828A[P]. 2010-12-29.
	Kou X K, Wang G, Liu J H. Method for extracting lithium from salt lake brine by adsorption method: 101928828A[P]. 2010-12-29.
30	Hu F P, Lin S, Li P, et al. Quantitative effects of desorption intensity on structural stability and readsorption performance of lithium/aluminum layered double hydroxides in cyclic Li⁺ extraction from brines with ultrahigh Mg/Li ratio[J]. Industrial & Engineering Chemistry Research, 2020, 59(30): 13539-13548.

吸附剂种类	结构中Li/Al摩尔比
吸附剂种类	洗脱前	洗脱后
A	0.28	0.20
B	0.48	0.20
C	0.35	0.20

吸附剂种类	结构中Li/Al摩尔比
吸附剂种类	洗脱前	洗脱后
A	0.28	0.20
B	0.48	0.20
C	0.35	0.20

吸附剂种类	Q_e实验值/(mg·g^-1)	拟一级动力学			拟二级动力学
吸附剂种类	Q_e实验值/(mg·g^-1)	Q_e/(mg·g^-1)	k₁/h^-1	R²	Q_e/(mg·g^-1)	k₂/(mg·g^-1·h^-1)	R²
A	2.3456	1.9270	0.0458	0.9555	2.4499	0.0612	0.9870
B	0.4544	0.3677	0.0632	0.9861	0.4763	0.4810	0.9842
C	4.9212	3.3955	0.0855	0.9841	5.0615	0.0830	0.9980

吸附剂种类	Q_e实验值/(mg·g^-1)	拟一级动力学			拟二级动力学
吸附剂种类	Q_e实验值/(mg·g^-1)	Q_e/(mg·g^-1)	k₁/h^-1	R²	Q_e/(mg·g^-1)	k₂/(mg·g^-1·h^-1)	R²
A	2.3456	1.9270	0.0458	0.9555	2.4499	0.0612	0.9870
B	0.4544	0.3677	0.0632	0.9861	0.4763	0.4810	0.9842
C	4.9212	3.3955	0.0855	0.9841	5.0615	0.0830	0.9980

吸附剂	Freundlich			Langmuir			Sips
吸附剂	K_F/(L·g^-1)	1/n_F	R²	Q_m/(mg·g^-1)	K_L(L·mg^-1)	R²	a_S	K_S/(L·g^-1)	β	R²
A	0.4181	0.3002	0.8549	3.0813	0.0101	0.8919	4.5100×10^-12	1.04×10^-11	5.3985	0.9888
B	0.3569	0.1601	0.7044	0.9552	0.0374	0.9019	0.0011	9.4100×10^-4	1.9241	0.9439
C	2.8978	0.1101	0.8664	4.9467	0.5494	0.9629	0.6806	3.5641	0.6659	0.9979