粉煤灰合成分子筛及处理含氟废水的研究郝培亮

:,,1965,,。#。粉煤灰合成分子筛及处理含氟废水的研究郝培亮1石泽华1李晓峰2窦涛2王增长1#(1.,030024;2.,030024)　　———XP,。XRD,,XP68%～75%55%。,NaF。,X,74%～98%,25.0～30.0mg/g。,,、、。　　Preparationandcharacterizationofflyashbasedzeolitesforfluorideremoval　HaoPeiliang1,ShiZehua1,LiXiao-feng2,DouTao2,WangZengzhang1.(1.CollegeofEnvironmentScienceandEngineeringAcademy,TaiyuanUni-versityofTechnology,TaiyuanShanxi030024;2.InstituteofSpecialChemical,TaiyuanUniversityofTechnolo-gy,TaiyuanShanxi030024)Abstract:　Twotypesofmolecularsieveadsorbents(zeolites)werepreparedfrompowerplantresidualcircula-tionfluidizedbedflyashbyhydrothermalreactions.TheXandPzeoliteswereproducedbybakingwithoutpretrea-tingtherawmaterials.TheXRDcharacterizationsshowthatrelativecrystallinityoftheXandPzeoliteswere68%-75%and55%,respectively.FeCl3wasemployedforimpregnationofFe3+ontheXzeolite,andtheeffectsofFeCl3loading,impregnationtemperatureandcontacttimeonthemodifiedzeolite'scapacityweredetermined.TheFeim-pregnatedXzeoliteremoved74%-98%ofF-inthetestrunswithanadsorptivecapacityof25.0-30.0mg/g;itdem-onstratedahighercapacity,fasterandmorecompleteremovalofF-thantheoriginalXzeolites,naturalzeolite,clayandflyash.TheformationofFeF3-nn(n=1-6)resultedinahighercapacityduetochemicaladsorption.Keywords:　CirculatingfluidizedbedflyashesZeolitesSynthesisFe3+loadingFluorideremoval　　,,,[1-4]。,、,,。,。1000℃,,,。、。　　,,(、),。,,。1　1.1仪器、原料及试剂　　,Y-2000,PXS-215,PHS-3C,PF-1B,;NaOH(),,FeCl3(),NaF(),NaCl(),(),(),。1.2分子筛的合成实验　　(A)(B),。　　:,、、NaOH、,·832·　　29　11　200711DOI:10.15985/j.cnki.1001-3865.2007.11.01150℃,95～100℃,pH9,、,。1.3物相表征　　XRDY-2000,Ni,CuKa,40kV,20mA,0.1°/s,5°～35°。　　。,(1)。α=α0I/I0(1):α,%;α0,%,α0=100%;II0。1.4载铁改性及除氟实验1.4.1　　　FeCl3,,4h,、、。1.4.2　TISAB　　NaCl60g,64g,5g,14.4mL,1000mL,TISAB。1.4.3　　　NaF。1100、110、11mg/L(F-,)NaF50mL,30min,,TISABF-,。2　2.1分子筛的合成2.1.1　　　,(1),。ABSiO2Al2O385.96%78.06%;AB11.00%15.00%,,,ABSiO2/Al2O3(,)2.021.73。,ABSiO2/Al2O3X、A,,。SiO2/Al2O3。2.1.2　　　2、、,:SiO2/Al2O31.73～3.70、Na2O/SiO2()1.2～1.5、H2O/Na2O()40～70。,95～100℃。1　1)Table1　CompositionofthecirculationfluidizedbedflyashsamplesSiO2Al2O3FeOMgOCaONa2OK2OLOI2)A/%46.7739.190.830.030.020.020.0411.0097.90B/%39.3238.743.090.020.440.230.3015.0097.14　　:1);2)。2　Table2　PreparationandcrystalcharacteristicsoftheexperimentalzeolitesSiO2/Al2O3NaOH/(mol·L-1)/h/%1#A2.022.645-2#A2.022.649X(A)403#A2.022.6416X(A)534#A2.022.6419X(P)675#A3.701.3216X416#A3.702.2016X757#A3.702.8516P(X)-8#B3.701.3216X449#B3.702.2016X6810#B3.702.8516P(X)-11#B1.732.644-12#B1.732.646A(P)3713#B1.732.856A(P)5014#B1.732.859P55·833·　　　2,1#～4#A,SiO2/Al2O3NaOH,:5h(1#);9hX(A,2#);16h53%(3#);19hAP(4#)。X,,AP。　　5#～7#A,SiO2/Al2O3,16h,NaOH1.32mol/L2.20mol/LX,41%75%;NaOH2.85mol/L,P。　　8#～10#B,5#～7#。16h,NaOH1.32mol/L2.20mol/LX,44%68%;NaOH2.85mol/L,P。,XP。　　11#、12#B、SiO2/Al2O31.73、NaOH2.64mol/L,4h,6hA(P)。13#、14#B、SiO2/Al2O31.73、NaOH2.85mol/L,6h9h,A(P)P。12#、13#B、SiO2/Al2O31.73、NaOH2.64mol/L2.85mol/L,6h,A(P),37%、50%。2.1.3　　　NaOH、SiO2/Al2O3。2,:(1)AB,,SiO2/Al2O3AX,SiO2/Al2O3BA;AB,SiO2/Al2O3;(2)X:SiO2/Al2O33.70,NaOH2.20mol/L,16h;P:SiO2/Al2O31.73,NaOH2.85mol/L,9h;(3)NaOH、,NaOH,,NaOH,A※PX※P;(4)ANAND、、。ANAND[5-9]。,,。2.1.4　XRD　　136#、9#、14#XRD。,13,,。13(1),X(6#、9#)1　6#XRDFig.1　XRDofNo.6zeolite(Xtype,75%relativecrystallinity,fromAflyash)2　9#XRDFig.2　XRDofNo.9zeolite(Xtype,68%relativecrystallinity,fromBflyash)3　14#XRDFig.3　XRDofNo.14zeolite(Ptype,55%relativecrystallinity,fromBflyash)·834·　　29　11　20071175%68%,P(14#)55%。2.2合成和载铁合成分子筛的除氟性能2.2.1　　　6#、9#、14#,。,X(6#)(4)。X、,,(F-1100mg/L,)42%;(F-11mg/L,)79%;(F-110mg/L,)92%。X、、,74%,,;98%,F-2mg/L,;97%,。4　X(6#)Fig.4　EffectofFeimpregnationonfluorideremoval2.2.2　　　35,X4,、,;,3　5Table3　FlourideremovalperformanceoftheexperimentalzeolitesandotherabsorbentsXX/(mg·g-1)25.0～30.018.00.50.22.0～3.0/%74～9870～804090～9963()/min20～3020～303060～18030,。,80%,,、,。,[10,11]。X,,,、、,,,。2.3除氟性能的影响因素分析2.3.1　、　　6#、9#、14#,(4)。,、,6#9#,14#。6#9#X,14#P,。,,6#9#,。,XP,,。4　、Table4　Fluorideremovalperformancedataof3experimentalzeolites6#9#14#XXP/%75685574.072.067.2/%99.896.294.598.694.374.02.3.2　FeCl3/X　　6#X,,FeCl3/X(,XX,)X。5,FeCl3/X,FeCl3/X。FeCl3/X。,FeCl3/X0.40～0.50。·835·　5　FeCl3/XFig.5　EffectofFeCl3/Xonfluorideremoval2.3.3　　　6#X,FeCl3/X0.40,6。6,180℃,FeCl3Fe2O3Fe3O4;140℃,,Fe3+,Fe3+。,,150～180℃。6　Fig.6　Effectofimpregnationtemperatureonfluorideremoval2.3.4　　　7,,、15min,15min;30min。X8。8,X,,。,50mL2.5～3.5gX;、50mL1.0～2.0gX。,,XpH(pH6～10)。7　Fig.7　Effectofcontacttimeonfluorideremoval8　X1)Fig.8　Effectofzeolitedoseonfluorideremoval:1)50mL。2.4载铁合成分子筛除氟机理的分析　　,SiO4AlO4,。SiAl,,。,。Fe3+,,F-,Fe3+,FeF3-nn(n=1～6),,。F-,。F-A13+、Ca2+,。,F-[12]。,F-,,。(下转第840页)·836·　　29　11　2007113　　　　,。、、、C—OC—O—C。pH3.5～4.0,,。Pb2+,,Cr3+、Cu2+。,。Pb2+,Cr3+、Cu2+。Cr3+、Cu2+。[1]　,,,.[J].,2003,25(6):28-32.[2]　SERPILC,EROLP.Theuseofflyashasalowcost,environ-mentallyfriendlyalternativetoactivatedcarbonfortheremovalofheavymetalsfromaqueoussolutions[J].ColloidsandSur-facesA:PhysicochemicalandEngineeringAspects,2007,298(1):83-87.[3]　JOHNSONPD,WATSONMA,BROWNJ,etal.PeanuthullpelletsasasingleusesorbentforthecaptureofCu(Ⅱ)fromwastewater[J].WasteManagement,2002,22(5):471-480.[4]　PAULI