正钒酸钙去除铀(VI)的性能与机理

doi:10.15541/jim20250009

无机材料学报 ›› 2025, Vol. 40 ›› Issue (11): 1268-1276.DOI: 10.15541/jim20250009

正钒酸钙去除铀(VI)的性能与机理

王红琴¹^,²(), 邓浩², 梁华¹, 田强¹, 晏敏皓¹, 黄毅¹()

1.西南科技大学环境友好能源材料国家重点实验室, 绵阳 621010
2.西南科技大学材料与化学学院, 绵阳 621010

收稿日期:2025-01-07 修回日期:2025-03-10 出版日期:2025-04-02 网络出版日期:2025-04-02
通讯作者: 黄毅, 讲师. E-mail: huangyi516@163.com
作者简介:王红琴(1999-), 女, 硕士研究生. E-mail: 1523555457@qq.com
基金资助:
四川省自然科学基金(2022JDTD0017)

Properties and Mechanism of U(VI) Removal by Calcium Orthovanadate

WANG Hongqin¹^,²(), DENG Hao², LIANG Hua¹, TIAN Qiang¹, YAN Minhao¹, HUANG Yi¹()

1. State Key Laboratory of Environment-friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, China
2. School of Materials and Chemistry, Southwest University of Science and Technology, Mianyang 621010, China

Received:2025-01-07 Revised:2025-03-10 Published:2025-04-02 Online:2025-04-02
Contact: HUANG Yi, lecturer. E-mail: huangyi516@163.com
About author:WANG Hongqin (1999-), female, Master candidate. E-mail: 1523555457@qq.com
Supported by:
Natural Science Foundation of Sichuan Province(2022JDTD0017)

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:

Mining process of natural uranium ore generates uranium-containing wastewater, while 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. Adsorption performance of Ca₃(VO₄)₂ powder under varying conditions and its underlying mechanism were investigated. Results demonstrated that under optimal conditions (pH 6, adsorption for 2 h, adsorbent dosage at 0.1 g·L^-1, initial U(VI) mass concentration at 120 mg·L^-1, temperature at 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, forming metatyuyamunite (Ca(UO₂)₂(VO₄)₂·3H₂O) on the powder surface after adsorption. Even in the environment 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, 2025, 40(11): 1268-1276.

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, 2025, 40(11): 1268-1276.

图/表 14

表1 共存离子溶液中各金属离子的初始质量浓度

Table 1 Initial mass concentrations of several metal ions in coexisting ionic solution

Metal ion	ρ₀/(mg·L^-1)	Metal ion	ρ₀/(mg·L^-1)
Zn²⁺	648.63	Co²⁺	67.12
Cr³⁺	101.22	Ba²⁺	64.22
Cu²⁺	72.55	U(VI)	121.49
Ni²⁺	133.04

图1 Ca3(VO4)2粉末的表征结果

Fig. 1 Characterization results of Ca3(VO4)2 powder (a) XRD patterns of Ca3(VO4)2 prepared at different temperatures for 4 h; (b-h) FT-IR spectrum (b), particle size distribution (c), nitrogen adsorption-desorption curves (d), SEM image (e) and EDS mappings (f-h) of Ca3(VO4)2 prepared at 1100 ℃ for 4 h

图2 pH、吸附时间对Ca3(VO4)2去除铀(VI)的影响

Fig. 2 Effect of pH and adsorption time on removal of U(VI) by Ca3(VO4)2 (a) Species distribution of U(VI) with different pH (U(VI) at mass concentration of 120 mg·L-1 under 308 K); (b, c) Adsorption capacity and removal rate of U(VI) with different pH (b) and durations (c); (d-f) Pseudo-first-order (d), pseudo-second-order (e) and Weber-Morris (f) models fitting (temperature at 308 K, initial U(VI) mass concentration at 120 mg·L-1, adsorbent dosage at 0.1 g·L-1)

表2 准一级和准二级动力学模型的拟合参数

Table 2 Fitting parameters of pseudo-first-order and pseudo-second-order kinetic models

Material	Pseudo-first-order		Pseudo-second-order
Material	k₁/min^-1	R²	k₂/(g·mg^-1·min^-1)	R²
Ca₃(VO₄)₂	0.01	0.447	2.62×10^-4	0.999

表3 Weber-Morris动力学模型的拟合参数

Table 3 Fitting parameters of Weber-Morris dynamic model

Material	Weber-Morris
Material	k_p,1/(mg·g^-1·min^-1/2)	R₁²	k_p,2/(mg·g^-1·min^-1/2)	R₂²
Ca₃(VO₄)₂	312.25	0.956	7.65	0.400

图3 吸附剂质量浓度、初始铀(VI)质量浓度和温度对Ca3(VO4)2去除铀(VI)的影响

Fig. 3 Effects of adsorbent dosage, initial U(VI) mass concentration, and temperature on removal of U(VI) by Ca3(VO4)2 (a, b) Adsorption capacity and removal rate of U(VI) with different adsorbent dosages (a) and initial U(VI) mass concentrations (b);(c, d) Langmuir (c) and Freundlich (d) isothermal adsorption models fitting; (e) Adsorption capacity and removal rate of U(VI) at different temperatures; (f) Relationship between lnK and 1/T (temperature at 308 K, pH 6, adsorption time at 2 h)

表4 Freundlich和Langmuir等温吸附模型的拟合参数

Table 4 Fitting parameters of Freundlich and Langmuir isothermal adsorption models

Material	Freundlich		Langmuir
Material	k_F/(mg·g^-1)·(mg·L^-1)^-1/ⁿ	R²	k_L/(L·mg^-1)	R²
Ca₃(VO₄)₂	623.24	0.969	0.09	0.975

表5 热力学拟合参数

Table 5 Thermodynamic fitting parameters

Material	∆H/(kJ·mol^-1)	∆S/(J·mol^-1·K^-1)	∆G/(kJ·mol^-1)
Material	∆H/(kJ·mol^-1)	∆S/(J·mol^-1·K^-1)	303 K	308 K	313 K	318 K	323 K
Ca₃(VO₄)₂	28.55	140.74	-14.09	-14.79	-15.50	-16.20	-16.91

图4 吸附铀(VI)前后Ca3(VO4)2的SEM照片和表面元素分布

Fig. 4 SEM images and surface element distributions of Ca3(VO4)2 before and after adsorption of U(VI) (a, b) SEM images of Ca3(VO4)2 before (a) and after (b) adsorption of U(VI); (c-f) EDS mappings of Ca3(VO4)2 after adsorption of U(VI)

图5 吸附铀(VI)前后Ca3(VO4)2的表征结果

Fig. 5 Characterization results of Ca3(VO4)2 before and after adsorption of U(VI) (a) XPS spectra of Ca3(VO4)2 and UO2(NO3)2·6H2O; (b) U4f XPS spectrum of Ca3(VO4)2 after adsorption of U(VI); (c, d) XRD patterns (c) and FT-IR spectra (d) of Ca3(VO4)2

表6 吸附后共存离子溶液中各金属离子的质量浓度

Table 6 Mass concentrations of several metal ions in coexisting ionic solution after adsorption

Metal ion	ρ₀/(mg·L^-1)	Metal ion	ρ₀/(mg·L^-1)
Zn²⁺	588.55	Co²⁺	63.66
Cr³⁺	0.01	Ba²⁺	60.51
Cu²⁺	0.90	U(VI)	0.10
Ni²⁺	126.60

图6 共存离子溶液中Ca3(VO4)2对各金属离子的吸附容量和去除率

Fig. 6 Adsorption capacity and removal rate of Ca3(VO4)2 for several metal ions in coexisting ionic solution pH 6; Adsorption time: 2 h; Adsorbent dosage: 0.1 g·L-1; Temperature: 308 K

表7 共存离子溶液中Ca3(VO4)2对各金属离子的选择性吸附参数

Table 7 Selective adsorption parameters of Ca3(VO4)2 for several metal ions in coexisting ionic solution

Metal ion	K_d/(L·g^-1)	k	Metal ion	K_d/(L·g^-1)	k
U(VI)	12039.43	1.00	Ni²⁺	0.51	23673.64
Zn²⁺	1.02	11793.32	Co²⁺	0.54	22142.30
Cr³⁺	168687.73	0.07	Ba²⁺	0.61	19636.28
Cu²⁺	791.97	15.20

表8 Ca3(VO4)2与其他吸附材料对铀(VI)的吸附容量[11-12,15,33-37]

Table 8 Adsorption capacity of Ca3(VO4)2 and other adsorbents for uranium (VI) removal[11-12,15,33-37]

Material	Adsorption capacity/(mg·g^-1)	pH	Ref.
Mg₂CO₃(OH)₂	370.00	5.0	[33]
Crab carapace	1.38	8.0	[11]
PG/SFA	84.60	6.0	[12]
HAP	130.08	5.0	[34]
Kaolinite	9.17	4.5	[35]
ZSM-12 zeolite	12.00	3.0	[36]
H₁₁Al₂V₆O_23.2	917.00	5.0	[37]
EuVO₄	276.16	4.5	[15]
Ca₃(VO₄)₂	1179.92	6.0	This study

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正钒酸钙去除铀(VI)的性能与机理

Properties and Mechanism of U(VI) Removal by Calcium Orthovanadate

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