铝系成型锂吸附剂性能测试评价与对比

doi:10.11949/0438-1157.20201717

化工学报 ›› 2021, Vol. 72 ›› Issue (6): 3053-3062.DOI: 10.11949/0438-1157.20201717

• 青海盐湖资源综合利用专栏 • 上一篇下一篇

铝系成型锂吸附剂性能测试评价与对比

张瑞^1,²(),陆旗玮³,林森^1,²(),于建国^1,²()

^1.华东理工大学国家盐湖资源综合利用工程技术研究中心，上海 200237
^2.华东理工大学资源过程工程教育部工程研究中心，上海 200237
^3.上海国玻汽车科技有限公司，上海 200131

收稿日期:2020-11-30 修回日期:2021-03-12 出版日期:2021-06-05 发布日期:2021-06-05
通讯作者: 林森,于建国
作者简介:张瑞（1998—），女，博士研究生， kathyzhang98@163.com
基金资助:
国家自然科学基金项目(U20A20142);青海省重大科技专项(2019-GX-A7)

Performance evaluation and comparison of aluminum-based granulated lithium adsorbent

ZHANG Rui^1,²(),LU Qiwei³,LIN Sen^1,²(),YU Jianguo^1,²()

^1.National Engineering Research Center for Integrated Utilization of Salt Lake Resources, East China University of Science and Technology, Shanghai 200237, China
^2.Engineering Research Center of Salt Lake Resources Process Engineering, Ministry of Education, East China University of Science and Technology, Shanghai 200237, China
^3.Shanghai Guobo Automotive Science and Technology Co. , Ltd. , Shanghai 200131, China

Received:2020-11-30 Revised:2021-03-12 Online:2021-06-05 Published:2021-06-05
Contact: LIN Sen,YU Jianguo

摘要/Abstract

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

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

中图分类号:

TQ 133.1

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.

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.

图/表 16

表1 实验所用察尔汗盐湖老卤性质参数及主要阳离子浓度

Table 1 Characteristic parameters and main cation concentration of Qaerhan Salt Lake

Li⁺/(g·L^-1)	Mg²⁺/(g·L^-1)	Na⁺/(g·L^-1)	K⁺/(g·L^-1)	Ca²⁺/(g·L^-1)	密度/(g·ml^-1)	黏度/(Pa·s)	pH
0.399	120.330	1.394	0.478	0.046	1.32	14.01×10^-3	5.6

表2 洗脱前后锂铝摩尔比

Table 2 The Li/Al molar ratio before and after elution

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

图1 三种成型吸附剂的XRD谱图

Fig.1 XRD patterns of three granulated adsorbents

图2 三种成型吸附剂的红外光谱图

Fig.2 FTIR spectra of three granulated adsorbents

图3 三种吸附剂的表观形貌和能谱分析

Fig.3 SEM and EDS of three granulated adsorbents

图4 N2 77 K下成型吸附剂C的吸附-脱附等温线（a）和孔径分布（b）

Fig.4 N2 adsorption/desorption isotherm (a) and pore size distributions (b) on granulated adsorbent C at 77 K

表3 成型吸附剂C的孔结构参数

Table 3 Pore structure of granulated adsorbent C

样品	比表面积/(m²·g^-1)	孔容/(cm³·g^-1)	平均孔径/nm
成型吸附剂C	61.11	0.19	8.75

图5 25℃下三种吸附剂对锂离子的吸附动力学

Fig.5 Adsorption of Li+ of three granulated adsorbents as a function of time at 25℃

图6 25℃下拟一级动力学（a）和拟二级动力学（b）

Fig.6 Fitting curves of pseudo-first-order kinetics (a) and pseudo-second-order kinetics (b) at 25℃

表4 25℃下平衡吸附量实验值、换算值及拟一、二级动力学方程参数

Table 4 Experimental value, conversion value and fitting parameters of pseudo-first-order and pseudo-second-order kinetics at 25℃

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

图7 15℃下吸附剂A、B和C的Langmuir、Freundlich、Sips吸附等温线

Fig7 Langmuir, Freundlich, Sips adsorption isotherms of adsorbents A, B and C at 15℃

图8 30℃下吸附剂A、B和C的Langmuir、Freundlich、Sips吸附等温线

Fig.8 Langmuir, Freundlich, Sips adsorption isotherms of adsorbents A, B and C at 30℃

图9 45℃下吸附剂A、B和C的Langmuir、Freundlich、Sips吸附等温线

Fig.9 Langmuir, Freundlich, Sips adsorption isotherms of adsorbents A, B and C at 45℃

表5 15℃下吸附剂A、B和C的Langmuir、Freundlich、Sips吸附等温方程参数

Table 5 Fitting parameters of Langmuir, Freundlich and Sips model of adsorbents A, B and C at 15℃

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

表6 30℃下吸附剂A、B和C的Langmuir、Freundlich、Sips吸附等温方程参数

Table 6 Fitting parameters of Langmuir, Freundlich and Sips model of adsorbents A, B and C at 30℃

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	0.1633	0.5228	0.8366	5.7700	0.0041	0.8362	0.0077	0.0782	0.7171	0.8368
B	0.2332	0.2836	0.9309	1.3672	0.0176	0.9952	0.0123	0.0162	1.1022	0.9944
C	2.3780	0.1460	0.9429	4.8441	0.2725	0.9136	0.4295	2.4821	0.5071	0.9925

表7 45℃下吸附剂A、B和C的Langmuir、Freundlich、Sips吸附等温方程参数

Table 7 Fitting parameters of Langmuir, Freundlich and Sips model of adsorbents A, B and C at 45℃

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	0.3023	0.4312	0.9082	5.42	0.0061	0.9333	1.900×10^-7	7.1600×10^-7	3.2498	0.9731
B	0.1389	0.2905	0.9575	0.9025	0.0131	0.9877	0.0016	0.0013	1.5088	0.9920
C	2.1364	0.1868	0.9282	5.4823	0.1392	0.9194	0.2519	1.6664	0.5708	0.9776

参考文献 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.

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[2]	朱冬生,汪立军,谭盈科. 化学聚合法强化吸附剂热传导 [J]. CIESC Journal, 1999, 50(2): 235-241.

铝系成型锂吸附剂性能测试评价与对比

Performance evaluation and comparison of aluminum-based granulated lithium adsorbent

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