Application of nanofiltration membrane in concentration of ionic rare earth leach solution

doi:10.11949/0438-1157.20250093

CIESC Journal ›› 2025, Vol. 76 ›› Issue (8): 4095-4107.DOI: 10.11949/0438-1157.20250093

• Separation engineering • Previous Articles Next Articles

Application of nanofiltration membrane in concentration of ionic rare earth leach solution

Huiqin ZHANG¹(), Hongjun ZHAO², Zhengjun FU³, Li ZHUANG⁴, Kai DONG⁵, Tianzhi JIA¹(), Xueli CAO²(), Shipeng SUN¹^,²

^1.NJTECH University Suzhou Future Membrane Technology Innovation Center, Suzhou 215519, Jiangsu, China
^2.State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^3.Weihua Membrane (Kunshan) Technology Company, Kunshan 215337, Jiangsu, China
^4.Jiangsu Jiuwu High-Tech Company, Nanjing 211806, Jiangsu, China
^5.Jianghai Environmental Protection Company, Changzhou 213017, Jiangsu, China

Received:2025-01-22 Revised:2025-03-10 Online:2025-09-17 Published:2025-08-25
Contact: Tianzhi JIA, Xueli CAO

纳滤膜在离子型稀土浸出液提浓中的应用研究

张荟钦¹(), 赵泓竣², 付正军³, 庄力⁴, 董凯⁵, 贾添智¹(), 曹雪丽²(), 孙世鹏¹^,²

^1.南京工业大学苏州未来膜技术创新中心，江苏苏州 215519
^2.南京工业大学化工学院，国家特种分离膜工程技术研究中心，江苏南京 211816
^3.蔚华膜（昆山）科技有限公司，江苏昆山 215337
^4.江苏久吾高科技股份有限公司，江苏南京 211806
^5.江海环保有限公司，江苏常州 213017

通讯作者: 贾添智,曹雪丽
作者简介:张荟钦（1984—），男，博士，zhanghuiqin@jsfmtic.com
基金资助:
国家重点研发计划项目(2023YFE0100900);国家自然科学基金面上项目(22478181);江苏省创新能力建设计划——江苏省技术创新中心课题项目(BM2021804);西南林业大学西南山地森林资源保育与利用教育部重点实验室开放课题项目(LXXK-2023M12)

Abstract

Abstract:

This paper evaluates the potential of nanofiltration membrane technology for concentrating rare earth elements. Commercial nanofiltration membranes were screened in terms of rare earth ion retention and anti-fouling performance, and it was found that improving the saturated solubility of calcium sulfate is the key to improving the concentration rate. Further investigations were conducted to explore the relationship between CaSO₄ solubility and solution conditions, leading to the optimization of the nanofiltration process. Adjusting the solution pH effectively controlled CaSO₄ scaling on the membrane surface, improving membrane performance and increasing rare earth ion concentration. Additionally, the impact of membrane fouling under various operating conditions was analyzed using the Hermia model, providing a theoretical foundation for membrane cleaning and extending service life. This study offers an efficient and environmentally friendly solution for concentrating rare earth leach solutions, with significant application potential.

Key words: nanofiltration, concentration, membrane fouling, rare earth element separation, solubility

摘要：

本研究旨在评估纳滤膜技术在稀土浸出液膜法提浓过程中的应用潜力。从稀土离子截留与抗污染性能方面，对商业膜进行了筛选，发现提高硫酸钙饱和溶解度是提高浓缩倍率的关键。进一步深入研究了硫酸钙溶解度与纳滤膜过程的关系，并对纳滤膜的分离工艺进行了优化。通过调节溶液的pH，有效控制了硫酸钙在膜表面的沉积现象，进而提高了膜处理的效率以及稀土离子的浓缩倍率。此外，应用Hermia模型分析了不同运行条件下膜污染的影响，为膜清洗和延长使用寿命提供了理论依据。本研究为稀土浸出液的提浓提供了一种高效且环保的解决方案，具有显著的应用前景。

关键词: 纳滤, 浓缩, 膜污染, 稀土元素分离, 溶解性

CLC Number:

TQ 028.8

Huiqin ZHANG, Hongjun ZHAO, Zhengjun FU, Li ZHUANG, Kai DONG, Tianzhi JIA, Xueli CAO, Shipeng SUN. Application of nanofiltration membrane in concentration of ionic rare earth leach solution[J]. CIESC Journal, 2025, 76(8): 4095-4107.

张荟钦, 赵泓竣, 付正军, 庄力, 董凯, 贾添智, 曹雪丽, 孙世鹏. 纳滤膜在离子型稀土浸出液提浓中的应用研究[J]. 化工学报, 2025, 76(8): 4095-4107.

Figures/Tables 22

Table 1 The main ionic components of the actual rare earth leaching solution

离子	离子浓度/ (mg/L)
Ca²⁺	158.6
Mg²⁺	1106
Ce³⁺	3.415
La³⁺	56.92

Fig.1 Pure water permeability and rejection of commercial membranes

Fig.2 Change of normalized flux of commercial membrane and the rejection of La3+ in the concentration process of rare earth leaching solution

Fig.3 SEM images of commercial membrane surface before and after the experiment

Table 2 Residual ion concentration on the membrane surface

离子		MNF	MNF-Acid	Duracid	TW-30
Ca²⁺	实验组/(10^-2 mg/L)	4.35	5.10	3.01	6.00
Ca²⁺	浸泡组/(10^-2 mg/L)	低于检测限
La³⁺	实验组/(10^-2 mg/L)	0.14	0.15	0.11	0.23
La³⁺	浸泡组/(10^-2 mg/L)	低于检测限

Fig.4 Residual contaminants on the membrane surface after the experiment

Fig.5 The rejection and Zeta potential of MNF, MNF-Acid, and Duracid membranes

Fig.6 SEM images of the surface of MNF-Acid, and Duracid membranes before and after experiments under different pH conditions

Fig.7 The normalized flux changes of Duracid during the concentration process of simulated rare earth leaching solutions with different concentrations

Table 3 Solubility of CaSO4 under different conditions

项目	浓度/(g/L)			饱和溶解度/(g/L)
项目	Mg²⁺	MgSO₄	La³⁺	Ca²⁺	CaSO₄
pH=5.8	1.4	7	0.4	0.51	1.73
pH=3				0.54	1.84
pH=1				0.82	2.79
1%（质量分数）H₂SO₄				0.66	2.24
pH=5.8	1.4	7	0.4	0.51	1.73
	2	10		0.48	1.63
	2.8	14		0.46	1.56
pH=1	1.4	7	0.05	0.58	1.97
			0.2	0.73	2.48
			0.4	0.82	2.79

Fig.8 The performance changes of MNF-Acid membrane during the concentration process of rare earth leaching solution under different pH conditions

Table 4 The fitting results of Hermia model for membrane fouling process under different pH conditions

pH	Hermia模型拟合精度
pH	完全孔堵塞	中间孔堵塞	标准孔堵塞
5.8	0.9169	0.8806	0.9472
3	0.9779	0.9702	0.9360
1	0.9648	0.9640	0.9284

Fig.9 SEM images of the membrane surface before and after the experiment with MNF-Acid and Duracid under the condition of pH=1

Fig.10 The performance changes of MNF-Acid and Duracid membranes during the concentration process of rare earth leaching solution under the condition of pH=1

Table 5 Solubility of CaSO4 under different recovery rates

pH	浓度/(g/L)			饱和溶解度/(g/L)
pH	Mg²⁺	MgSO₄	La³⁺	Ca²⁺	CaSO₄
5.8	1.4	7	0.4	0.51	1.73
5.8	1.75	8.75	0.5	0.50	1.7
5.8	2.1	10.5	0.6	0.48	1.63
5.8	2	10	0.57	0.50	1.7
5.8	2.8	14	0.8	0.49	1.67
3	1.4	7	0.4	0.54	1.84
3	2	10	0.57	0.51	1.73
3	2.8	14	0.8	0.5	1.7
1	1.4	7	0.4	0.82	2.79
1	2	10	0.57	0.75	2.55
1	2.8	14	0.8	0.75	2.55

Fig.11 The performance changes of MNF-Acid membrane during the concentration process of rare earth leaching solution under different pressure conditions

Table 6 The performance changes of MNF-Acid membrane during the concentration process of rare earth leaching solution under different pressure conditions

压力/bar	Hermia模型拟合精度
压力/bar	完全孔堵塞	中间孔堵塞	标准孔堵塞
4	0.9423	0.9336	0.9464
6	0.9648	0.9640	0.9284
8	0.9601	0.9488	0.9554

Fig.12 The performance changes of MNF-Acid membrane during the concentration process of rare earth leaching solution under different feed flow rate

Table 7 The performance changes of MNF-Acid membrane during the concentration process of rare earth leaching solution under different feed flow rate

流量/(L/h)	Hermia模型拟合精度
流量/(L/h)	完全孔堵塞	中间孔堵塞	标准孔堵塞
30	不适用	0.9154	0.9893
60	0.9864	0.9681	0.9740
90	0.9626	0.9562	0.7371

Fig.13 Concentration test results of membrane modules under different pH conditions

Table 8 Component concentration efficiency and flux attenuation degree

处理效率/(L/h)

最大通量衰减

程度/%

不可逆通量

衰减程度/%

Table 9 Real ion concentration and theoretical concentration during the concentration process of components

pH	离子	时间/(min)	浓度/(g/L)
pH	离子	时间/(min)	真实	理论
5.8	Ca²⁺	35	0.797	0.791
	Ca²⁺	65	1.247	1.4
	La³⁺	35	0.528	0.525
	La³⁺	65	1.062	0.96
1	Ca²⁺	55	1.359	1.3
1	La³⁺	55	0.925	0.893

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Application of nanofiltration membrane in concentration of ionic rare earth leach solution

纳滤膜在离子型稀土浸出液提浓中的应用研究

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