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Preparation ChinaPetroleumProcessingandPetrochemicalTechnology 2010,Vo1.12,No.4,PP23-29 PreparationofAluminaAbrasion-ResistantCeramic GrindingBallwithSpentFCCEquilibriumCatalyst LiangZhiyu;YanGuiyang;ZhengLiuping;WengXiulan;HuangZheqiang f.CollegeofChemistryandMaterialsScience,FujianNormalUniversity,Fuzhou350007; 2.MeizhouwanEnvironmentalMonitoringStation..

    Preparation

    ChinaPetroleumProcessingandPetrochemicalTechnology

    2010,Vo1.12,No.4,PP23-29

    PreparationofAluminaAbrasion-ResistantCeramic

    GrindingBallwithSpentFCCEquilibriumCatalyst

    LiangZhiyu;YanGuiyang;ZhengLiuping;WengXiulan;HuangZheqiang

    f.CollegeofChemistryandMaterialsScience,FujianNormalUniversity,Fuzhou350007; 2.MeizhouwanEnvironmentalMonitoringStation,Putian351158)

    Abstract:Thechemicalcomposition,structureandthermalstabilityofthespentFCCequilibriumcatalystfroman

    oilrefinerywerecharacterizedbyXRD,FTIR,DTA

    TG,BET,completechemicalanalysis,SEM,andXRF.The

    spentFCCequilibriumcatalyst,clay,bariumcarbonate,andtalcwereusedasthemainrawmaterialstopreparethe

    aluminaabrasion

    resistantceramicballstobeusedinthepowdergrindingmillformanufactureofarchitecturetiles.

    Theresultsshowedthatafterproperformulationstudy,thespentFCCequilibriumcatalystcouldreplaceindustrial

    aluminatopreparehighperformancegrindingballs.Meanwhile,thevariOUSperformanceindicesofthegrindingball

    couldmeetthequalitystandardforsimilarproducts,andadditionally,theenergysavingeffectwasachievedinthe

    operationofthegrindingsection,resultinginaSUCCESSfulcomprehensiveutilizationofsolidwastes.

    Keywords:spentFCCequilibriumcatalyst;alumina;abrasion

    resistantceramicball;solidwaste;utilization

1Introduction

    Thealuminafrictionmediumfeaturinghighwearresistance, highhardness,goodhightemperatureperformance,good

    chemicalstability,highinsulatingperformance,andlow frictioncoefficienthasbeenextensivelyappliedinthein

    dustry.Atpresentthealuminafrictionmediumismostly manufacturedthroughagglutinatinghigh--aluminabaux._ iteortechnica1aluminumoxidemixedwithfldefinite amountofclay[.thedisseminationandapplicationof whichhasbeengreatlyaffectedbyitshighproductioncost andhighenergyconsumption.

    InthepetroleumrefiningindustrytheequilibriumFCC catalystusedintheRFCCunitusuallyadoptsA1203asthe matrix[4I.ThedeactivatedFCCcatalystisgenerallydis

    posedofthroughlandfilling,whichcouldcausenotonly environmentalpollution,butalsosquanderingofresources. Theresearchteam,afterhavingobtainedfromtheFujian RefiningandPetrochemicalComplex(FRPC)abatchof spentFCCequilibriumcatalysttobeusedasthemainsource ofalumina,hasbeenexploringthewaysformanufactureof ceramicgrindingballsandapplicationofthismaterialin thepowdergrindingsectionofthearchitecturetilesafter conductingcomprehensiveevaluationoftheseceramic balls.Thismeasurecanrealizethere.useofresourcesand minimizeenvironmentalpollutionwithremarkablepracti

    calsignificance.

    23

    2Experimental

    2.1Apparatusandchemicalreagents

    EquilibriumFCCcatalyst(originatedfromthespentFCC

    catalystattheoilrefinery);fatclay(originatedfromXinhui city,Guangdongprovince);talc(originatedfromHaicheng city.Liaordngprovince);andbariumcarbonatefprovided bytheShanghaiYaojiangTitaniumOxideChemicalProd

    uctsCo.,Ltd.)

    Hydraulicpress(manufacturedbytheZhoucunXiangpeng Machiner5Factory);programmablehightemperaturere

    sistancefftrnace(manufacturedbytheShanghaiExperi

    mentalElectricFurnaceFactory);planetarylightdutyball

    mill(manufacturedbytheNanjingUniversityTianzhen ElectronicCompany);hydraulicdigitalfold--resistantma-

    chine(manufacturedbytheXiangtanTristarInstrument Co..Ltd.,landHV1000typemicrohardnessmeter

    (manufacturedbytheShanghaiMaterialTestingMachine Factory).

    2.2Chararcterizationofphysicochemicalpropertiesof

    spentFCCequilibriumcatalyst

    2.2.1X-raYpowderdiffractomertry(XRD)

    Xraydiffraction(XRD)patternsofsampleswererecorded CorrespondingAuthor:Prof.YanGuiyang.Telphone:+86

    13809566652;Email:ygyOnu@163.corn

    LiangZhiyu,etal?PreparationofAluminaAbrasion

    ResistantCeramicGrindingBallwithSpentFCC EquilibriumCatalyst

    onaPhilipsX'PertMPDdiffractometerusingCuKaradia. tionatatubevoltageof40kVandatubecurrentof40mA. TheKsofcoppertargetwas0.154nm.thescanningangle (20)was10.90.withascanningspeedof2(.)/min.

    2.2.2Fouriertransforminfraredspectr0scopy(FT.IR) InfraredspectraofKBrdiskswererecordedonaThermo

    Nicolet340infraredspectrometerwithascanningrangeof 4000cm一一400cm1.

    2.2.3Thermogravimetricanalysis(DTA-TG)

    Differentialthermalanalysesofsampleswereconducted onaGermanNETZSCHSTA449Ctypethermogravimetric meterwithanairflowrateof30mL/min..,atemperature riserateof10k/min,andatemperatureriserangeof30

    1000?.usingOc-A1203asthereferencesubstance. 2.2.4Specificsurfaceareaanalysis(BET)

    ABeckmannSA3100surfaceareaanalyzerwasemployed todeterminethespecificsurfaceareaofsamplesthrough measuringN2adsorption/desorptionisotherms. 2.2.5Fullchemicalanalysis

    Fullchemicalanalyticalmethodswereusedtodetermine thechemicalcompositionofrawspentFCCcatalyst,clay andtalcformanufactureofthetargetproduct. 2.2.6Scanningelectronmicroscopy(SEM)

    Thesampleaftersurfacesprayingwithgoldwasinspected byaJSM7500FFESEMscanningelectronmicroscopeata maximumworkingvoltageof30kV.

    2.2.7Xrayfluorescencespectroscopy(XRF)

    APhilipsPW2424FMagiXX--rayfluorescencespectrom-? eterwasemployedtoanalyzethespentFCCequilibrium catalystsamples.

    2.3Preparationofaluminaceramicballs

    Inordertoguaranteeastableformulationandavoidcrack

    ingofceramicballsresultedfromexcessivecontraction duringagglomerationofceramicballs,thespentFCCcata

    lystmustbecalcinedpriortopreparationofaluminaabra

    sionresistantceramicbails.Accordingtotheinformation mentionedinthereferenceTM,thespentFCCcatalystmate

    rialshouldbepreheatedto1350?.thencooleddownand

    crushedtoformtheclinkertomakethespentFCCcatalyst morecatalyticallyreactive.

    Itisnecessarytoincludemoredosageofspentequilibrium FCCcatalystasfaraspossibleifthepropertyofthefinal productcanmeetthequalitystandard.Afterreferringtothe dosageandkindoffluxesappliedintheoverseassimilar products,theBaOMgO-SiO2A1203systemwasselected

    amongfourconventionalsystems(namelyMgOSiO2-

    A1203,CaOSiO2-A1203,CaOMgOSlOEA1203,andBaO

    MgOSiO2A1203)coupledwithtalcandbariumcarbonate usedasthefluxwiththetalc/BaCO3ratioequatingto2:1. Amixturecomposedof75m%clinker,16m%clay,6m% talc.and3m%bariumcarbonate【】waspreciselyweighted

    andwasgroundinaballmillinawettedstatefor24hours withtheratioofA1203ceramicball/water/clinkerbeingmain

    tainedat2:1.1:1.Thewatersolidslurryaftergrindingin

    ballmillshouldbefilteredthroughthe200-meshscreen withthefilterresiduecontrolledatlessthan0.1%.The filteredslurrywasbakedtoawatercontentofaround6% andthenwassievedthroughascreenofbetween20mesh tO80meshtodiscardverytinyandlargeparticles.The therebypreparedpowderedmaterialwassubjectedto sammingfor24hourspriortobeformedintothehalf-fin

    ishedproduct(bodystock)underapressureof25MPafor 10seconds.Theformedbodystockwasdriedinairfor24 hoursandwasthendriedinadryingovenatIO0~Cuntil

thewatercontentinthebodystockwasreducedto?1%.

    Finallythedriedceramicballswascalcinedat1410?for

    2hourstoyieldthequalifiedproduct.

    2.4Measurementofphysicalprope~iesofceramicballs Thequalityindicesofceramicballsgenerallyincludet7-91: compressionstrength,microhardness,attritionrate,bulk densityandwateradsorptionrate.Thecompressionstrength ofceramicballsismeasuredbymeansofbendingatthree

    1986, pointsaccordingtothenationalstandardGB6569

    andtheVickershardnessofsinteredsamplesismeasured bymeansofaHV.1000typesmal1loadVickershardness

    testeraccordingtothenationa1standardGB/T16534

    1996.Theattritionrateofsamplesisdeterminedbycalcu

    latingtheratiobetweenthewornweightandtheoriginal weightofsampleinapredeterminedtimeaccordingtothe testmethodJC/T848.1-1999.andthebulkdensityismea- suredaccordingtothenationalstandardGB/T16458.2

    1996,whilethewateradsorptionrateofceramicballsis determinedaccordingtothenationalstandardGB/T3810 3l999.

    3ResultsandDiscussion

    3.1Chemicalanalysisofmaterialsformanufactureof ceramicballs

    Themainrawmaterialsformanufactureofceramicballs include:therawspentFCCequilibriumcatalystprovided bytherefinery,clayandtalc,withtheirchemicalcomposi

    tionspresentedinTable1.

    Table1Chemicalcompositionofmajorrawmaterialsm% ItemsRawequilibriumFCCcatalystClayTalc

    Si0:42.0372.0660_44

A1:O352.0718.561.19

    Fe2O3O.931.050.14

    TiO21.050.09

    CaO1.970.073.1

    MgO0.I40.2l29.02

    K2o0.190.85

    Na2OO.190.09

    Weightlossafter

    1.457.0l5.32

    calcination

    ItcanbeseenfromthedatalistedinTable1thattheweight lOSSofrawmaterialsaftercalcinationswassmal1.whilethe SiO2andA1203contentswerequitehigh.Duringtheex

    perimentsinordertoreducethecontractionrateandin. creasethebulkdensityofceramicballsitwasnecessaryto preheattherawequilibriumFCCcatalyst.

    3.2Analysisofphysieo-chemicalpropertiesofequilib- riumFCCcatalyst

    3.2.1XRDanalyses

    TheXRDpatternsofspentequilibriumFCCcatalystare presentedinFigurel,whichindicatedthatintheregion betweenthepeakandthebaselinetherewasabreadlike

    noncrystallinearea,indicatingtotheexistenceofYA1203

    crystals,Si0:crystals,andamorphousYAl2O3andSiO!.

    Thesurfacenonhomogeneityresultedfromthelattice defects,vacancyanddislocationontheparticlesurface couldcausethepolarizeddeformationandrearrangement ontheparticlesurfacetoinducethelatticeaberrationon thesurfacewithareducedorderedstate.Thissurfacenon

    homogeneitycouldcontinuouslydevelopindepthwitha

    decreasingparticlesizetomakethemolecularstructureof 25

    102O3O4050607080

    2(.)

    Figure1XRDpatternofequilibriumFCCcatalyst theequilibriumFCCcatalystbecomeamorphousthatwould showflbreadlikeareainsteadofpeaksontheXRDpatterns. ThispartofmoleculesoftheequilibriumFCCcatalystwas unstableandinahighenergystatuswithhighactivitythat couldexertabigpropulsiveforcetothediffusion,solid

    phasereactionandagglomerationofparticlesathightern

    peraturetofavortheformationandagglomerationofsyn

    theticproducts.Sincesomeparticlesoftheequilibrium FCCcatalysthadasizearoundonemicrometer,theYA1203

    particlescouldberecognizedascrystallinewiththechar

    acteristicpeaksofcrystalsontheirXRDpatterns. 3.2.2FTIRspectroscopy

    ItcanbeseenfromFigure2thattherewasflbroadabsor

    bancebandat3448cmthatwasascribedtostretching

    vibrationsof0Hgroups.indicatingtoalotofhydroxyl radicalsintheequilibriumFCCcatalyst,andat1385cm. therewasastrongandnarrowabsorbancebandthatwas ascribedtobendingvibrationsof0Hgroups.Theasym

    metricvibrationsofSiOradicalsatl08lcmhadmoved

    towardsthehighfrequencydirectionwithalesssymmetri

    calnatureofband.indicatingtothepolymerizationofSi

    OgroupstoformSi0Sibonds.Abettersymmetryof

    bandwasfoundat837cm,whichwascausedbyvibra.

    400035003000250020001500l000500

    Wavenumber,cm'

    Figure2FT-IRpatternofequilibriumFCCcatalyst LiangZhiyu,etal?PreparationofAluminaAbrasion

    ResistantCeramicGrindingBallwithSpentFCC EquilibriumCatalyst

    tionsoffourcoordinatedAlOradicals.showingthatthe

    formationOfSi0Aland

    tionofAIforSiinthe[SiO4

    3.2.3DTA-TGanalyses

    Al0bondsaftersubstitu.

    tetrahedralradicals.

    TheoverallthermogravimetriccurvesofthespentFCC equilibriumcatalystarepresentedinFigure3.Itcanbe seenfromthecurvesshowninFigure3thatontheTG curvetheweightlossintherangefromtheambienttem

    peratureto100?correspondedtothedeliveryofhygro

    scopicallyformedwaterfromtherawmateria1.Theweight lossoftherawmaterialintherangebetween780.Cand 1000?wasequaltoaround10%,whichwasascribedto thetransformationincrystallineformofA1203andSi02 containedintherawmaterialwithanincreasing temperature,anditcanberecognizedthatmullitewas formedfollowingthereactionsofA12OsuponSiO2judging fromtheheatabsorptionpeakataround780~ContheDTA Cl1rVe

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    98

    96

    94

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    92

90

    88

    0

    -

    l

    -

    2

    .

    .

    3

    200400600800l000

    Temperature,?

    Figure3DTA-TGofequilibriumFCCcatalyst

    3.2.4BETanalyses

    ItcanbeseenfromFigure4thattheN2adsorptionisothernl hadaS,shapedformthatcouldbeclassifiedasthetypeIV isothermaccordingtotheIUPACclassificationguideline. InthehighP/Poregionadsorptionwasapparentlyincreased withanapparenthystereticring,indicatingtotheoccur

    renceofcapillarycondensation,whichcouldreflectdiffer

    entmodesofparticlebuildupinthestructureofthesample withmultipletypesofpores.Analysishasshownthatthe specificsurfaceareaofthesamplewas88.13cm/g.Itcan beseenthroughanalyzingtheporestructure(Figure5)that

    0.070cm/gandthe theporevolumewasbetween0.040

    porediameterwasintherangeof2-128nm.Itisevident thatthissamplehadamediumspecificsurfaceareawitha 26

    00.20.40.60.81.0

    Relativepressure|P3

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