Preparation and Lithium Adsorption Performance of Particulate Titanium-Based Lithium Ion Sieve

doi:10.19894/j.issn.1000-0518.240309

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (4): 552-564.DOI: 10.19894/j.issn.1000-0518.240309

• Full Papers • Previous Articles Next Articles

Preparation and Lithium Adsorption Performance of Particulate Titanium-Based Lithium Ion Sieve

Zhen-Zhu WANG¹, Zheng-Guang HE¹(), Bing HE², Ke LIANG¹, Yi-Wei BAI¹, Yu-Xin JIA¹

^1.College of Ecology and Environment，Zhengzhou University，Zhengzhou 450001，China
^2.Henan Province Zhengzhou Ecological Environment Monitoring Center，Zhengzhou 450046，China

Received:2024-09-29 Accepted:2025-03-21 Published:2025-04-01 Online:2025-05-14
Contact: Zheng-Guang HE
Supported by:
the National Science and Technology Major Special Project for Water-related Issues of the 13th Five-Year Plan(2017ZX07602-001-002)

Abstract

Abstract:

Titanium-based lithium ion sieves have strong Ti—O bonds， which give them the advantages of structural stability and good resistance to acid and alkali. They are often used as adsorbent materials for lithium extraction from salt lakes， but traditional powder lithium ion sieves synthesized from a single lithium source have problems such as low adsorption capacity， low adsorption rate， and poor cycling performance. Using Li₂CO₃ and LiNO₃ as mixed lithium sources， the modified lithium ion sieve precursor （LTO） was synthesized through a high-temperature solid-phase method with nano-TiO₂， nitric lithium modified powder titanium-based lithium-ion sieve （HTO-X） was obtained after acid washing.Further research on shaping was conducted based on HTO-X， and granular titanium-based lithium-ion sieve （PVB-HTO） was synthesized. The crystal structure， microscopic morphology and adsorption mechanism were investigated using X-ray diffraction （XRD）， scanning electron microscopy （SEM） and N₂ adsorption-desorption methods. The adsorption and regeneration performance of PVB-HTO was studied through lithium-ion adsorption experiments. The results show that the HTO-X has larger specific surface area and pore volume， higher adsorption capacity and adsorption rate， and the adsorption process is single molecular layer chemisorption. After using 0.2 mol/L hydrochloric acid pickling， the Li⁺equilibrium adsorption capacity of the modified HTO-X was 35.82 mg/g， the adsorption rate was 75% higher than that before modification， and the Li⁺ equilibrium adsorption capacity of PVB-HTO was 32.32 mg/g. After 20 cycles， the adsorption rate of Li⁺ remains above 92%， and the dissolution loss rate of titanium is below 0.15%. The modified lithium-ion sieves （HTO-X and PVB-HTO） demonstrated significant advantages in lithium-ion adsorption capacity， adsorption rate， and cycling performance， especially in the field of lithium recovery from brine.

Key words: Titanium-based lithium ion sieve, Lithium adsorption capacity, Adsorption rate, Salt lake brine

CLC Number:

O647.3

Zhen-Zhu WANG, Zheng-Guang HE, Bing HE, Ke LIANG, Yi-Wei BAI, Yu-Xin JIA. Preparation and Lithium Adsorption Performance of Particulate Titanium-Based Lithium Ion Sieve[J]. Chinese Journal of Applied Chemistry, 2025, 42(4): 552-564.

Figures/Tables 18

Table 1 The concentration of ions in the brine of Dongtai Genel Salt Lake

Ion	Li⁺	Na⁺	K⁺	Ca²⁺	Mg²⁺	Cl^-	SO $42$ ^-	CO $32$ ^-
ρ/（mg·L^-1）	150	116 500	3 780	435	5 700	187 000	18 000	230

Table 1 The concentration of ions in the brine of Dongtai Genel Salt Lake

Ion	Li⁺	Na⁺	K⁺	Ca²⁺	Mg²⁺	Cl^-	SO $42$ ^-	CO $32$ ^-
ρ/（mg·L^-1）	150	116 500	3 780	435	5 700	187 000	18 000	230

Fig.1 XRD pattern of LTO and HTO with different LiNO3 addition ratio

Fig.2 Effect of different addition ratio of LiNO3 on adsorption capacity of Li+

Fig.3 SEM images of LTO （A， B）， HTO-X （C， D） and PVB-HTO （E， F）

Fig.4 The N2 adsorption-desorption isotherms and pore size distribution diagrams of HTO-X （A， B） and PVB-HTO （C， B）

Fig.5 Effect of pH value on adsorption capacity of two lithium ion sieves

Fig.6 Effect of temperature on adsorption capacity of HTO-X and PVB-HTO

Fig.7 Effect of different acid concentration on elution rate of lithium titanium

Fig.8 Adsorption selectivity of two lithium ion sieves

Table 2 Two lithium ion sieves simulate selective parameters in salt lake brine

Metal ions	Li⁺	Na⁺	K⁺	Ca²⁺	Mg²⁺
K_d/（mL·g^-1）-HTO-X	534.61	0.019 6	0.248 0	9.139 1	0.760 2
$α M L i$ （HTO-X）	1	27 276	2 156	58	703
K_d/（mL·g^-1）-PVB-HTO	497.02	0.018 0	0.233 1	8.356 0	0.714 1
$α M L i$ （PVB-HTO）	1	27 612	2 132	59	696

Table 2 Two lithium ion sieves simulate selective parameters in salt lake brine

Metal ions	Li⁺	Na⁺	K⁺	Ca²⁺	Mg²⁺
K_d/（mL·g^-1）-HTO-X	534.61	0.019 6	0.248 0	9.139 1	0.760 2
$α M L i$ （HTO-X）	1	27 276	2 156	58	703
K_d/（mL·g^-1）-PVB-HTO	497.02	0.018 0	0.233 1	8.356 0	0.714 1
$α M L i$ （PVB-HTO）	1	27 612	2 132	59	696

Fig.9 Cyclic performance of HTO-X （A） and PVB-HTO （B）

Fig.10 Photograph （A） and SEM images （B， C， D） of PVB-HTO after multiple cycles

Fig.11 Crystal structures of （A） LTO，（B） HTO and （C） HTO （Li）

Fig.12 Adsorption kinetics curves of two kinds of lithium ion sieves

Table 3 Adsorption kinetic parameters of two kinds of lithium ion sieves

	Pseudo-first order model			Pseudo-second order model
	k₁/h^-1	q_e1/（mg·g^-1）	R²	k₂/（g·mg^-1·h^-1）	q_e2/（mg·g^-1）	R²
HTO-X	0.194 6	34.67	0.985 8	0.234 9	35.94	0.996 3
PVB-HTO	0.168 1	31.43	0.990 3	0.216 2	32.48	0.998 7

Fig.13 The adsorption isotherm curves of two ion sieves are fitted

Table 4 Adsorption isotherm fitting parameters of two kinds of lithium ion sieves

	Langmuir model			Freundlich model
	k_N/（L·mg^-1）	q_m/（mg·g^-1）	R²	k_L/（L·mg^-1）	n	R²
HTO-X	0.009 8	50.22	0.990 5	3.415 2	2.350 7	0.950 2
PVB-HTO	0.010 1	45.36	0.988 0	3.238 0	2.391 8	0.942 2

Table 5 Comparison of adsorption effect between the studied material and other materials

Ion-sieve	Material synthesis method	Li⁺ uptake/（mg·g^-1）	Adsorption time/h	Cycle number	Ref.
HTO	Solid phase reaction Li₂CO₃+TiO₂	29	24	/	［23］
HTO	Solid phase reaction C₂H₃LiO_2·2H₂O+TiO₂	24.5	12	5	［12］
HTO	Solid phase reaction LiOH_·H₂O+TiO₂	27.8	24	5	［6］
HTO	Sol-gel CH₃COOLi +Ti（OC₄H₉）₄	24.6	22	/	［9］
HTO-X	Solid phase reaction Li₂CO₃+LiNO₃+TiO₂	35.82	6	5	This work
HAS	Solid phase reaction Li₂CO₃+Al（OH）₃+SiO₂	26.28	8	10	［25］
HTO	Hydrothermal synthesis TTIP+LiOH+H₂O₂	26.85	9	5	［14］
PVA-HTO	Solid phase reaction Li₂CO₃+TiO₂	13.54	12	5	［16］
PVC-HTO	Solid phase reaction Li₂CO₃+TiO₂	9	12	5	［13］
PVC-LMZO	Solid phase reaction Li_1.6Mn_1.6O₄+Zr（NO₃）₄·5H₂O	18.33	6	15	［26］
HTO-P	Solid phase reaction Li₂CO₃+TiO₂	14.25	15	5	［27］
ATP-HTO	Solid phase reaction Li₂CO₃+ATP	29.18	10	5	［28］
PVB-HTO	Solid phase reaction Li₂CO₃+LiNO₃+TiO₂	32.32	6	20	This work

References 28

1	KIM J， KIM H， KANG K. Conversion‐based cathode materials for rechargeable sodium batteries［J］. Adv Energy Mater， 2018， 8（17）： 1702646-1702665.
2	余亮良，黄敏. 含锂资源提锂技术现状及研究进展［J］. 有色冶金设计与研究， 2024， 45（2）： 5-9， 24.
	YU L L， HUANG M. Current status and research progress of lithium resource extraction technology［J］， Nonfer Met Design Res， 2024， 45（2）： 5-9， 24.
3	LIU D， GAO X， AN H， et al. Supply and demand response trends of lithium resources driven by the demand of emerging renewable energy technologies in China［J］. Resources， Conservation Recycl， 2019， 145： 311-321.
4	SRIVASTAVA V， RANTALA V， MEHDIPOUR P， et al. A comprehensive review of the reclamation of resources from spent lithium-ion batteries［J］. Chem Eng J， 2023， 474： 145822-145840.
5	葛涛，徐亮，孟金伟，等. 盐湖卤水提锂工艺技术研究进展［J］. 有色金属工程， 2021， 11（2）： 55-62.
	GE T， XU L， MENG J W， et al. Research progress on lithium extraction technology from salt lake brine［J］. Nonfer Met Eng， 2021， 11（2）： 55-62.
6	WANG S， ZHANG M， ZHANG Y， et al. Application of citric acid as eluting medium for titanium type lithium ion sieve［J］. Hydrometallurgy， 2019， 183： 166-174.
7	LI X， CHEN L， CHAO Y， et al. Amorphous TiO₂-derived large-capacity lithium ion sieve for lithium recovery［J］. Chem Eng Technol， 2020， 43（9）： 1784-1791.
8	WANG S， ZHANG M， ZHANG Y， et al. High adsorption performance of the Mo-doped titanium oxide sieve for lithium ions［J］. Hydrometallurgy， 2019， 187： 30-37.
9	ZHANG L， ZHOU D， YAO Q， et al. Preparation of H₂TiO₃-lithium adsorbent by the sol-gel process and its adsorption performance［J］. Appl Surf Sci， 2016， 368： 82-87.
10	ZHANG L Y， LIU Y W， HUANG L， et al. A novel study on preparation of H₂TiO₃-lithium adsorbent with titanyl sulfate as titanium source by inorganic precipitation-peptization method［J］. RSC Adv， 2018， 8（3）： 1385-1391.
11	TANG D， ZHOU D， ZHOU J， et al. Preparation of H₂TiO₃-lithium adsorbent using low-grade titanium slag［J］. Hydrometallurgy， 2015， 157： 90-96.
12	GU D， SUN W， HAN G， et al. Lithium ion sieve synthesized via an improved solid state method and adsorption performance for West Taijinar Salt Lake brine［J］. Chem Eng J， 2018， 350： 474-483.
13	LIN H， YU X， LI M， et al. Synthesis of polyporous ion-sieve and its application for selective recovery of lithium from geothermal water［J］. ACS Appl Mater Interfaces， 2019， 11（29）： 26364-26372.
14	ZHAO B， QIAN Z， GUO M， et al. The performance and mechanism of recovering lithium on H₄Ti₅O₁₂ adsorbents influenced by （110） and （111） facets exposed［J］. Chem Eng J， 2021， 414： 128729-128741.
15	CHEN S， CHEN Z， WEI Z， et al. Titanium-based ion sieve with enhanced post-separation ability for high performance lithium recovery from geothermal water［J］. Chem Eng J， 2021， 410： 128320-128329.
16	LIMJUCO L A， NISOLA G M， LAWAGON C P， et al. H₂TiO₃ composite adsorbent foam for efficient and continuous recovery of Li⁺ from liquid resources［J］. Colloids Surf A， 2016， 504： 267-279.
17	郭佳明，刘明言，吴强，等. 硝酸锂改性钛系离子筛的制备及其吸附性能［J］. 化工学报， 2020， 71（2）： 879-888.
	GUO J M， LIU M Y， WU Q， et al. Preparation and adsorption performance of lithium nitrate modified titanium-based ion sieve［J］. J Chem Ind Eng， 2020， 71（2）： 879-888.
18	JANG Y， CHUNG E. Adsorption of lithium from shale gas produced water using titanium based adsorbent［J］. Ind Eng Chem Res， 2018， 57（25）： 8381-8387.
19	MARCUS Y. Theromdynamics of solavtion of ions. part 5. gibbs free-energy of hydration at 298.15 K［J］. J Chem Soc， Faraday Trans， 1991， 87（18）： 2995-2999.
20	HE G， ZHANG L， ZHOU D， et al. The optimal condition for H₂TiO₃ lithium adsorbent preparation and Li⁺ adsorption confirmed by an orthogonal test design［J］. Ionics， 2015， 21（8）： 2219-2226.
21	HOSOGI Y， KATO H， KUDO A. Visible light response of AgLi_1/3M_2/3O₂（M=Ti and Sn） synthesized from layered Li₂MO₃ using molten AgNO₃［J］. J Mater Chem， 2008， 18（6）： 647-653.
22	JI Z Y， YANG F J， ZHAO Y Y， et al. Preparation of titanium-base lithium ionic sieve with sodium persulfate as eluent and its performance［J］. Chem Eng J， 2017， 328： 768-775.
23	CHITRAKAR R， MAKITA Y， OOI K， et al. Lithium recovery from salt lake brine by H₂TiO₃［J］. Dalton Trans， 2014， 43（23）： 8933-8939.
24	WANG S， LI P， ZHANG X， et al. Selective adsorption of lithium from high Mg-containing brines using HxTiO₃ ion sieve［J］. Hydrometallurgy， 2017， 174： 21-28.
25	HU H， GUO J， LIU M， et al. Preparation and characterization of high-stability lithium ion-sieves with aluminosilicate framework ［J］. Hydrometallurgy， 2022， 213： 105929-105937.
26	WANG L， WANG L， LI L. Preparation of PVC-LMZO membrane and its lithium adsorption performance from brine［J］. Desalination， 2023， 561： 116689-1166104.
27	TANG C， ZHANG L， LI J， et al. Effect of buffer on direct lithium extraction from Tibetan brine by formed titanium-based lithium ion sieves［J］. New J Chem， 2024， 48（27）： 12450-12459.
28	XU J， CHEN P. Preparation and characterization of lithium-ion sieve with attapulgite［J］. Desalination， 2024， 571： 117111-117122.

Preparation and Lithium Adsorption Performance of Particulate Titanium-Based Lithium Ion Sieve

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 18

References 28

Related Articles 1

Recommended Articles

Metrics

Comments