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

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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4.46gMgCl₂/gF,进水流量为67.8×10^-4m³/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.

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	王亚东
	付梽浩
	周丹姮
	王晓昌
	金鹏康
	金鑫
	李志林

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

Abstract：In response to the challenge of coexisting high concentrations of fluoride (F^-) and sulfate (SO₄^2-) 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 4.46gMgCl₂/gF, flow rate 67.8x10^-4m³/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.

Key words： photovoltaic industry high concentration fluoride-containing wastewater nucleation crystallization pelleting process (NCP) fluoride sulfate

收稿日期: 2024-07-22

PACS:

X703

基金资助:国家自然科学基金资助项目(52230001)

通讯作者: 金鹏康,教授,pkjin@xjtu.edu.cn E-mail: pkjin@xjtu.edu.cn

作者简介: 王亚东(1994-),男,江苏南通人,西安建筑科技大学博士研究生,主要研究方向为污废水深度处理与资源化利用.发表论文2篇.1365663571@qq.com.

引用本文:

王亚东, 付梽浩, 周丹姮, 王晓昌, 金鹏康, 金鑫, 李志林. 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[J]. 中国环境科学, 2025, 45(2): 803-809. WANG Ya-dong, FU Zhi-hao, ZHOU Dan-heng, WANG Xiao-chang, JIN Peng-kang, JIN Xin, LI Zhi-lin. Study on recovery efficiency and mechanism of high concentration fluoride by a nucleation crystallization pelleting process in photovoltaic wastewater. CHINA ENVIRONMENTAL SCIENCECE, 2025, 45(2): 803-809.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2025/V45/I2/803

[1] Djouadi Belkada F, Kitous O, Drouiche N, et al. Electrodialysis for fluoride and nitrate removal from synthesized photovoltaic industry wastewater [J]. Separation and Purification Technology, 2018,204(2): 108-115.
[2] Hu X, Zhu F, Kong L, et al. A novel precipitant for the selective removal of fluoride ion from strongly acidic wastewater: Synthesis, efficiency, and mechanism [J]. Journal of Hazardous Materials, 2021, 403(5):124039.
[3] Deng L, Wang Y, Zhou J, et al. Impact of acid-base conditions on defluoridation by induced crystallization [J]. Journal of Industrial and Engineering Chemistry, 2020,83:35-45.
[4] Ayoob S, Gupta A K, Bhat V T. A conceptual overview on sustainable technologies for the defluoridation of drinking water [J]. Critical Reviews in Environmental Science and Technology, 2008,38(6):401-470.
[5] He J, Yang Y, Wu Z, et al. Review of fluoride removal from water environment by adsorption [J]. Journal of Environmental Chemical Engineering, 2020,8(6):104516.
[6] Qiu Y, Ren L F, Shao J, et al. An integrated separation technology for high fluoride-containing wastewater treatment: Fluoride removal, membrane fouling behavior and control [J]. Journal of Cleaner Production, 2022,349:131225.
[7] 唐婧,范开敏,王芬,等.两种改性膨润土对废水中F^-的吸附研究 [J]. 硅酸盐通报, 2018,37(10):3128-31,40.Tang J, Fan K M, Wang F, et al. Adsorption of fluoride ions from wastewater by two modified bentonites [J]. Journal of Chinese Ceramic Society, 2018,37(10):3128-31,40.
[8] Meenakshi S, Viswanathan N. Identification of selective ion-exchange resin for fluoride sorption [J]. Journal of Colloid and Interface Science, 2007,308(2):438-450.
[9] Damtie M M, Woo Y C, Kim B, et al. Removal of fluoride in membrane-based water and wastewater treatment technologies: Performance review [J]. Journal of Environmental Management, 2019, 251:109524.
[10] 魏永,李贤建,罗政博,等.氧化铝改性活性炭纤维电吸附除氟效能及机理 [J]. 中国环境科学, 2023,43(8):3974-3982.Wei Y, Li X J, Luo Z B, et al. Efficiency and mechanism of fluoride removal by electroadsorption of alumina modified activated carbon fiber [J]. China Environmental Science, 2023,43(8):3974-3982.
[11] 象豫,徐慧,李昆,等.铜绿微囊藻对混凝除氟的促进作用及机理分析 [J]. 中国环境科学, 2021,41(4):1900-1908.Xiang Y, Xu H, Li K, et al. Promotion effect of microcystis aeruginosa on defluorination by coagulation and its mechanism analysis [J]. China Environmental Science, 2021,41(4):1900-1908.
[12] 李含,赵雨,陈嘉超,等.Ce-La双金属氧化物同步去除酸性废水中磷酸盐和氟的性能与机理 [J]. 中国环境科学, 2023,43(10): 5148-5156.Li H, Zhao Y, Chen J C, et al. Simultaneous removal of phosphate and fluoride from acid wastewater by Ce-La bimetal oxides: Performance and mechanism [J]. China Environmental Science, 2023,43(10):5148-5156.
[13] Deng L, Wang Y, Yang H, et al. New insights into defluoridation via induced crystallization: Implications of phosphate species regulation for process efficiency and economics [J]. Separation and Purification Technology, 2024,348:127706.
[14] Peng H, Guo J. Removal of chromium from wastewater by membrane filtration, chemical precipitation, ion exchange, adsorption electrocoagulation, electrochemical reduction, electrodialysis, electrodeionization, photocatalysis and nanotechnology: A review [J]. Environmental Chemistry Letters, 2020,18(6):2055-2068.
[15] Fuge R. Fluorine in the environment, a review of its sources and geochemistry [J]. Applied Geochemistry, 2019,100:393-406.
[16] Hu R, Fan Z, Liu Z, et al. Experimental study on the effects of different factors on the crystallization rate and products of Mn-Ca co-crystallization [J]. Environmental Science and Pollution Research, 2022,30(5):13521-13531.
[17] Chen Y, Fan R, Ad D, et al. Water softening by induced crystallization in fluidized bed [J]. Journal of Environmental Sciences, 2016,50: 109-116.
[18] Gui L, Yang H, Huang H, et al. Liquid solid fluidized bed crystallization granulation technology: Development, applications, properties, and prospects [J]. Journal of Water Process Engineering, 2022,45:102513.
[19] Lacson C F Z, Lu M C, Huang Y H. Chemical precipitation at extreme fluoride concentration and potential recovery of CaF₂particles by fluidized-bed homogenous crystallization process [J]. Chemical Engineering Journal, 2021,415:128917.
[20] Dubey S, Agarwal M, Gupta A B. Recent developments in defluoridation of drinking water in India [J]. Environmental Pollution. 2018,77:345-356.
[21] Tait S, Clarke W P, Keller J, et al. Removal of sulfate from high-strength wastewater by crystallisation [J]. Water Research, 2009, 43(3):762-772.
[22] NorrSström A C, Löv Å. Uranium theoretical speciation for drinking water from private drilled wells in Sweden-Implications for choice of removal method [J]. Applied Geochemistry, 2014,51:148-154.
[23] Shang Y, Wang Y, Li K, et al. Nucleation crystallization pelleting process for highly efficient manganese ion recovery in electrolytic manganese wastewater [J]. Chemical Engineering Journal, 2023,475:146271.
[24] Wang Y, Shang Y, Li K, et al. Enhanced simultaneous phosphate recovery and organics removal by a nucleation crystallization pelleting process [J]. Separation and Purification Technology, 2024,349:127721.
[25] Li Y, Xin H, Zong Y, et al. A novel nucleation-induced crystallization process towards simultaneous removal of hardness and organics [J]. Separation and Purification Technology, 2023,307:122785.
[26] Xuan H, Chen X, Li N, et al. Experimental investigation on preparation of NaMgF₃ and MgF₂ from the leaching solution of SPL [J]. Jom, 2023,75(9):3480-3488.
[27] 唐亚陆.真空蒸发镀制氟化镁增透膜的实验研究 [J]. 中国陶瓷, 2008,(7):27-29,19.Tang Y L. Experimental study on magnesium fluoride antireflection film preparaed by vacuum evaporation plating [J]. Chinese Ceramics, 2008,(7):27-29,19.
[28] 张琳.浮选过程中矿物界面水化特性的研究进展 [J]. 中国有色金属学报, 2024,34(7):2419-2435.Zhang L. Research progress of interfacial hydration characteristics of minerals in flotation process [J]. Chinese Journal of Nonferrous Metals, 2024,34(7):2419-2435.