正钒酸钙去除铀(VI)的性能与机理

doi:10.15541/jim20250009

摘要/Abstract

摘要： 天然铀矿的开采过程会产生含铀废液,从含铀废液中去除铀(VI)已成为核工业亟待解决的关键问题。本研究基于“源于铀矿,归于铀矿”的核心理念,选择正钒酸钙(Ca₃(VO₄)₂)作为去除铀(VI)的吸附材料,系统研究了在不同吸附条件下,Ca₃(VO₄)₂粉末对铀(VI)的去除性能,并揭示其去除铀(VI)的机理。结果表明：在pH=6、吸附时间2 h、吸附剂质量浓度0.1 g·L^-1、初始铀(VI)质量浓度120 mg·L^-1、吸附温度308 K条件下,Ca₃(VO₄)₂粉末对铀(VI)具有较高的吸附容量(1179.92 mg·g^-1)和去除率(98.33%);Ca₃(VO₄)₂粉末对铀(VI)的去除机理为溶解和矿化,最终生成准钒钙铀矿(Ca(UO₂)₂(VO₄)₂·3H₂O)。在含有Zn²⁺、Cr³⁺、Cu²⁺、Ni²⁺、Co²⁺和Ba²⁺六种共存离子的水溶液中,Ca₃(VO₄)₂粉末对铀(VI)仍具有较高的吸附容量和去除率,且Ca₃(VO₄)₂粉末能够将铀(VI)质量浓度从121.49 mg·L^-1降低至0.1 mg·L^-1,该值低于相关国家排放标准(GB 23727-2020)。本研究制备的Ca₃(VO₄)₂粉末作为一种处理含铀(VI)废水的吸附材料具有较好的应用前景。

关键词: 正钒酸钙, 铀(VI), 吸附容量, 去除率, 矿化

Abstract: The mining process of natural uranium ore generates uranium-containing wastewater, and the removal of uranium(VI) from such wastewater has emerged as a critical challenge requiring urgent resolution in the nuclear industry. Guided by the principle of "from uranium mines, back to uranium mines," this study selected calcium orthovanadate (Ca₃(VO₄)₂) as an adsorbent for U(VI) removal. The adsorption performance of Ca₃(VO₄)₂ powder under varying conditions and its underlying mechanism were systematically investigated. Results demonstrated that under optimal conditions (pH 6, adsorption time=2 h, adsorbent dosage=0.1 g·L⁻¹, initial U(VI) mass concentration=120 mg·L⁻¹, temperature=308 K), Ca₃(VO₄)₂ powder exhibited a high adsorption capacity (1179.92 mg·g⁻¹) and removal efficiency (98.33%) for U(VI). Removal mechanism was attributed to dissolution and mineralization processes, with the formation of metatyuyamunite (Ca(UO₂)₂(VO₄)₂·3H₂O) on powder surface after adsorption. Even in the presence of six coexisting ions (Zn²⁺, Cr³⁺, Cu²⁺, Ni²⁺, Co²⁺, and Ba²⁺), Ca₃(VO₄)₂ maintained high adsorption performance, reducing U(VI) mass concentration from 121.49 to 0.1 mg·L⁻¹, which is below the limit specified by the national discharge standard (GB 23727-2020). These findings highlight Ca₃(VO₄)₂ as a promising adsorbent for efficient treatment of U(VI)-containing wastewater.

Key words: calcium orthovanadate, U(VI), adsorption capacity, removal rate, mineralization

中图分类号:

X591

王红琴, 邓浩, 梁华, 田强, 晏敏皓, 黄毅. 正钒酸钙去除铀(VI)的性能与机理[J]. 无机材料学报, DOI: 10.15541/jim20250009.

WANG Hongqin, DENG Hao, LIANG Hua, TIAN Qiang, YAN Minhao, HUANG Yi. Properties and Mechanism of U(VI) Removal by Calcium Orthovanadate[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250009.

参考文献

[1] XIE Y H, YU L, CHEN L,et al. Recent progress of radionuclides separation by porous materials. Science China Chemistry, 2024, 67(11): 3515.
[2] ZHANG X Y, YAN M J, CHEN P,et al. Emerging MOFs, COFs, and their derivatives for energy and environmental applications. The Innovation, 2025, 6(2): 100778.
[3] 谢永波, 曾涛涛, 王国华, 等. 铀矿山生态环境修复. 北京: 科学出版社, 2021.
[4] KHARE D, ACHARYA C.Uranium biomineralization by immobilizedChryseobacterium sp. strain PMSZPI cells for efficient uranium removal. Journal of Hazardous Materials, 2024, 465: 133503.
[5] MEZA I, HUA H, GAGNON K,et al. Removal of aqueous uranyl and arsenate mixtures after reaction with limestone, PO₄^3-, and Ca². Environmental Science & Technology, 2023, 57(49): 20881.
[6] YU Y, LIU J Y, CHEN S S,et al. Bioinspired electrostatic layer-by-layer assembly membranes constructed based on mild strategy for uranium extraction from seawater. Chemical Engineering Journal, 2024, 486: 149783.
[7] LI X, LIU Z R, HUANG M.Purification of uranium-containing wastewater by adsorption: a review of research on resin materials.Journal of Radioanalytical and Nuclear Chemistry, 2022, 331(7): 3043.
[8] YU C X, JIANG W, LEI M,et al. Fabrication of carboxylate-functionalized 2D MOF nanosheet with caged cavity for efficient and selective extraction of uranium from aqueous solution. Small, 2024, 20(23): 2308910.
[9] ZHONG X, TAN Y B, WU S Y,et al. Efficient and rapid capture of uranium(VI) in wastewater via multi-amine modified β-cyclodextrin porous polymer. Chinese Journal of Chemical Engineering, 2024, 68: 144.
[10] 王浩, 陈枫, 柯倩, 等. 氮化硼负载磷钨酸铁对U(Ⅵ)的吸附及其机理研究. 中国科学: 化学, 2019, 49(1): 123.
FENG S W, FENG L J, WANG M,et al. Highly efficient extraction of uranium from seawater by natural marine crab carapace. Chemical Engineering Journal, 2022, 430: 133038.
[12] 夏雪, 周磊, 杨国辉, 等. 磷石膏/固硫灰渣复合材料对铀(Ⅵ)的吸附行为及机理研究. 金属矿山, 2023(11): 81.
WU T N, WANG M B, ZHONG T T,et al. Behavior of uranium immobilization with hydroxyapatite and dissolution stability of the immobilization product. Journal of Radioanalytical and Nuclear Chemistry, 2023, 332(3): 647.
[14] DAN H, CHEN L Y, XIAN Q,et al. Tailored synthesis of SBA-15 rods using different types of acids and its application in adsorption of uranium. Separation and Purification Technology, 2019, 210: 491.
[15] LIN Y L, LIU Y H, ZHANG S,et al. Electrochemical synthesis of EuVO₄ for the adsorption of U(VI): performance and mechanism. Chemosphere, 2021, 273: 128569.
[16] LAUF R J.Mineralogy of uranium and thorium. Atglen: Schiffer Publishing, 2016.
[17] BANERJEE C, DUDWADKAR N, TRIPATHI S C,et al. Nano-cerium vanadate: a novel inorganic ion exchanger for removal of americium and uranium from simulated aqueous nuclear waste. Journal of Hazardous Materials, 2014, 280: 63.
[18] KARYAKIN N V, CHERNORUKOV N G, SULEIMANOV E V,et al. Thermodynamics of alkali metal uranovanadates. Russian Journal of General Chemistry, 2001, 71(9): 1333.
[19] KARYAKIN N V, CHERNORUKOV N G, SULEIMANOV E V,et al. Chemical thermodynamics of alkaline-earth metal uranovanadates. Radiochemistry, 2003, 45(5): 457.
[20] 杜浪, 李玉香, 马雪, 等. 偶氮胂Ⅲ分光光度法测定微量铀. 冶金分析, 2015, 35(1): 68.
门倩, 唐振平, 刘江, 等. 湘南某铀矿山周边水体放射性金属及重金属污染特征. 湖北农业科学, 2019, 58(15): 39. [22] YUE H R, XUE X X. Evolution of generated calcium vanadates at different locations in the vicinity of the V₂O₅/CaO interface with annealing parameters.Metallurgical and Materials Transactions B, 2020, 51(5): 2358.
[23] PARHI P, MANIVANNAN V, KOHLI S,et al. Synthesis and characterization of M₃V₂O₈(M = Ca, Sr and Ba) by a solid-state metathesis approach. Bulletin of Materials Science, 2008, 31(6): 885.
[24] CHEN J L, YANG X, WANG L Y,et al. Graphene oxide wrapped Cu-MOF as an efficient adsorbent for uranium extraction from aqueous solution. Journal of Radioanalytical and Nuclear Chemistry, 2024, 333(1): 263.
[25] LIAO J, HE X S, ZHANG Y,et al. The construction of magnetic hydroxyapatite-functionalized pig manure-derived biochar for the efficient uranium separation. Chemical Engineering Journal, 2023, 457: 141367.
[26] LIU Y F, NI S, WANG W J,et al. Facile and scalable synthesis of functionalized hierarchical porous polymers for efficient uranium adsorption. Water Research, 2024, 257: 121683.
[27] GUO X, FENG Y R, MA L,et al. Phosphoryl functionalized mesoporous silica for uranium adsorption. Applied Surface Science, 2017, 402: 53.
[28] PENG T Q, WANG Y F, XU Y F,et al. Synthesis, characterization and uranium (VI) adsorption mechanism of novel adsorption material poly (tetraethylenepentamine-trimesoyl chloride). Journal of Radioanalytical and Nuclear Chemistry, 2023, 332(2): 409.
[29] WANG Q, WANG Y, WU Y Q,et al. Salicylhydroxamic acid intercalated layered double hydroxide for efficient uranium uptake from seawater. Journal of Environmental Chemical Engineering, 2025, 13(1): 115055.
[30] CHERNORUKOV N G, NIPRUK O V, KNYAZEV A V,et al. Uranyl orthovanadate of composition (UO₂)₃(VO₄)₂·4H₂O: synthesis and characterization. Russian Journal of Inorganic Chemistry, 2013, 58(5): 506.
[31] MOLLICK S, SAURABH S, MORE Y D,et al. Benchmark uranium extraction from seawater using an ionic macroporous metal-organic framework. Energy & Environmental Science, 2022, 15(8): 3462.
[32] 赵凯鑫, 高琼, 田强, 等. 磷酸三钙去除U(Ⅵ)的性能与机理研究. 核化学与放射化学, 2023, 45(4): 364.
[33] ZHANG L, JING X Y, LI R M, et al. Magnesium carbonate basic coating on cotton cloth as a novel adsorbent for the removal of uranium. RSC Advances, 2015, 5(30): 23144.
[34] LI L X, ZHOU Z K, WANG G H, et al. Adsorption performance and its mechanism of uranium using rod-like hydroxyapatite by one-step hydrothermal method. Physica Scripta, 2024, 99(8): 085944.
[35] ISSA R A M, AMARI A O E, ALHANASH H B, et al. Removal of uranium (VI) ion from aqueous solution using kaolinite. Kuwait Journal of Science, 2023, 50(4): 609.
[36] KHEMAISSIA S, ABAIDIA R, HOUHOUNE F,et al. Synthesis and characterization of ZSM-12 zeolite for uranium(VI) adsorption: isotherm, kinetic, and thermodynamic investigations. Comptes Rendus Chimie, 2025, 28: 79.
[37] LUO J Q, CHEN J L, CHEN J,et al. Aluminum vanadate microspheres is a simple but effective material for uranium extraction: performance and mechanism. Journal of Solid State Chemistry, 2022, 312: 123237.

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