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J4 ›› 2016, Vol. 22 ›› Issue (2): 289-.

• 矿物、岩石及地球化学 • 上一篇    下一篇

羟基磷灰石除氟的实验地球化学研究

任超,王洪涛*,季峻峰,李伟*   

  • 出版日期:2016-06-20 发布日期:2016-07-07

Macroscopic and Spectroscopic Study on Fluoride Sorption by HAP

REN Chao, WANG Hongtao*, JI Junfeng, LI Wei*   

  • Online:2016-06-20 Published:2016-07-07

摘要:

中国和世界上许多国家(地区) 都面临着饮用水氟含量超标的问题,因此研究氟的环境地球化学行为以及探索除氟
技术和原理至关重要。本实验采用廉价的非金属矿物羟基磷灰石作为吸附材料,研究羟基磷灰石吸附溶解态F-的地球化学
行为和机制,考察反应时间、pH、初始F-浓度等环境参数对吸附反应的影响。实验结果发现羟基磷灰石对F-的吸附反应需
进行到48 h以上时才接近反应平衡。在实验条件下(pH≥4),F-的吸附量随pH升高而降低,羟基磷灰石对F-的吸附受pH
调控。同时还发现羟基磷灰石在pH=6条件下对F-的吸附等温线既满足Langmuir等温模式(R2=0.89) 同时也满足Freundlich
等温模式(R2=0.99),并推导出该条件的理论最大吸附量为21.6×10-3。本研究还进一步采用了先进的XRD、SEM、
HR-TEM、19F NMR手段,系统地表征了反应前后吸附产物的形态和成分变化,发现在高F-浓度条件下,F-在羟基磷灰石表
面的吸附机制不再是单层的表面配位。核磁共振的结果表明F-可部分取代羟基磷灰石结构中的隧道羟基而形成含氟羟基磷
灰石。研究结果表明羟基磷灰石是一种相当具有潜力的除氟材料,值得进一步开发。

关键词: 羟基磷灰石, 氟, 吸附, 核磁共振, 透射电子显微镜

Abstract:

Geologic fluoride pollution is a worldwide environmental problem, as numerous countries and regions are facing problems
that drinking water contains excess F concentration. In this research, we adopted low-cost non-metal mineral hydroxyapatite (HAP) as adsorbent to study the geochemical behavior and mechanism of F adsorption as a function of reaction time, pH, and initial F concentration. After 48 hours, the reaction reached equilibrium and yielded a maximum adsorption amount of 21.6 mg/g at pH 6 through regression analysis using Langmuir equation. To further understand the mechanisms of F adsorption on HAP, we employed advanced geochemical approaches, such as XRD, SEM, HR-TEM, and 19F solid state NMR, to characterize the sorption products before and after reaction. It can be concluded that formation of F-Hap (s) solid-solution is the dominant mechanism at high F initial concentration (>10 ppm). This study demonstrates that hydroxyapatite is a good candidate material for fluoride removal.

Key words: hydroxyapatite, fluoride, adsorption, NMR, TEM