钙－铝－铈三元复合物吸附脱除氟离子的性能及机理

刘雨秋; 高子航; 周慧; 张永奎; 王雅博

doi:10.12476/kczhly.202208250537

钙－铝－铈三元复合物吸附脱除氟离子的性能及机理

四川大学化学工程学院，四川　成都　610065

基金项目: 四川大学“化工之星”优秀青年人才培养计划（2021）

详细信息

作者简介: 刘雨秋（1997-），男，硕士研究生，研究方向为水体中氟污染物去除

通讯作者: 王雅博（1985-），男，博士，副教授，研究方向为先进功能材料合成及水体污染物去除。

中图分类号: TD985

收稿日期: 2022-08-25

刊出日期: 2025-06-25

Fluoride Removal by Calcium-aluminum-cerium Ternary Composite: Adsorption Performances and Mechanism

School of Chemical Engineering, Sichuan University, Chengdu , Sichuan 610065, China

More Information

Corresponding author: WANG Yabo, 53794574@qq.com

Received Date: 25 August 2022

Publish Date: 25 June 2025

摘要

摘要:
工业产出大量氟污染废水，对环境安全与人类的健康有着严重的威胁。本文以共沉淀法合成了钙-铝-铈三元复合物（CAC），用XRD、FT-IR、N₂吸附、SEM等对其进行了表征，并系统探究了CAC对氟的吸附性能及机理。结果表明，在弱酸性环境（pH值 5.0）下CAC对氟离子的吸附性能较好；CAC对氟离子的吸附属于自发、吸热的过程，且符合Langmuir模型，通过模型拟合计算出对氟离子的最大吸附容量为56.28 mg/g；CAC对氟离子的吸附在12 h时平衡，符合拟二级动力学模型；溶液中共存的CO₃^2-、HCO₃^-等对氟离子的吸附有较大影响。CAC吸附除氟的机理主要是静电吸引作用和离子交换。
- 三元复合物 /
- 稀土 /
- 氟离子 /
- 吸附 /
- 废水
Abstract:
Fluoride-containing industrial wastewater poses great threat to environmental safety and human health. In this study, calcium-aluminum-cerium ternary composite (CAC) was synthesized by co-precipitation method, and characterized by XRD, FTIR, N₂ adsorption, SEM, etc.. The performances and mechanisms of F^- adsorption by CAC were thoroughly investigated. Experimental results showed that weakly acidic environment (pH 5.0) was favorable for F^- removal by CAC adsorption. F^- adsorption by CAC was a spontaneous and endothermic process, which could be well described by the Langmuir model. The maximum adsorption capacity was calculated to be 56.28 mg/g, while the adsorption equilibrium reached at about 12 h. The pseudo-second-order kinetic model fitted the adsorption kinetic well. F^- adsorption was remarkably affected by the co-existing CO₃^2- and HCO₃^-, while Cl^-, Br^-, SO₄^2- influenced F^- adsorption little. Electrostatic attraction and ion exchange were considered to be the main adsorption mechanisms.
- ternary composite /
- rare earth /
- fluoride ion /
- adsorption /
- wastewater

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图 1 CAC的X射线衍射图谱(a)、红外表征图谱(b)和零点电荷的测定(c)

Figure 1.

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图 2 CAC的FESEM

Figure 2.

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图 3 CAC的氮气吸附脱附曲线(a)和孔径分布(b)

Figure 3.

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图 4 溶液初始pH值对氟离子去除效率的影响

Figure 4.

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图 5 CAC吸附氟离子的吸附等温线(a)，Langmuir线性拟合(b)，Freundlich线性拟合(c)和Temkin线性拟合(d)

Figure 5.

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图 6 反应温度对氟离子吸附的影响(a)和范德霍夫曲线(b)

Figure 6.

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图 7 CAC吸附氟离子的吸附动力学曲线(a)，拟一阶动力学模型拟合(b)，拟二阶动力学模型拟合(c)和颗粒内扩散模型拟合(d)

Figure 7.

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图 8 共存阴离子对CAC吸附除氟的影响

Figure 8.

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图 9 CAC吸附氟前后的XPS(a)，F 1s(b)，O 1s(c)和Ce 3d(d)的高分辨率XPS

Figure 9.

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表 1 CAC吸附氟离子的等温线参数

Table 1. Parameters of isotherm models of CAC

Isotherm 模型	在298 K, pH=5.0时的拟合参数
Langmuir	K_L=0.815 9 L/mg, q_m=56.28 mg/g, R²=0.995 5
Freundlich	K_F=26.5015/g, n^-1=0.212 0, R²=0.676 3
Temkin	β=334.0486, A_T=38.317 2 L m/g, R²=0.787 4

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表 2 不同材料对氟离子的吸附能力比较

Table 2. Comparison of maximum adsorption capacity of fluoride by various samples

吸附剂	pH值	反应时间/h	q_m/(mg/g)
活性氧化铝^[19]	7.0	16	0.96
Fe-Al-Ce复合材料^[20]	7.0	36	2.22
Ce(Ⅳ)+Zr(Ⅴ) 混合氧化物^[21]	6.0	2	19.50
Fe-La 复合材料^[22]	6.0	--	27.42
Al-Ce 氧化物^[23]	6.0	24	27.50
棉状 Ca-Al-La 复合材料^[24]	7.0	3	29.30
Ca-Al-Ce 三元复合材料	5.0	12	56.28
分层钙铁 Ca-Fe 双金属氧化物^[25]	5.0	0.67	60.97
层状 Al-Zr-La 三金属氢氧化物^[26]	3.0	24	90.68

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表 3 CAC吸附氟的热力学参数

Table 3. Thermodynamic parameters of fluoride adsorption by CAC

温度/ K	ΔG⁰/ (kJ/mol)	ΔH⁰/ (kJ/mol)	ΔS⁰/ (J/(mol·K))
288	-5.86	114.91	420.34
298	-10.89
308	-14.79
318	-18.51

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表 4 CAC吸附氟的动力学参数

Table 4. Kinetic parameters of fluoride adsorption by CAC

动力模型	在298 K, pH = 5.0时的拟合参数
伪一阶	q_{e, cal} =10.43 mg/g, K₁ =0.0016 min/(g·min), R²=0.955 4
伪二阶	q_{e, cal} =36.49 mg/g, K₂ =0.0013 min/(g·min)^, R²=0.996 6
粒子内扩散	K_i1 =0.826 1 min/(g·min), R²=0.972 8 K_i2 =0.354 0 min/(g·min), R²=0.998 0 K_i3 =0.068 7 min/(g·min), R²=0.999 9

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