硫化、磁化、氧化对零价铁还原偶氮染料的去除

硫化、磁化、氧化对零价铁还原偶氮染料的去除许春华，张炳亮，范涤敏，石振清JoelZ.Bandstra，PaulG.Tratnyek山东大学2018.6.28青岛2018（第十三届）青岛国际水大会山东大学主要内容1.ZVI的特性及发展研究现状2.染料废水的产生和危害3.硫化改性零价铁及弱磁场及去除偶氮染料的研究4.主要结论零价铁（ZeroValentIron,ZVI）特征：含量丰富、廉价易得（地壳含量：氧硅铝铁钙，铁排第四，含量4.75%）无毒、环境友好、还原能力强（Eθ(Fe2+/Fe0)=-0.44V）1.ZVI的特性及发展研究现状1.1ZVI的特点AdvantagesofZVItechnologyCheapandavailableStrongerreductionabilityNontoxicityenvironmen-tallyfriendlyAbletoremoveavarietyofpollutantsRichincontentGuanetal.WaterRes.(2015)LowreactivityduetotheoxidefilmonpristineZVINarrowworkingpHrangeReactivitylossduetothecorrosionproductsLowselectivitytowardstargetedcontaminantsPassivationofFe0bysomecontaminantsCoexistingsolutes-inducedreductioninitsreactivityLowreactivitytowardsomerefractorycontaminantsAccumulationoftoxicbyproductsDemeritsofZVItechnology1.1ZVI的特点1.ZVI的特性及发展研究现状Acid-washingpretreatmentforpristineZVIDesignationofZVI-PRBasastandardremediationtechnologybyUSEPAInitiationoftheuseofnZVIforgroundwaterremediationInstallmentofthefirstfull-scaleZVI-PRBUltrasoundpretreatmentforpristineZVIH2pretreatmentforpristineZVIExplorationofzerovalentbimetalsUVlightassistedZVItechnologyMicrowaveassistedZVItechnologyWeakmagneticfieldassistedZVItechnology

CouplingZVIwithactivatedcarbonCouplingZVIwithbentonite

CouplingZVIwithIronoxide

ThefirstfielddemonstrationofgroundwaterremediationwithnZVI

Publicationoftwofullpapersondegra-dationofhalogenatedaliphaticsby

ZVICouplingZVIwithzeoliteFacileSynthesisandofFe/FeS

Nanoparticles2014201220102008200620042002200019981996199419921990FirstfieldapplicationofZVItotreatTCEinBorden,Ontario,andCanadaGuanetal.WaterRes.(2015)1.2ZVI技术发展历程1.ZVI的特性及发展研究现状2.1染料及染料废水染料废水主要来源于染料的生产加工过程中产生的废水以及印染行业产生的废水。全世界每年生产160万吨的染料，其中占总体积的10-15%的量被当作废水排放。我国是染料生产大国，仅2014年其产量已达到91.72万吨，居世界产量之首。2.染料废水的产生和危害2.1染料废水的危害高色度的染料废水排放到水体会对水生动植物带来严重的威胁，阻碍阳光的透射且扰乱生物的代谢过程，破坏水生生物生态系统。过多接触染料废水会对皮肤、肾脏、肝脏、呼吸系统、生殖系统、大脑和中枢神经系统带来一定的危害，同时还有部分染料废水具有致癌、致畸和致敏效应。2.染料废水的产生和危害3.1零价铁去除染料文献数量随年份变化Xuetal.ES&T(2016a)FigureS1.Chronologyofresearchpapersontreatmentofdyecontaminatedwaterusingzerovalentiron.Datacompiledfrommultiplesources(WebofScience,ElsevierScienceDirect,ACSPublications).3.硫化改性零价铁及弱磁场去除偶氮染料的研究FigureS2.SEManalysisforZVIfromthisstudy.(A)untreatedFe/FeO,(B)Fe/FeOafter30minexposuretomedium+OrangeI,withWMF,(C)freshlypreparedFe/FeS,(D)Fe/FeSafter30minexposuretomedium+OrangeI,withoutWMF.3.2Fe/FeO与硫化零价铁Fe/FeS的制备与表征FigureS3.EDSanalysisforZVIfromthisstudy.(A)untreatedFe/FeO,(B)Fe/FeOafter30minexposuretomedium+OrangeI,withWMF,(C)freshlypreparedFe/FeS,(D)Fe/FeSafter30minexposuretomedium+OrangeI,withoutWMF.3.2Fe/FeO与硫化零价铁Fe/FeS的制备与表征FigureS4.Fe2p(A-D)andS2p(E)XPSspectraforZVIinthisstudy.Conditions:pH=7,OrangeIC0=100mg/L,Fe/FeS=2g/L,RPM=400,T=25°C.(A)Fe/FeS0min,(B)Fe/FeSafterreaction30minwithoutWMF,(C)Fe/FeSafterreaction120minwithoutWMF,(D)Fe/FeO0min,(E)Fe/FeS0min.3.2Fe/FeO与硫化零价铁Fe/FeS的制备与表征Figure1.Timeseriesplotsshowingtheeffectofsulfidationwith(+)andwithout(–)WMFon(A)OrangeIremovalbyZVIand(B-D)DO,Fe(II),andEh.Alldatawereobtainedfromstirred,openbatchreactorswith2.0g/LFe/FeOorFe/FeS,100mg/LOrangeI,pH=7,andRPM=400.ContinuouscurvesinArepresentthefitstopseudofirst-orderkinetics,whereastheotherdatawerenotmodeledandthelinesonlyconnectdatapoints.3.3研究结果硫化和弱磁场影响的时间序列FigureS6.Matrixoftimeseriescorrelationsforeachcombinationofsynchronouslymeasuredexperimentalparameters(C/C0forOrangeI,DO,Fe(II),andEh).TreatmenteffectsincludeWMF(color)andFe/FeOand

Fe/FeS(symbols).DataarefromthesameseriesofexperimentsinFigureS5,allofwhichweredoneinstirred,openbatchreactorswithpH

=7,OrangeIC0=100mg/L,Fe/FeOor

Fe/FeS=2g/L,RPM=400,T=25°C.3.3研究结果实验参数(C/C0,DO,Fe(II)和Eh)的时间序列相关性矩阵图3.3研究结果不同反应条件反应速率常数对比分析反应速率常数提高2.4~71.8倍。Therewasappearanceofoneproductpeakat251nmin,whichisattributableto1-amino-4-naphthol零价铁/硫化零价铁去除橙黄I的紫外波长扫描图3.4零价铁去除橙黄I的机理研究anotherpossibleproduct,sulfanilicacid,hasaλmax=249nm,soitcannotbeexcludedbyUV−vis.橙黄I及其产物的HPLC-MS分析图橙黄I及其产物的HPLC-MS分析结果由UV-Vis波长扫描图和HPLC-MS图可知橙黄I的偶氮键断裂且生成了对氨基苯磺酸和1-氨基-4-萘酚。（Fe/FeO投加量为2.0g/L，橙黄I初始浓度为100mg/L，初始pH为7.0）3.4零价铁去除橙黄I的机理研究零价铁/硫化零价铁和橙黄I反应后的FTIR图谱3.4零价铁去除橙黄I的机理研究每一种反应条件都在波数为3172cm-1时出现了N-H键，说明部分氮氮双键已经断裂并且有一部分反应产物被铁氧化物或氢氧化物所吸附。零价铁/硫化零价铁去除橙黄I的反应路径图3.4零价铁去除橙黄I的机理研究Figure3.Time-seriesplotsof(A)dyeconcentration,(B)dissolvedoxygenconcentrationand(C)redoxpotentialforre-spikebatchexperimentsconductedwithFe/FeO，Fe/FeSandinthepresence(orabsence)ofaWMFduringeachcycle(indicatedinthelegendby+or−).3.5硫化和弱磁场的持续性影响零价铁/硫化零价铁去除橙黄I的重复性实验图Figure4.SummaryofkobsforOrangeIdecolorizationby(A)Fe/FeOand(B)Fe/FeSinsequentialrespikeexperimentswith(+)andwithout(−)WMF.Alldatawereobtainedfromstirred,openbatchreactorswith2.0g/LFe/FeOorFe/FeS,100mg/LOrangeI,pH=7,andRPM=400.3.5硫化和弱磁场的持续性影响零价铁/硫化零价铁去除橙黄I重复性实验的kobs图FigureS11.Dissolvedoxygensagcurves(A)Fe/FeO−WMF,(B)Fe/FeS−WMF,(C)Fe/FeO+WMF,and(D)Fe/FeS+WMFforvaryinglevelsofOrangeIexposure(indicatedinthelegend).3.6

溶解氧模型的构建提出假设：零价铁表面的钝化作用主要是受溶解氧的影响，零价铁的腐蚀和钝化膜的生成过程是并存的。反应溶液中的溶解氧变化图(4)将式(1)-(3)进行积分，如下式(4)-(6)式中Sa和Sp分别代表了表面活性位点和表面非活性（钝化）位点，krxn,kO2,depl和kO2,ra分别代表染料和活性位点的反应速率常数，溶解氧的消耗速率常数和复氧速率常数。3.6

溶解氧模型的构建(3)(2)(1)(5)(6)3.6

溶解氧模型的构建模型拟合出的数据和原始数据吻合度较高。Figure5.Representativefitsoftheoxygen-drivenpassivationmodeltothedissolvedoxygendata.Alldatawereobtainedfromstirred,openbatchreactorswith100mg/LOrangeI,pH=7,andRPM=400.3.6

溶解氧模型的构建四组代表性的溶解氧驱动钝化模型拟合图模型拟合出的数据和原始数据吻合度较高。Figure6.Pseudo-first-orderdyedisappearancerateconstantsforallsurfacetreatmentsplottedagainstaverageactivesiteconcentrationsgeneratedbyglobalfittingofequations(4–6)toalldissolvedoxygentimeseriesdata.Dashedlinesindicatecycleswithinarespikeexperiment.Thelinearfittestswhetherthereactionispseudofirst-orderin[Sa],