基于萃取色层法分离锆铪的萃淋树脂制备、结构与性能

doi:10.16085/j.issn.1000-6613.2024-1443

摘要/Abstract

摘要：

锆、铪是核工业中无法替代的材料，其分离技术的发展在高端技术领域至关重要。萃取色层法结合了离子交换法和溶剂萃取法的优点，生产能力大、分离效率高、选择性好，在锆铪分离中展现出巨大潜力，其中起关键作用的是萃淋树脂。本文按照萃取官能团的酸碱性，将已报道的锆铪分离萃淋树脂按照中性基团（酮类、中性磷类、冠醚类、酰胺类）、酸性基团（有机磷酸类、磺酸类）和碱性基团（含N类、季铵盐类）修饰的萃淋树脂进行分类，对其制备方法、结构与性能进行了讨论与总结。酮类基团修饰的萃淋树脂对锆铪吸附能力很弱，锆铪分离效率低；中性磷类基团、含N类和季铵盐类基团修饰的萃淋树脂需在高酸度下分离锆铪，分离体系腐蚀性大，对设备要求高；冠醚类基团可识别并匹配锆、铪金属离子，但价格十分昂贵，其应用受限；酰胺类基团修饰的萃淋树脂对锆、铪的饱和吸附量较大，但研究有限；酸性基团修饰的萃淋树脂对锆、铪具有强吸附能力和高饱和吸附量，但锆铪分离系数较低，且反萃困难。鉴于此，开发支链较多的二烷基次膦酸官能团修饰的萃淋树脂可有利于实现锆铪的高效吸附分离。

关键词: 锆, 铪, 分离, 萃取色层法, 萃淋树脂

Abstract:

Zirconium(Zr) and hafnium(Hf) are indispensable materials in the nuclear industry and their separation technology is crucial to the development of advanced technological fields. The extraction chromatography method, which combines the advantages of ion exchange and solvent extraction, offers high production capacity, high separation efficiency and excellent selectivity, demonstrating great potential in Zr/Hf separation with the extractant-loaded resin playing a key role. This paper categorized the reported Zr/Hf separation extractant-loaded resins based on the acidity/basicity of the extraction functional groups into neutral (ketones, neutral phosphorus, crown ethers, amides), acidic (organic phosphates, sulfonic acids) and basic (N-containing basic groups, quaternary ammonium salts) groups. Their preparation, structures and properties were discussed and summarized. Ketone group-modified extraction resins had a weak adsorption capacity for Zr/Hf and low separation efficiency for Zr/Hf. Neutral phosphorus-based groups, nitrogen-containing basic groups and quaternary ammonium salt group-modified extraction resins required high acidity for the separation of Zr/Hf, requiring high quality of the equipment on corrosion resistance. Crown ether groups can recognize and match Zr/Hf metal ions, but their high cost restricted their application. Amide group-modified extraction resins had a significant saturation adsorption capacity for Zr/Hf, but research in this area was limited. Acidic group-modified extraction resins exhibited strong adsorption capacity and high saturation adsorption capacity for Zr/Hf, but the separation factor between these elements was low and the stripping was difficult. In view of this, the development of branched dialkyl phosphinic acid group-modified extraction resins could facilitate the efficient adsorption separation of Zr/Hf.

Key words: zirconium, hafnium, separation, chromatography, extraction resin

中图分类号:

TQ028

杨秀敏, 胡成强, 王俊莲, 李勇, 刘新宇. 基于萃取色层法分离锆铪的萃淋树脂制备、结构与性能[J]. 化工进展, 2025, 44(10): 5991-6003.

YANG Xiumin, HU Chengqiang, WANG Junlian, LI Yong, LIU Xinyu. Preparation, structures and performance of extraction resins based on zirconium and hafnium separation with extraction chromatography[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5991-6003.

图/表 10

参考文献 69

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树脂	官能团	基底	制备方法	体系最佳条件	选择性	Q_max(Hf)/mg·g^-1	Q_max(Zr)/mg·g^-1	分离系数β	参考文献
SIR-MIBK/HPD100		HPD100	浸渍法	[NH₄SCN]=0.5mol/L,[HCl]=1.1mol/L	Hf	14.33	473.80	—	[14]
SIR-TBP/PEG-coated-SPIONs		PEG-coated-γ-Fe₂O₃	浸渍法	[HNO₃]=4.0mol/L	Zr	—	—	β_Zr/Hf=5	[40]
SIR-TBP/PEG-coated-SPIONs		PEG-coated-γ-Fe₂O₃	浸渍法	[HCl]=4.0mol/L	Hf	—	—	β_Hf/Zr=1.4	[40]
UTEVA		—	浸渍法	[HCl]=5.6mol/L	Zr	—	—	β_Zr/Hf>9.4	[13]
				[HNO₃]=4.9mol/L	Zr	—	—	β_Zr/Hf=10±1
				[H₂SO₄]=12.1mol/L	Hf	—	—	β_Hf/Zr=2.0±0.2
MPFSG		SiO₂	接枝法	HNO₃, pH=1.8	Zr	11.8	12.3	β_Zr/Hf=1.1	[41]
BPFSG		SiO₂	接枝法	HNO₃, pH=1.8	Zr	15	16.7	β_Zr/Hf=1.2	[41]
AAPPFSG		SiO₂	接枝法	HNO₃, pH=1.8	Zr	24	29	β_Zr/Hf=11.0	[41]
SGN18		SiO₂	接枝法	HCl, pH=1.5	Zr	3.3	38.3	β_Zr/Hf=5.72	[45]
SIR-Calix[4]arene-R14/SiO₂-P		SiO₂-P	浸渍法	[HCl]=1mol/L	Zr	—	—	β_Zr/Hf=1.4	[44]
SIR-TODGA/SiO₂-P		SiO₂-P	浸渍法	[HCl]=1.5mol/L	Zr	75.85	44.24	β_Zr/Hf=5.2	[44]
R-PO₄H₂		GMA/DVB 修饰的 Fe₃O₄	接枝法	HCl, pH=2.5	Zr	42.88	85.75	β_Zr/Hf=6	[50]
TVEX-P507		苯乙烯-二乙烯基共聚物	原位聚合法	[H₂SO₄]=0.08mol/L	Hf	0.21	—	β_Hf/Zr=6.81	[51]
SiO₂-POOH		SiO₂	接枝法	[H₂SO₄]=0.5mol/L	Hf	31.62	—	β_Hf/Z_r =4.69	[54]
Mer-CON-POOH-HYY2		氯球	接枝法	[H₂SO₄]=0.3mol/L	Hf	13.16	—	β_Hf/Zr=4.33	[55]
Mer-CON-POOH-272		氯球	接枝法	[H₂SO₄]=0.3mol/L	Hf	11.11	—	β_Hf/Zr=2.96	[55]
PS-G1.0-MSNs		SiO₂	接枝法	HNO₃, pH=0.5	Hf	5.36	25.7	β_Hf/Zr=2.0	[58]
Marathon C	—SO₃H	苯乙烯-二乙烯基共聚物	接枝法	H₂SO₄, pH=2.5	Hf	24.92	103.74	β_Hf/Zr=2.63	[59]
Diphonix	—PO₄H₂、—SO₃H、—COOH	苯乙烯-二乙烯基共聚物	接枝法	[H₂SO₄]=1mol/L	Hf	—	—	β_Hf/Zr=1.47	[60]
Purolite S-957	—PO₄H₂、—SO₃H	苯乙烯-二乙烯基共聚物	接枝法	[H₂SO₄]=0.5mol/L	Hf	—	—	β_Hf/Zr=2.8	[61]
SIR-BTP/ SiO₂-P		SiO₂-P	浸渍法	[HCl]=1mol/L	Hf	—	—	β_Hf/Zr=1.1	[44]
Reillex PVP		苯乙烯-二乙烯基共聚物	接枝法	[HCl]=9.5mol/L	Zr	—	—	β_Zr/Hf=10.4	[67]
TEVA		—	浸渍法	[HCl]=8.4mol/L	Zr	—	—	β_Zr/Hf=18±8	[13]
Amberjet 4200 Cl		苯乙烯-二乙烯基共聚物	接枝法	[HCl]=9.5mol/L	Zr	—	86	β_Zr/Hf=11.4	[67]
Reillex HPQ		聚乙烯基吡咯烷酮-二乙烯基苯	—	[HCl]=9.5mol/L	Zr	—	—	β_Zr/Hf=9.7	[67]

树脂	官能团	基底	制备方法	体系最佳条件	选择性	Q_max(Hf)/mg·g^-1	Q_max(Zr)/mg·g^-1	分离系数β	参考文献
SIR-MIBK/HPD100		HPD100	浸渍法	[NH₄SCN]=0.5mol/L,[HCl]=1.1mol/L	Hf	14.33	473.80	—	[14]
SIR-TBP/PEG-coated-SPIONs		PEG-coated-γ-Fe₂O₃	浸渍法	[HNO₃]=4.0mol/L	Zr	—	—	β_Zr/Hf=5	[40]
SIR-TBP/PEG-coated-SPIONs		PEG-coated-γ-Fe₂O₃	浸渍法	[HCl]=4.0mol/L	Hf	—	—	β_Hf/Zr=1.4	[40]
UTEVA		—	浸渍法	[HCl]=5.6mol/L	Zr	—	—	β_Zr/Hf>9.4	[13]
				[HNO₃]=4.9mol/L	Zr	—	—	β_Zr/Hf=10±1
				[H₂SO₄]=12.1mol/L	Hf	—	—	β_Hf/Zr=2.0±0.2
MPFSG		SiO₂	接枝法	HNO₃, pH=1.8	Zr	11.8	12.3	β_Zr/Hf=1.1	[41]
BPFSG		SiO₂	接枝法	HNO₃, pH=1.8	Zr	15	16.7	β_Zr/Hf=1.2	[41]
AAPPFSG		SiO₂	接枝法	HNO₃, pH=1.8	Zr	24	29	β_Zr/Hf=11.0	[41]
SGN18		SiO₂	接枝法	HCl, pH=1.5	Zr	3.3	38.3	β_Zr/Hf=5.72	[45]
SIR-Calix[4]arene-R14/SiO₂-P		SiO₂-P	浸渍法	[HCl]=1mol/L	Zr	—	—	β_Zr/Hf=1.4	[44]
SIR-TODGA/SiO₂-P		SiO₂-P	浸渍法	[HCl]=1.5mol/L	Zr	75.85	44.24	β_Zr/Hf=5.2	[44]
R-PO₄H₂		GMA/DVB 修饰的 Fe₃O₄	接枝法	HCl, pH=2.5	Zr	42.88	85.75	β_Zr/Hf=6	[50]
TVEX-P507		苯乙烯-二乙烯基共聚物	原位聚合法	[H₂SO₄]=0.08mol/L	Hf	0.21	—	β_Hf/Zr=6.81	[51]
SiO₂-POOH		SiO₂	接枝法	[H₂SO₄]=0.5mol/L	Hf	31.62	—	β_Hf/Z_r =4.69	[54]
Mer-CON-POOH-HYY2		氯球	接枝法	[H₂SO₄]=0.3mol/L	Hf	13.16	—	β_Hf/Zr=4.33	[55]
Mer-CON-POOH-272		氯球	接枝法	[H₂SO₄]=0.3mol/L	Hf	11.11	—	β_Hf/Zr=2.96	[55]
PS-G1.0-MSNs		SiO₂	接枝法	HNO₃, pH=0.5	Hf	5.36	25.7	β_Hf/Zr=2.0	[58]
Marathon C	—SO₃H	苯乙烯-二乙烯基共聚物	接枝法	H₂SO₄, pH=2.5	Hf	24.92	103.74	β_Hf/Zr=2.63	[59]
Diphonix	—PO₄H₂、—SO₃H、—COOH	苯乙烯-二乙烯基共聚物	接枝法	[H₂SO₄]=1mol/L	Hf	—	—	β_Hf/Zr=1.47	[60]
Purolite S-957	—PO₄H₂、—SO₃H	苯乙烯-二乙烯基共聚物	接枝法	[H₂SO₄]=0.5mol/L	Hf	—	—	β_Hf/Zr=2.8	[61]
SIR-BTP/ SiO₂-P		SiO₂-P	浸渍法	[HCl]=1mol/L	Hf	—	—	β_Hf/Zr=1.1	[44]
Reillex PVP		苯乙烯-二乙烯基共聚物	接枝法	[HCl]=9.5mol/L	Zr	—	—	β_Zr/Hf=10.4	[67]
TEVA		—	浸渍法	[HCl]=8.4mol/L	Zr	—	—	β_Zr/Hf=18±8	[13]
Amberjet 4200 Cl		苯乙烯-二乙烯基共聚物	接枝法	[HCl]=9.5mol/L	Zr	—	86	β_Zr/Hf=11.4	[67]
Reillex HPQ		聚乙烯基吡咯烷酮-二乙烯基苯	—	[HCl]=9.5mol/L	Zr	—	—	β_Zr/Hf=9.7	[67]