改性羟基磷灰石对矿井水中氟的去除性能研究

金属矿山 ›› 2026, Vol. 55 ›› Issue (2): 243-250.

改性羟基磷灰石对矿井水中氟的去除性能研究

田红云¹　罗　盼¹　刘晓程¹　胡雪仪²　曾煜卿²　黄永炳²

1. 中国一冶集团有限公司城市建设分公司,湖北武汉 430080;2. 武汉理工大学资源与环境工程学院,湖北武汉 430070

出版日期:2026-02-15 发布日期:2026-03-04
作者简介:田红云(1975—),女,高级工程师。
基金资助:
国家自然科学基金面上项目(编号:42477412)。

Research on the Removal Performance of Fluorine in Mine Water by Modified Hydroxyapatite

TIAN Hongyun¹　LUO Pan¹　LIU Xiaocheng¹　HU Xueyi²　ZENG Yuqing²　HUANG Yongbing²

1. City Construction Branch,China First Metallurgical Group Co. ,Ltd. ,Wuhan 430080,China;
2. School of Resources and Environmental Engineering,Wuhan University of Technology,Wuhan 430070,China

Online:2026-02-15 Published:2026-03-04

摘要/Abstract

摘要： 针对我国西北煤炭开采区矿井水氟污染严重、传统处理方法成本高且易产生二次污染等问题,研究采
用水热合成法制备纳米羟基磷灰石(nHAP),并通过Al³⁺掺杂改性(nAl / nCa+Al =3%)开发了Al-nHAP 吸附材料,系统评
价其对模拟矿井水中氟的去除性能与作用机制。优化后的nHAP 合成条件为反应温度120 ℃、时间12 h、Ca 与P 摩
尔比1. 67,该条件下nHAP 对初始氟浓度10 mg/ L 溶液的最大吸附容量为3. 57 mg/ g。Al³⁺ 改性后,材料晶体沿特定
晶面择优生长(XRD),表面羟基被部分取代且磷酸根配位增强(FTIR),孔结构仍保持介孔特征(BET),共同促使AlnHAP
在相同吸附条件下对氟的去除率提升至91. 48%,吸附容量达4. 96 mg/ g,较未改性nHAP 提高约39%。吸附行
为更符合准二级动力学模型(R² =0. 998 3)与Langmuir 等温模型(25 ℃下饱和吸附量为16. 61 mg/ g),表明该过程以
化学吸附与单分子层吸附为主。抗干扰试验表明,Al-nHAP 对Cl^- 、NO^-₃ 、SO^2-₄ 等常见阴离子具有良好的耐受性,但CO^2-
₃ 与PO^3-₄ 会因竞争吸附导致除氟率下降约30%。本研究为高氟矿井水治理提供了一种高效、具环境适应性的吸
附材料,具有一定应用潜力。

关键词: 含氟水　羟基磷灰石　铝改性纳米羟基磷灰石　矿井水　吸附除氟

Abstract: In response to the severe fluoride contamination in mine water from coal mining areas of Northwest China and
the limitations of conventional treatment methods such as high cost and secondary pollution,this study developed Al3+ -doped
nano-hydroxyapatite (Al-nHAP,with nAl / nCa+Al = 3%) via a hydrothermal method,systematically evaluating its performance
and mechanism for fluoride removal from simulated mine water. The optimal synthesis conditions for nHAP were determined as
follows:reaction temperature of 120 ℃,time of 12 h,and Ca/ P molar ratio of 1. 67,under which the maximum adsorption capacity
of nHAP for an initial fluoride concentration of 10 mg/ L reached 3. 57 mg/ g. After Al3+ modification,the material exhibited
enhanced crystal growth along specific facets (XRD),partial substitution of surface hydroxyl groups and strengthened
phosphate coordination (FTIR),while maintaining a mesoporous structure (BET). These changes collectively contributed to a
fluoride removal efficiency of 91. 48% and an adsorption capacity of 4. 96 mg/ g under the same conditions,representing an approximately
39% improvement over unmodified nHAP. The adsorption process was better described by the pseudo-second-order
kinetic model (R2 =0. 998 3) and the Langmuir isotherm model (maximum adsorption capacity of 16. 61 mg/ g at 25 ℃),indicating
chemisorption-dominated monolayer adsorption. Interference tests confirmed that Al-nHAP maintained strong tolerance
towards common anions such as Cl^- ,NO^-₃ ,and SO^2-₄ ,although the presence of CO^2-₃ and PO^3-₄ led to a decrease in fluoride removal
by approximately 30% due to competitive adsorption. This study provides an efficient and environmentally adaptable adsorbent
for treating high-fluoride mine water,demonstrating promising application potential.

Key words: fluoride-containing water,hydroxyapatite,Al-modified nano-hydroxyapatite,mine water,fluoride removal by
adsorption

中图分类号:

X523
TB383

田红云　罗　盼　刘晓程　胡雪仪　曾煜卿　黄永炳. 改性羟基磷灰石对矿井水中氟的去除性能研究[J]. 金属矿山, 2026, 55(2): 243-250.

TIAN Hongyun　LUO Pan　LIU Xiaocheng　HU Xueyi　ZENG Yuqing　HUANG Yongbing. Research on the Removal Performance of Fluorine in Mine Water by Modified Hydroxyapatite[J]. Metal Mine, 2026, 55(2): 243-250.

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