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

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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 $_{4}^{2}$ ^-	CO $_{3}^{2}$ ^-
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 $_{4}^{2}$ ^-	CO $_{3}^{2}$ ^-
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

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

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