Coal Geology & Exploration
Abstract
Objective The mine water associated with coal mining tends to be rich in fluoride ions. If discharged directly without effective treatment, such water will cause severe pollution to regional ecology, affecting the quality of water resources and the stability of the ecosystem. Methods This study focuses on the challenging treatment of the fluoride pollution caused by coal mining-associated mine water. To overcome the bottlenecks including low efficiency and weak anti-interference of traditional methods for fluoride removal, this study designed a setup for fluoride removal using the nucleation crystallization pelleting (NCP) processing and proposed a novel fluoride removal method—NCP chemical precipitation. The fluoride pollution of mine water poses great environmental risks since the resulting fluoride mass concentration in surface water might exceed relevant standards by 8‒15 times. The deep fluoride removal in a complex water quality environment is challenging in the prevention and control of fluoride pollution. This study developed a coordinated regulating mechanism integrating multi-phase reactions: chemical precipitation, nucleation induction, and porous adsorption. Process optimization experiments on a laboratory scale were conducted using a continuous flow chemistry system with a hydraulic retention time (HRT) of 45 min and an upward flow rate of 1.8 m/h. Then, this study systematically determined the dynamic process of fluorine migration and transformation using advanced characterization techniques such as X-ray photoelectron spectroscopy (XPS) and in-situ Fourier transform infrared (FTIR) spectroscopy. Results and Conclusions The results indicate that the mass concentration of fluoride dropped from 12.6 mg/L to 7.6 mg/L (removal rate: 39.8%) after only a single stage of processing under the optimized conditions (i.e., a nucleation inducer (CaCl2) dosage of 1 200 mg/L and a seed loading ratio of 1∶50), with efficiency being 2.3 times higher than that of conventional coagulating sedimentation. X-ray diffraction (XRD) corroborated that thermodynamically stable aragonite and vaterite crystals were generated from reactions between Ca2+ and F–. Notably, coexisting carbonates enhanced fluoride removal by forming CaCO3·CaF2 composite precipitates (FTIR reveals a characteristic peak at 1 080 cm–1) or porous calcite carriers (SEM images indicate a porosity increase of 62.76%). This study revealed the regulation pattern of interfacial reactions in a carbonate system. Energy dispersive spectroscopy (EDS) confirmed the gradient distribution of fluorine elements in the cross section of formed particles, revealing the progressive removal mechanism from surface adsorption to lattice fixation. The NCP technique can effectively remove fluoride ions in mine water with complex water quality and can deal with the complex chemical composition in mine water. The results of this study will lay a foundation for the engineering application of the fluoride removal technology based on the NCP process while also providing a feasible technical route for solving the environmental pollution caused by fluoride-bearing mine water.
Keywords
mine water, nucleation crystallization pelleting (NCP) process, fluoride ion, calcium fluoride, migration and transformation, removal mechanism
DOI
10.12363/issn.1001-1986.24.10.0637
Recommended Citation
ZHANG Xiyu, DONG Shuning, WANG Hao,
et al.
(2025)
"Fluoride ion removal from mine water via nucleation crystallization pelleting process,"
Coal Geology & Exploration: Vol. 53:
Iss.
5, Article 17.
DOI: 10.12363/issn.1001-1986.24.10.0637
Available at:
https://cge.researchcommons.org/journal/vol53/iss5/17
Reference
[1] LIU Ting,LIU Shimin. The impacts of coal dust on miners’ health:A review[J]. Environmental Research,2020,190:109849.
[2] YANG Kang,HONG Xiuping,LIANG Handong. Fluorine pollution in a sheep fluorosis area of the northern Helan Mountains,Ningxia,China[J]. Environmental Science Advances,2024,3(1):36−43.
[3] BORGOHAIN X,BORUAH A,SARMA G K,et al. Rapid and extremely high adsorption performance of porous MgO nanostructures for fluoride removal from water[J]. Journal of Molecular Liquids,2020,305:112799.
[4] 王皓,董书宁,尚宏波,等. 国内外矿井水处理及资源化利用研究进展[J]. 煤田地质与勘探,2023,51(1):222−236.
WANG Hao,DONG Shuning,SHANG Hongbo,et al. Domestic and foreign progress of mine water treatment and resource utilization[J]. Coal Geology & Exploration,2023,51(1):222−236.
[5] 李秋宇,袁可,袁进,等. 混凝处理对煤矿矿井水溶解性污染物影响研究[J/OL]. 工业水处理,2024:1–10 [2024-05-27]. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=GYSC20240 523003&dbname=CJFD&dbcode=CJFQ.
LI Qiuyu,YUAN Ke,YUAN Jin,et al. Study on the effect of coagulation treatment on dissolved pollutants in coal mine water[J/OL]. Industrial Water Treatment,2024:1–10 [2024-05-27]. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=GYSC20240 523003&dbname=CJFD&dbcode=CJFQ.
[6] 唐佳伟,张锁,刘兆峰,等. 吸附法去除矿井水中F–研究进展[J]. 煤炭科学技术,2023,51(5):269−283.
TANG Jiawei,ZHANG Suo,LIU Zhaofeng,et al. Research progress in the removal of fluoride ions from mine water by adsorption method[J]. Coal Science and Technology,2023,51(5):269−283.
[7] TEUTLI–SEQUEIRA A,SOLACHE–RÍOS M,MARTÍNEZ–MIRANDA V,et al. Comparison of aluminum modified natural materials in the removal of fluoride ions[J]. Journal of Colloid and Interface Science,2014,418:254−260.
[8] KAGNE S,JAGTAP S,DHAWADE P,et al. Hydrated cement:A promising adsorbent for the removal of fluoride from aqueous solution[J]. Journal of Hazardous Materials,2008,154(1/2/3):88−95.
[9] DAYANANDA D,SARVA V R,PRASAD S V,et al. Preparation of CaO loaded mesoporous Al2O3:Efficient adsorbent for fluoride removal from water[J]. Chemical Engineering Journal,2014,248:430−439.
[10] 何绪文,王绍州,张学伟,等. 煤矿矿井水资源化绿色短流程关键技术与装备[J]. 煤炭学报,2024,49(2):958−966.
HE Xuwen,WANG Shaozhou,ZHANG Xuewei,et al. Key technologies and equipment for green short process of coal mine drainage resource utilization[J]. Journal of China Coal Society,2024,49(2):958−966.
[11] 张海琴,包一翔,唐佳伟,等. 神东矿区天然矿物中的氟化物浸出规律研究[J]. 煤炭科学技术,2023,51(2):436−448.
ZHANG Haiqin,BAO Yixiang,TANG Jiawei,et al. Study on fluoride leaching regularity of natural minerals in Shendong Mining Area[J]. Coal Science and Technology,2023,51(2):436−448.
[12] 张溪彧,董书宁,王锐,等. 含悬浮物矿井水微絮凝–多级过滤工艺研究[J]. 水文地质工程地质,2023,50(5):222−230.
ZHANG Xiyu,DONG Shuning,WANG Rui,et al. A study of the microflocculation–multistage filtration technology of mine water containing suspended solids[J]. Hydrogeology & Engineering Geology,2023,50(5):222−230.
[13] SHANG Yabo,WANG Yadong,LI Keqian,et al. Nucleation crystallization pelleting process for highly efficient manganese ion recovery in electrolytic manganese wastewater[J]. Chemical Engineering Journal,2023,475:146271.
[14] LI Yao,XIN Haoran,ZONG Yukai,et al. A novel nucleation–induced crystallization process towards simultaneous removal of hardness and organics[J]. Separation and Purification Technology,2023,307:122785.
[15] WANG Yadong,SHANG Yabo,LI Keqian,et al. Enhanced simultaneous phosphate recovery and organics removal by a nucleation crystallization pelleting process[J]. Separation and Purification Technology,2024,349:127721.
[16] YOU Shaowei,CAO Shaotao,MO Chunyang,et al. Synthesis of high purity calcium fluoride from fluoride–containing wastewater[J]. Chemical Engineering Journal,2023,453:139733.
[17] ZHANG Daoyong,LIN Qinghua,XUE Nana,et al. The kinetics,thermodynamics and mineral crystallography of CaCO3 precipitation by dissolved organic matter and salinity[J]. Science of the Total Environment,2019,673:546−552.
[18] GOPI S,SUBRAMANIAN V K,PALANISAMY K. Aragonite–calcite–vaterite:A temperature influenced sequential polymorphic transformation of CaCO3 in the presence of DTPA[J]. Materials Research Bulletin,2013,48(5):1906−1912.
[19] PÉREZ–VILLAREJO L,TAKABAIT F,MAHTOUT L,et al. Synthesis of vaterite CaCO3 as submicron and nanosized particles using inorganic precursors and sucrose in aqueous medium[J]. Ceramics International,2018,44(5):5291−5296.
[20] NIE Xiaobao,WANG Zhengbo,WAN Junli,et al. Competition between homogeneous and heterogeneous crystallization of CaCO3 during water softening[J]. Water Research,2024,250:121061.
[21] CHHIM N,KHARBACHI C,NEVEUX T,et al. Inhibition of calcium carbonate crystal growth by organic additives using the constant composition method in conditions of recirculating cooling circuits[J]. Journal of Crystal Growth,2017,472:35−45.
[22] BUDYANTO S,KUO Yulin,LIU J C. Adsorption and precipitation of fluoride on calcite nanoparticles:A spectroscopic study[J]. Separation and Purification Technology,2015,150:325−331.
[23] WANG Zhao,SU Junfeng,HU Xiaofen,et al. Isolation of biosynthetic crystals by microbially induced calcium carbonate precipitation and their utilization for fluoride removal from groundwater[J]. Journal of Hazardous Materials,2021,406:124748.
[24] ZENG Guisheng,LING Bo,LI Zhongjun,et al. Fluorine removal and calcium fluoride recovery from rare–earth smelting wastewater using fluidized bed crystallization process[J]. Journal of Hazardous Materials,2019,373:313−320.
[25] WANG Zheng,LI Mengxiao,LIAO Yufeng,et al. Formation of disinfection byproducts from chlorinated soluble microbial products:Effect of carbon sources in wastewater denitrification processes[J]. Chemical Engineering Journal,2022,432:134237.
[26] BOWKER M,MADIX R J. XPS,UPS and thermal desorption studies of alcohol adsorption on Cu (110):II. Higher alcohols[J]. Surface Science,1982,116(3):549−572.
[27] KHANRA P,KUILA T,KIM N H,et al. Simultaneous bio–functionalization and reduction of graphene oxide by baker’s yeast[J]. Chemical Engineering Journal,2012,183:526−533.
[28] JOSEPH S,LEE J M,BENZIGAR M R,et al. Milk derived highly ordered mesoporous carbon with CaF2 nanoclusters as an efficient electrode for supercapacitors[J]. Carbon,2021,180:101−109.
[29] DOS S BEZERRA C,VALERIO M E G. Structural and optical study of CaF2 nanoparticles produced by a microwave–assisted hydrothermal method[J]. Physica B:Condensed Matter,2016,501:106−112.
[30] MIAO Xiwang,BAI Zhitao,QIU Guibo,et al. Preparation of transparent Mn–doped CaF2 glass–ceramics from silicon–manganese slag:Dependence of colour–controllable change on slag addition and crystallization behavior[J]. Journal of the European Ceramic Society,2020,40(8):3249−3261.
[31] LI Yao,JIN Xin,ZONG Yukai,et al. Regulation of hydrogen bonding on microbubble flocs in the hybrid ozonation–coagulation (HOC) process enhances organic matter removal[J]. Journal of Cleaner Production,2022,352:131617.
[32] HUANG Guocheng,XIAO Zhengtao,ZHEN Weiqian,et al. Hydrogen production from natural organic matter via cascading oxic–anoxic photocatalytic processes:An energy recovering water purification technology[J]. Water Research,2020,175:115684.
[33] FAHAMI A,NASIRI–TABRIZI B. Mechanochemical behavior of CaCO3–P2O5–CaF2 system to produce carbonated fluorapatite nanopowder[J]. Ceramics International,2014,40(9):14939−14946.
[34] NOGUEIRA L F B,MANIGLIA B C,PEREIRA L S,et al. Formation of carrageenan–CaCO3 bioactive membranes[J]. Materials Science and Engineering:C,2016,58:1−6.
[35] 王亚东,殷伟民,张亚强,等. 循环冷却水中镁离子强化去除的核晶造粒工艺技术研究[J]. 给水排水,2025,51(1):84−91.
WANG Yadong,YIN Weimin,ZHANG Yaqiang,et al. Research on nucleation crystallization pelleting process (NCP) for enhanced removal of magnesium ions from recirculated cooling water[J]. Water & Wastewater Engineering,2025,51(1):84−91.
[36] ABDULAZIZ F,LATIF S,TAHA T A M. Preparation of Co–CaCO3 catalysts for improved hydrogen production from sodium borohydride[J]. International Journal of Hydrogen Energy,2024,56:271−279.
[37] LEE S K,OH T,KIM G W,et al. Benefits of CaCO3 nanoparticles for the strain hardening behavior of high-strength alkali-activated composites based on blast furnace slag and liquid crystal display glass powder[J]. Construction and Building Materials. 2024,449:138314.
Included in
Earth Sciences Commons, Mining Engineering Commons, Oil, Gas, and Energy Commons, Sustainability Commons