光伏行业废水中高浓度氟离子核晶造粒回收效能与机制研究  

Study on recovery efficiency and mechanism of high concentration fluoride by a nucleation crystallization pelleting process in photovoltaic wastewater

作　　者：王亚东 付梽浩 周丹姮 王晓昌[1] 金鹏康[1,2] 金鑫 李志林[3] WANG Ya-dong;FU Zhi-hao;ZHOU Dan-heng;WANG Xiao-chang;JIN Peng-kang;JIN Xin;LI Zhi-lin(Department of Environmental and Municipal Engineering,Xi’an University of Architecture and Technology,Xi’an 710055,China;School of Human Settlements and Architectural Engineering,Xi’an Jiaotong University,Xi’an 710049,China;Fluorine Industry Environmental Protection Technology(YUNNAN)Co.,Ltd,Kunming 652199,China)

机构地区：[1]西安建筑科技大学环境与市政工程学院,陕西西安710055 [2]西安交通大学人居环境与建筑工程学院,陕西西安710049 [3]云南氟业环保科技股份有限公司,云南昆明652199

出　　处：《中国环境科学》2025年第2期803-809,共7页China Environmental Science

基　　金：国家自然科学基金资助项目(52230001)。

摘　　要：针对光伏废水中高浓度氟离子与硫酸根共存的特征,基于核晶造粒技术原理,深入解析了该技术对于上述离子共存体系中氟离子的回收效能与机制.研究结果表明:当诱晶剂投加量为4.46gMgCl_(2)/gF,进水流量为67.8×10^(-4)m^(3)/h,静态床高为30%,且晶种粒径为80~100目时,氟离子去除率高达90%.为进一步验证工艺系统稳定性,开展了为期120h的连续流除氟实验,第一阶段(0~40h)系统出水除氟效能可稳定在89%左右,第二阶段(40~120h)增加至92%左右,最终形成的造粒体纯度可达90%以上.结合X射线衍射(XRD)及拉曼光谱(Raman)等表征结果发现氟离子主要以氟化镁及氟镁酸钠的形式附着于晶种表面,且由静态水接触角测试结果及扫描电镜-能谱(SEM-EDS)表征结果发现造粒体表面相较于原晶种更为疏水,且形成了疏松多孔的结构,致使其比表面积更大,强化了造粒体对于氟离子的富集去除.经晶种表面电势电位(ZP)的测定发现,在pH值为6~8内,晶种表面荷正点,且氟离子主要通过静电引力富集于晶种表面,并在诱晶剂的驱动下,在晶种表面成核并生长成致密的造粒体,从水中分离.In response to the challenge of coexisting high concentrations of fluoride(F-)and sulfate(SO_(4)^(2-))in photovoltaic wastewater,based on the principle of nucleation crystallization pelleting process(NCP),its efficacy and mechanisms for removing F-in such ion coexistence systems were thoroughly investigated.Our study demonstrated that under conditions(nucleation inducer dosage 4.46gMgCl_(2)/gF,flow rate 67.8×10^(-4)m^(3)/h,static bed height 30%,and seed particle size 80~100mesh,F-removal efficiency reached up to 90%.To further validate the stability of the process system,continuous flow defluorination experiments were conducted over 120h.In the first stage(0~40hours),F-removal efficiency stabilized at approximately 89%,increasing to over 92%in the second stage(40~120hours),with granule purity exceeding 90%.Analysis using XRD and Roman revealed that F-predominantly adhered to seed surfaces in the forms of magnesium fluoride(MgF2)and sodium magnesium fluoride(NaMgF3).Static water contact angle tests and SEM-EDS characterization indicated that granules exhibited greater hydrophobicity compared to the raw seeds and formed a loose porous structure,thereby increasing their specific surface area and enhancing F-removal.The ZP revealed that in pH 6~8,the seed surface was positively charged,and F-was mainly concentrated around the surface of the seeds by electrostatic attraction,and then driven by the inducer to nucleate and grow into dense granulation on the surface of the seeds,effectively separating F-from water.

关 键 词：光伏行业 高浓度含氟废水 核晶造粒 氟离子 硫酸根离子 

分 类 号：X703[环境科学与工程—环境工程]