利用混晶TiO2为钛源合成高耐酸性钛系锂离子筛的研究

doi:10.19964/j.issn.1006-4990.2024-0349

Abstract

Abstract:

To improve acid resistance of Ti-based lithium ionic sieve β-H₂TiO₃ in the process of engineering application，the high acid-resistant β-H₂TiO₃ was synthesized in this study using different proportions of rutile and anatase TiO₂ as mixed Ti sources.And the effect of the ratio of mixed crystal TiO₂ on the adsorption capacity，ion selectivity and acid resistance of lithium ion sieve was studied.The optimal ratio of mixed crystal titanium source was also optimized and cyclic stability of the lithium ion sieve was tested.The resuils showed that when the mass content of anatase TiO₂ in titanium source for synthesis of β-H₂TiO₃ were 0，20%，40%，60%，80% and 100%，increasing the anatase TiO₂ content in the titanium source led to an increase in the adsorption capacity of β-H₂TiO₃，and there was no significant negative effect on ion selectivity.The acid resistance test results showed that when the content of anatase TiO₂ in the titanium source was 40%，the mass residual rate of β-H₂TiO₃ after acid soaking could be significantly increased，which was 65%，and the attenuation degree of adsorption properties of the remaining was minimal.XRD and SEM characterization results of the residue after acid soaking showed the β-H₂TiO₃ synthesized from single crystal TiO₂ as titanium source could form anatase type TiO₂ new phase after soaking in 1 mol/L hydrochloric acid.When the anatase TiO₂ content in the titanium source was 40%，no new phase formed after the β-H₂TiO₃ soaked with acid.The adsorption capacity of the β-H₂TiO₃ remained stable at about 17 mg/g after 30 cycles of testing，which was better than that of β-H₂TiO₃ synthesized by single crystal TiO₂ as titanium source.In summary，using mixed crystal TiO₂ as titanium source to synthesize lithium ion sieve could improve the acid resistance and cycle life.It provided direction and guidance for preparation of high stability Ti-based lithium ion sieve in engineering.

Key words: lithium extraction from salt lake, Ti-based lithium ion sieve, mixed crystal TiO₂, acid resistance, adsorption capacity

CLC Number:

TQ134.11

YANG Hengyu, MO Hengliang, LI Tianyu, LÜ Long, CHEN Yili, WANG Luocong, ZHAO Wenfang, LIU Manman. Study on synthesis of high acid resistant Ti-based lithium ion sieve using mixed crystal TiO₂ as titanium source[J]. Inorganic Chemicals Industry, 2025, 57(7): 57-63.

Figures/Tables 9

Table 1

Fig.1

Fig.2

Fig.3

Fig.4

Table 2

Fig.5

Fig.6

Fig.7

References 18

[1]	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 Yuanyuan.Supply-demand situation and external dependence of China′s lithium resource［J］.Resources & Industries，2019，21（3）：46-50.
[2]	曹倩，沙秋，刘人和，等.国内外锂产业发展现状和思考［J］.石油科技论坛，2024，43（1）：94-102.
	CAO Qian， SHA Qiu， LIU Renhe，et al.Present conditions and thinking of Chinese and foreign lithium industrial development［J］.Petroleum Science and Technology Forum，2024，43（1）：94-102.
[3]	韩佳欢，郑绵平，乜贞，等.我国深层地下卤水钾、锂资源及其开发前景［J］.盐湖研究，2024，32（2）：90-100.
	HAN Jiahuan， ZHENG Mianping， NIE Zhen，et al.Lithium and potassium resources of oilfield brine and development prospects in China［J］.Journal of Salt Lake Research，2024，32（2）：90-100.
[4]	靳佳奇，李岩，林森.盐湖卤水吸附提锂技术研究进展［J］.化学工程，2023，51（5）：20-25.
	JIN Jiaqi， LI Yan， LIN Sen.Research progress of lithium extraction from salt lake brine by adsorption［J］.Chemical Engineering（China），2023，51（5）：20-25.
[5]	张建勇.国内外提锂工艺综述［J］.山东化工，2023，52（19）：120-122，127.
	ZHANG Jianyong.Review of lithium extraction technology at home and abroad［J］.Shandong Chemical Industry，2023，52（19）：120-122，127.
[6]	路青强，陈琳琳，巢艳红，等.钛系锂离子筛用于盐湖提锂的研究进展［J］.化工进展，2021，40（S1）：1-12.
	LU Qingqiang， CHEN Linlin， CHAO Yanhong，et al.Research progress of titanium-based lithium ion sieve for extracting lithium from salt lake brine［J］.Chemical Industry and Engineering Progress，2021，40（S1）：1-12.
[7]	ZHONG Jing， LIN Sen， YU Jianguo.Li⁺ adsorption performance and mechanism using lithium/aluminum layered double hydroxides in low grade brines［J］.Desalination，2021，505：114983.
[8]	ZHANG Guotai， Chunxi HAI， ZHOU Yuan，et al.Al and F ions co-modified Li_1.6Mn_1.6O₄ with obviously enhanced Li⁺ adsorption performances［J］.Chemical Engineering Journal，2022，450：137912.
[9]	冀颖，张颖，侯雪超，等.钛系吸附剂在西藏碳酸盐型盐湖中的应用研究［J］.无机盐工业，2023，55（11）：70-77.
	JI Ying， ZHANG Ying， HOU Xuechao，et al.Application research of titanium adsorbent of carbonate-type salt lake in Tibet［J］.Inorganic Chemicals Industry，2023，55（11）：70-77.
[10]	黄江龙，赵文芳，莫恒亮，等.两种基于钛酸锂型锂离子筛的性能差异研究［J］.现代化工，2024，44（3）：140-144.
	HUANG Jianglong， ZHAO Wenfang， MO Hengliang，et al.Study on performance difference between two types of lithium titanate-based lithium ionic sieve［J］.Modern Chemical Industry，2024，44（3）：140-144.
[11]	PU Xinghong， DU Xinhe， JING Peng，et al.Interface and defect engineering enable fast and high-efficiency Li extraction of metatitanic acid adsorbent［J］.Chemical Engineering Journal，2021，425：130550.
[12]	胡月，莫恒亮，李天玉，等.钛系锂离子筛粉体与PVDF树脂纺丝成型及性能研究［J］.无机盐工业，2023，55（11）：58-63.
	HU Yue， MO Hengliang， LI Tianyu，et al.Study on spinning molding and performance of Ti-based lithium ion sieve powder and PVDF resin［J］.Inorganic Chemicals Industry，2023，55（11）：58-63.
[13]	ZHANG Liyuan， HE Gang， ZHOU Dali，et al.Study on transformation mechanism of lithium titanate modified with hydrochloric acid［J］.Ionics，2016，22（11）：2007-2014.
[14]	王玉光.纳米二氧化钛光催化材料研究现状［J］.无机盐工业，2012，44（3）：50-53.
	WANG Yuguang.Present research status of nano-sized TiO₂ photocatalyst［J］.Inorganic Chemicals Industry，2012，44（3）：50-53.
[15]	HE Gang， ZHANG Liyuan， ZHOU Dali，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.
[16]	ZHANG Liyuan， ZHOU Dali， HE Gang，et al.Effect of crystal phases of titanium dioxide on adsorption performance of H₂TiO₃-lithium adsorbent［J］.Materials Letters，2014，135：206-209.
[17]	LI Xiaowei， CHAO Yanhong， CHEN Linlin，et al.Taming wettability of lithium ion sieve via different TiO₂ precursors for effective Li recovery from aqueous lithium resources［J］.Chemical Engineering Journal，2020，392：123731.
[18]	葛昊.尖晶石型钛酸锂的制备及电化学行为［D］.哈尔滨：哈尔滨工业大学，2009.
	GE Hao.Synthesis and electrochemical performance of spinel lithium titanate［D］.Harbin：Harbin Institute of Technology，2009.

ρ（Li⁺）	ρ（Na⁺）	ρ（K⁺）	ρ（Ca²⁺）	ρ（Mg²⁺）	ρ（B）
0.24	15.3	2.23	0.023	0.76	0.71
ρ（SiO₃^2-）	ρ（Cl^-）	ρ（SO₄^2-）	ρ（CO₃^2-）	ρ（HCO₃^-）
0.008	11.59	19.14	1.78	1.37

样品	吸附容量/ （mg·g^-1）	离子选择性
样品	吸附容量/ （mg·g^-1）	Li/Na	Li/K	Li/Mg	Li/Ca
HTO-0	9.6	13.5	13.0	1.5	1.9
HTO-40%	17.2	15.3	42.4	30.6	23.8
HTO-100%	13.9	15.2	28.6	3.6	5.5

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on synthesis of high acid resistant Ti-based lithium ion sieve using mixed crystal TiO₂ as titanium source

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 18

Related Articles 6

Metrics

Comments

Recommended 0

[1]	HAN Hongjing, ZHANG Jingze, LAMAO Zhuoma, HAN Jizhe, WU Yongmin, TANG Weiping. Preparation of Al-Co co-doped lithium manganese oxide and its adsorption performance of lithium [J]. Inorganic Chemicals Industry, 2023, 55(7): 38-44.
[2]	HU Yue, MO Hengliang, LI Tianyu, PENG Wenjuan, SUN Guangdong, XIAO Hongkang, CHEN Yili, LI Suoding, TANG Yang. Study on spinning molding and performance of Ti-based lithium ion sieve powder and PVDF resin [J]. Inorganic Chemicals Industry, 2023, 55(11): 58-63.
[3]	LI Sen, WANG Jin, WANG Yingying, CAI Mingfang. Synthesis and modification of NaA zeolite and its application in polyurethane system [J]. Inorganic Chemicals Industry, 2023, 55(10): 78-85.
[4]	LIN Yuqing,ZHANG Yiren,QIU Yulong,ZHANG Jiayu,YU Jianguo. Progress and prospect of membrane technology in lithium extraction from salt lake brine [J]. Inorganic Chemicals Industry, 2023, 55(1): 33-45.
[5]	ZHAO Zhanyi,ZHONG Yongheng,LIU Jia,LI Xiaoyan,YONG Meijing. Research on global patent distribution and development countermeasures of lithium industry [J]. Inorganic Chemicals Industry, 2022, 54(7): 10-17.
[6]	Jin Qingqing,Liang Xiaoyi,Zhang Jia′nan,Zhou Xiaolong. Study on adsorption performance of modified spherical activated carbon for ammonia [J]. Inorganic Chemicals Industry, 2021, 53(4): 61-66.

Study on synthesis of high acid resistant Ti-based lithium ion sieve using mixed crystal TiO2 as titanium source