氟是人体重要的微量元素之一,但过量氟摄入会导致骨骼变形,甚至引起机体慢性中毒,氟污染已成为每个国家都面临的一个难题。在众多除氟方法中,羟基磷灰石(HAP)因具有成本低、内含与F-相近半径和电荷的羟基基团等特点,成为最具潜力的吸氟材料。但纯HAP由于孔隙率低、活性位点少、粒径大使F-内部扩散交换速率受限等缺点,氟吸附容量非常有限,因此多与其他材料联用,以形成比表面积更大、活性位点更多、粒径更小且稳定性更加优良的除氟复合材料。综述了近年HAP与金属阳离子、天然矿物、有机物、碳纳米粒子等相复合后,新型复合HAP的物理化学结构特征、除氟容量及其应用领域。
Fluoride is one of the important trace elements for human,but excessive fluoride intake will lead to bone deformation,and even cause chronic poisoning of the body.The fluoride pollution has become a problem that every country is facing.Among many methods of fluoride removal,hydroxyapatite (HAP) has become the most potential fluoride adsorbing material because of its low cost and containing hydroxyl groups with similar radius and charge to F-.However,the fluoride adsorption capacity of HAP is very limited due to the disadvantages of low porosity,less active site,large particle size and limited internal diffusion exchange rate,so more combination with other material,in order to form larger surface area,more active sites,smaller particle size and better stability of the composite material.The physicochemical structure,fluoride removal capacity and application of HAP composite with metal cations,natural minerals,organic compounds and carbon nanoparticles in recent years were reviewed.
[1] 何令令,何守阳,陈琢玉,等.环境中氟污染与人体氟效应[J].地球与环境,2020,48(1):87-95.
[2] 苏双青,赵焰,徐志清,等.我国煤矿矿井水氟污染现状及除氟技术研究[J].能源与环保,2020,42(11):5-10.
[3] 王飞.石灰混合溶液除氟工艺在矿井水中的应用技术探讨[J].煤,2019,28(7):92-93.
[4] Mousazadeh M,Alizadeh S M,Frontistis Z,et al.Electrocoagulation as a promising defluoridation technology from water:a review of state of the art of removal mechanisms and performance trends[J].Water,2021,13(5):656.
[5] 吴承慧,陈长安,梁震,等.纳米级Fe3O4对水中氟的吸附性能研究[J].绿色科技,2019(22):79-82.
[6] 蒋雯雯,聂鹏飞,胡彬.Al2O3/AC正极选择性电容吸附水中氟离子[J].化工学报,2021,72(5):2817-2825.
[7] Liu C C,Liu J C.Coupled precipitation-ultrafiltration for treatment of high fluoride-content wastewater[J].Journal of the Taiwan Institute of Chemical Engineers,2016,58:259-263.
[8] 何瑞敏.改性高分子除氟吸附材料的研究进展[J].高分子通报,2018(12):1-8.
[9] 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.
[10] 宋宝城.活性氧化铝除氟材料研究进展[J].化学工程与装备,2021(8):223-225.
[11] 崔灵周,肖继波,洪玉芳.悬挂铁改性活性炭的美人蕉浮床除氟效果试验[J].环境污染与防治,2020,42(8):971-974.
[12] Sawangjang B,Induvesa P,Wongrueng A,et al.Evaluation of fluoride adsorption mechanism and capacity of different types of bone char[J].International Journal of Environmental Research and Public Health,2021,18(13):6878.
[13] Li X L,Yu X W,Liu L,et al.Preparation,characterization serpentine-loaded hydroxyapatite and its simultaneous removal performance for fluoride,iron and manganese[J].RSC Advances,2021,11(27):16201-16215.
[14] 陈杰山.国内除氟吸附剂的研究进展[J].广州化工,2015,43(19):18-20.
[15] 卫军华,张璐璐,肖进彬,等.我国活性炭吸附处理含氟废水研究进展[J].广东化工,2020,47(2):117-118,129.
[16] 王涌.饮用水骨炭除氟机理的研究[J].广州大学学报(自然科学版),2003,2(5):423-426.
[17] 汤庆子.羟基磷灰石及其复合材料的制备、表征和除氟性能研究[D].南昌:南昌大学,2017.
[18] 王萍,李国昌.羟基磷灰石的制备及除氟性能研究[J].环境工程学报,2009,3(3):564-568.
[19] Ghahremani D,Mobasherpour I,Salahi E,et al.Potential of nano crystalline calcium hydroxyapatite for Tin(Ⅱ) removal from aqueous solutions:equilibria and kinetic processes[J].Arabian Journal of Chemistry,2017,10:S461-S471.
[20] 郑搏英,张亮亮,张襄,等.我国吸附法处理含氟废水研究进展[J].广东化工,2022,49(3):140-142.
[21] 田键,汤钒,胡攀,等.羟基磷灰石复合及掺杂改性研究进展[J].有色金属材料与工程,2021,42(4):55-60.
[22] Pai S,Kini M S,Selvaraj R.A review on adsorptive removal of dyes from wastewater by hydroxyapatite nanocomposites[J].Environmental Science and Pollution Research,2021,28(10):11835-11849.
[23] 范云辉,王世革,黄明贤.羟基磷灰石相关复合材料的研究进展[J].广州化学,2021,46(3):22-28,36.
[24] Gong L Y,Feng L,Preparation and defluorination mechanism of a novel copolymerized hydroxyapatite-aluminium chloride material[J].RSC Advances,2015,5(115):95334-95343.
[25] George S,Mehta D,Saharan V K.Application of hydroxyapatite and its modified forms as adsorbents for water defluoridation:an insight into process synthesis[J].Reviews in Chemical Engineering,2018,36(3):369-400.
[26] Evis Z,Webster T J.Nanosize hydroxyapatite:doping with various ions[J].Advances in Applied Ceramics,2013,110(5):311-320.
[27] Sahu H,Mohanty K.Al grafted natural hydroxyapatite for neem oil transesterification:kinetic study at optimal point[J].Chemical Engineering Journal,2015,280:564-574.
[28] 童庆,徐慧,樊华,等.Al13改性羟基磷灰石的除氟性能研究[J].环境科学学报,2021,41(7):2748-2757.
[29] Huang S,Hu M,Li D,et al.Fluoride sorption from aqueous solution using Al(OH)3-modified hydroxyapatite nanosheet[J].Fuel,2020,279(1-241):118486.
[30] Mondal P,Mehta D,George S.Defluoridation studies with synthesized magnesium-incorporated hydroxyapatite and parameter optimization using response surface methodology[J].Desalination and Water Treatment,2016,57(56):27294-27313.
[31] 赵瑨云,胡家朋,林皓,等.Ag+改性羟基磷灰石制备及其除氟抑菌特性研究[J].硅酸盐通报,2020,39(12):3977-3984.
[32] Chen Z,Liu Y,Mao L,et al.Effect of cation doping on the structure of hydroxyapatite and the mechanism of defluoridation[J].Ceramics International,2017,44(6):6002-6009.
[33] Gao S,Sun R,Wei Z,et al.Size-dependent defluoridation properties of synthetic hydroxyapatite[J].Journal of Fluorine Chemistry,2009,130(6):550-556.
[34] 林皓,齐小宝,胡家朋,等.吸附除氟材料研究新进展[J].化工新型材料,2018,46(3):37-41.
[35] Tomar G,Thareja A,Sarkar S.Enhanced fluoride removal by hydroxyapatite-modified activated alumina[J].International Journal of Environmental Science & Technology,2015,12(9):2809-2818.
[36] Gómez-Hortigüela L,Pérez-Pariente J,Chebude Y,et al.Controlled growth of hydroxyapatite on the surface of natural stilbite from Ethiopia:application in mitigation of fluorosis[J].Rsc Advances,2014,4(16):7998.
[37] Sani T,Gómez-Hortigüela L,Mayoral Á,et al.Controlled growth of nano-hydroxyapatite on stilbite:defluoridation performance[J].Microporous & Mesoporous Materials,2017,254:86-95.
[38] Xu F,Jiang C,Li D.Defluoridation of wastewaters using HAP-coated-limestone[J].Separation Science & Technology,2018,54(14):2304-2313.
[39] Workeneh K,Zereffa E A,Segne T A,et al.Eggshell-derived nanohydroxyapatite adsorbent for defluoridation of drinking water from bofo of ethiopia[J].Journal of Nanomaterials,2019,2:1-12.
[40] 干成果,冯莉.负载羟基磷灰石活性炭的制备及除氟性能[J].功能材料,2013,44(22):3243-3246.
[41] Sani T,Adem M,Fetter G,et al.Defluoridation performance comparison of nano-hydrotalcite/hydroxyapatite composite with calcined hydrotalcite and hydroxyapatite[J].Water Air & Soil Pollution,2016,227(3):90.
[42] 胡家朋.羟基磷灰石复合改性材料的制备及其除氟性能研究[D].南昌:南昌大学,2016.
[43] 赵瑨云,刘瑞来,徐婕,等.原位合成羟基磷灰石/壳聚糖复合吸附剂及除氟特性研究[J].高分子通报,2021(2):54-62.
[44] Sundaram C,Viswanathan N,Meenakshi S.Uptake of fluoride by nano-hydroxyapatite /chitosan,a bioinorganic composite[J].Bioresource Technology,2008,99(17):8226-8230.
[45] 柳波,邱开雄,端木雯婧,等.羟基磷灰石-聚乙烯醇复合剂处理含氟废水的研究[J].昆明医科大学学报,2013,34(1):62-64.
[46] Nijhawan A,Butler E C,Sabatini D A.Macroporous hydroxyapatite ceramic beads for fluoride removal fromdrinking water[J].Journal of Chemical Technology & Biotechnology,2017,92(8):1868-1875.
[47] Nunes-Pereira J,Lima R,Choudhary G,et al.Highly efficient removal of fluoride from aqueous media through polymer composite membranes[J].Separation and Purification Technology,2018,205:1-10.
[48] Huang L,Wan K,Yan J,et al.Nanomaterials in water applications:adsorbing materials for fluoride removal[J].Nanomaterials,2021,11(7):1866.
[49] Ruan Z Y,Tian Y X,Ruan J F,et al.Synthesis of hydroxyapatite/multi-walled carbon nanotubes for the removal of fluoride ions from solution[J].Applied Surface Science,2017,412:578-590.
[50] 章萍,杨陈凯,马若男,等.碳纳米管/羟基磷灰石复合材料对水体F-的去除研究[J].中国环境科学,2019,39(1):179-187.
[51] Tang Q,Duan T,Peng L,et al.Enhanced defluoridation capacity from aqueous media via hydroxyapatite decorated with carbon nanotube[J].Front Chem,2018,6:104.
[52] Prabhu S M,Elanchezhiyan S S D,Lee G,et al.Assembly of nano-sized hydroxyapatite onto graphene oxide sheets via in-situ fabrication method and its prospective application for defluoridation studies[J].Chemical Engineering Journal,2016,300:334-342.
基金资助
陕西省科技重点资助项目(2020GY-238);西安市科技计划项目(20NYYF0047)
PDF
