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

Abstract
Figure/Table
References
Related Citation (3)

Download: PDF (1971 KB) HTML (1 KB)
Export: BibTeX | EndNote (RIS)

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

Received: 22 July 2024

PACS:

X703

	Service

	E-mail this article
	Add to my bookshelf
	Add to citation manager
	E-mail Alert
	RSS
	Articles by authors
	WANG Ya-dong
	FU Zhi-hao
	ZHOU Dan-heng
	WANG Xiao-chang
	JIN Peng-kang
	JIN Xin
	LI Zhi-lin

Cite this article:

WANG Ya-dong,FU Zhi-hao,ZHOU Dan-heng等. Study on recovery efficiency and mechanism of high concentration fluoride by a nucleation crystallization pelleting process in photovoltaic wastewater[J]. CHINA ENVIRONMENTAL SCIENCECE, 2025, 45(2): 803-809.

URL:

http://www.zghjkx.com.cn/EN/ OR http://www.zghjkx.com.cn/EN/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.