氟磷灰石对酸性水溶液中铀(VI)的去除研究

doi:10.15541/jim20210255

无机材料学报 ›› 2022, Vol. 37 ›› Issue (4): 395-403.DOI: 10.15541/jim20210255

所属专题：【能源环境】水体污染物去除

氟磷灰石对酸性水溶液中铀(VI)的去除研究

马磊¹^,²(), 黄毅¹(), 邓浩², 银航¹^,², 田强¹, 晏敏皓¹

1.西南科技大学环境友好能源材料国家重点实验室
2.西南科技大学材料科学与工程学院, 绵阳 621010

收稿日期:2021-04-15 修回日期:2021-05-27 出版日期:2022-04-20 网络出版日期:2021-06-30
通讯作者: 黄毅, 讲师. E-mail: huangyi516@163.com
作者简介:马磊(1996-), 男, 硕士研究生. E-mail: 2219835537@qq.com
基金资助:
国家自然科学基金(11405139)

Removal of Uranium (VI) from Acidic Aqueous Solution by Fluorapatite

MA Lei¹^,²(), HUANG Yi¹(), DENG Hao², YIN Hang¹^,², TIAN Qiang¹, YAN Minghao¹

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

Received:2021-04-15 Revised:2021-05-27 Published:2022-04-20 Online:2021-06-30
Contact: HUANG Yi, lecturer. E-mail: huangyi516@163.com
About author:MA Lei(1996-), male, Master candidate. E-mail: 2219835537@qq.com
Supported by:
National Natural Science Foundation(11405139)

摘要/Abstract

摘要：

随着全球核能的开发利用, 铀已成为土壤、地表水和地下水的常见污染物, 从含铀废水中去除铀(VI)已成为迫切需要。本工作以氟化钙、焦磷酸钙、氢氧化钙为反应原料合成氟磷灰石, 系统研究了其对铀(VI)的去除性能并采用不同测试手段对吸附铀(VI)前后的氟磷灰石进行表征, 揭示了其相关去除机理。结果表明: 在温度为308 K, pH=3, 固液比为0.12 g/L, 平衡时间为120 min, 初始铀浓度为100 mg/L的条件下, 氟磷灰石对铀(VI)的吸附容量可达655.17 mg/g, 其吸附过程符合准二级动力学和Langmuir等温吸附模型, 且为自发和吸热过程。氟磷灰石对铀(VI)的去除机理为表面矿化, 吸附铀(VI)的氟磷灰石表面产生了新相准钙铀云母[Ca(UO₂)₂(PO₄)₂·6H₂O], 准钙铀云母在pH≥3水溶液中能保持较高稳定性。因此, 氟磷灰石可以作为一种有前景的矿化剂, 用于含铀废水的净化和固体化处理。

关键词: 氟磷灰石, 铀(VI), 去除, 酸性水溶液, 表面矿化机制

Abstract:

Removal of uranium (VI) from uranium (VI) containing waste water is urgently needed with the global nuclear energy exploitation. The present work completed synthesis of fluorapatite and removal of uranium (VI). Fluorapatite was synthesized using calcium fluoride, calcium pyrophosphate and calcium hydroxide as the raw materials. The fluorapatite before and after adsorption of uranium (VI) was characterized. The experimental results show that, at condition of 308 K, pH=3, solid-liquid ratio of 0.12 g/L, equilibrium time of 120 min and initial uranyl ion concentration of 100 mg/L, the adsorption capacity of uranium (VI) by fluorapatite reaches 655.17 mg/g. Adsorption process of uranium (VI) by fluorapatite is in accordance with the pseudo-second-order kinetics and Langmuir isotherm adsorption model. Adsorption of uranium (VI) by fluorapatite is a spontaneous and endothermic reaction. The removal of uranium (VI) by fluorapatite is ascribed to surface mineralization. After uranium (VI) is absorbed, a new phase of meta-autunite [Ca(UO₂)₂(PO₄)₂·6H₂O] is generated on the surface of fluorapatite. The meta-autunite can maintain high stability in the pH≥3 aqueous solution. Above results indicate that fluorapatite can be used as a promising mineralizer for purification and solidification of uranium (VI) containing waste water.

Key words: fluorapatite, uranium (VI), removal, acidic aqueous solution, surface mineralization mechanism

中图分类号:

X591

马磊, 黄毅, 邓浩, 银航, 田强, 晏敏皓. 氟磷灰石对酸性水溶液中铀(VI)的去除研究[J]. 无机材料学报, 2022, 37(4): 395-403.

MA Lei, HUANG Yi, DENG Hao, YIN Hang, TIAN Qiang, YAN Minghao. Removal of Uranium (VI) from Acidic Aqueous Solution by Fluorapatite[J]. Journal of Inorganic Materials, 2022, 37(4): 395-403.

图/表 10

图1 合成氟磷灰石粉体XRD图谱(a), FT-IR谱图 (b), 粒径分布图(c)和SEM照片(d)

Fig. 1 XRD pattern(a), FT-IR spectrum(b), particle size distribution (c) and SEM image (d) of synthetic fluorapatite powder

图2 (a)铀(VI)在不同pH水溶液中的种态分布图(C0=100 mg/L, T=308 K); (b)不同pH水溶液中氟磷灰石对铀(VI)的吸附容量和去除率; (c)不同pH水溶液中氟磷灰石的Zeta电位; (d)固液比对氟磷灰石吸附铀(VI)的影响(pH=3); (e)氟磷灰石吸附铀(VI)随吸附时间的变化(pH=3, 固液比0.12 g/L); (f)初始铀(VI)浓度对氟磷灰石吸附铀(VI)的影响(pH=3, 固液比0.12 g/L, 吸附时间120 min)

Fig. 2 (a) Distribution of uranium (VI) species in the solution with different pH (C0=100 mg/L, T= 308 K); (b) Adsorption capacity and removal rate of uranium (VI) by fluorapatite in the solution with different pH; (c) Zeta potential of fluorapatite in the solution with different pH; (d) Effect of solid-liquid ratio on adsorption of uranium (VI) by fluorapatite (pH3); (e) Change of the adsorption of uranium (VI) by fluorapatite with adsorption time (pH3, solid-liquid ratio at 0.12 g/L); (f) Effect of initial uranium (VI) concentration on adsorption of uranium (VI) by fluorapatite (pH3, solid-liquid ratio at 0.12 g/L, adsorption time=120 min)

图3 氟磷灰石(a)和吸附铀(VI)后的氟磷灰石(b)在不同pH水溶液中的溶解性

Fig. 3 Solubility of fluorapatite (a) and fluorapatite adsorbed with uranium (VI) (b) in the solutions with different pH

图4 (a)303~323 K吸附温度范围, 氟磷灰石对铀(VI)的吸附容量和去除率; (b)吸附过程的热力学模型的线性拟合; (c)准一级动力学模型的非线性拟合; (d)准二级动力学模型的非线性拟合; (e)Langmuir等温吸附模型的非线性拟合; (f) Freundlich等温吸附模型的非线性拟合

Fig. 4 (a) Adsorption capacity and removal rate of uranium (VI) by fluorapatite in the temperature range of 303-323 K; (b) Linear fitting of thermodynamic model for adsorption process; (c) Nonlinear fitting of pesudo-first-order kinetic model; (d) Nonlinear fitting of pesudo-second-order kinetic model; (e) Nonlinear fitting of Langmuir isotherm adsorption model; (f) Nonlinear fitting of Freundlich isotherm adsorption model

表1 吸附过程热力学模型的拟合参数

Table 1 Fitting parameters of thermodynamic model for adsorption

Materials	∆H/(kJ∙mol^-1)	∆S/(J∙mol^-1•K^-1)	∆G/(kJ•mol^-1)
Materials	∆H/(kJ∙mol^-1)	∆S/(J∙mol^-1•K^-1)	303 K	308 K	313 K	318 K	323 K
Fluorapatite	8.41	88.65	-8.47	-8.91	-9.31	-9.8	-10.24

表2 准一级和准二级动力学模型的拟合参数

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

Materials	Pseudo-first-order		Pseudo-second-order
Materials	K₁/min^-1	R²	K₂/ (g∙mg^-1∙min^-1)	R²
Fluorapatite	0.016	0.986	1.85×10^-5	0.999

表3 Langmuir和Freundlich等温吸附模型的拟合参数

Table 3 Fitting parameters of Langmuir and Freundlich isothermal adsorption models

Materials	Langmuir			Freundlich
Materials	q_max/(mg∙g^-1)	R²		n	R²
Fluorapatite	1300.35		0.998	2.18	0.969

图5 吸附铀(VI)前(a)后(b)的氟磷灰石SEM照片和吸附铀(VI)的氟磷灰石表面元素分布图(c~g)

Fig. 5 SEM images of fluorapatite before (a) and after (b) adsorption of uranium (VI), and element mappings (c-g) of the surface of fluorapatite after adsorption of uranium (VI)

图6 氟磷灰石吸附铀(VI)前后(a)和氟磷灰石吸附铀(VI)后U4f(b)的XPS谱图; 氟磷灰石吸附铀(VI))前后Ca2p(c)、O1s(d)、 P2p(e)和F1s(f)的XPS谱图

Fig. 6 (a) XPS spectra of fluorapatite before and after adsorption of uranium (VI) and (b) U4f on the fluorapatite after adsorption of uranium (VI) (b), and XPS spectra of Ca2p(c), O1s(d), P2p(e) and F1s(f) on the fluorapatite before and after adsorption of uranium (VI)

图7 氟磷灰石吸附铀(VI)前后的XRD图谱(a)和FT-IR图谱(b)

Fig. 7 (a) XRD pattern and (b) FT-IR spectra of fluorapatite before and after adsorption of uranium (VI)

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氟磷灰石对酸性水溶液中铀(VI)的去除研究

Removal of Uranium (VI) from Acidic Aqueous Solution by Fluorapatite

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