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1、ThermodynamicsofPtlCementClinkeringTheodeHanein1FredrikP.Glasser2MarcusBannerman11.SchoolofEngineeringUniversityofAberdeenAB243UEUnitedKingdom2.DepartmentofChemistryUniversityofAberdeenAB243UEUnitedKingdomAbstractTheusef

2、ulpropertiesofcementarisefromtheassemblageofsolidphasespresentwithinthecementclinker.ThephaseproptionsproducedfromagivenfeedstockareoftenpredictedusingwellestablishedstoichiometricrelationssuchastheBogueequations.Theseap

3、proachesarebasedonasingleestimationofthestablephasesproducedunderstardprocessingconditionssotheyarelimitedintheirgeneralapplication.Thiswkpresentsathermodynamicdatabasesimpleequilibriummodelwhichiscapableofpredictingceme

4、ntphasestabilityacrossthefullrangeofkilntemperaturesincludingtheeffectofatmosphericconditions.Thisistermeda“reactionpath”benchmarksthekiicsofprocessesoccurringinthekiln.Phasestabilityiscalculatedusingstoichiometricphased

5、ataGibbsfreeenergyminimizationundertheconstraintsofanelementalbalance.PredictionsofstablephasesstardphasediagramsarereproducedfthemanufactureofdinaryPtlcementvalidatedagainstresultsintheliterature.Thestabilityoflowtemper

6、aturephaseswhichmaybeimptantinkilnoperationisexpled.Finallyanoutlookonfutureapplicationsofthedatabaseinoptimizingcementplantoperationdevelopmentofnewcementfmulationsisprovided.iginalityThisreptdetailscrectionstoreference

7、thermodynamicdatawhicharerelevantfcementthermodynamiccalculations.Whencombinedwithasuitablethermodynamicmodelthisdataallowsthecalculationofthestablecementclinkerphasesacrossarangeoffeedstockcompositionsoperatingcondition

8、satmospheres.Herewepresentupdatedcalculationsofstardcementprocessingphasediagramsdata.Incomparisontootherstudiesthiswkincludesgreaternumbersofcomponentsamecomprehensivedatabaserevealingsolidgasreactionstheearlystagefmati

9、onofphasessuchasspurrite(C5S2C’)whoseimptancemaynotbefullyappreciated.Theaccuracyofthepredictionsdemonstratesthatastoichiometricapproachisusefulevenatthehighestkilntemperatures.Thedatabasealsoincludesenthalpicdatawhichca

10、nbeusedasthebasisofaprocessheattransfermodeltooptimizedesignentirecementproductionprocesses.Keywds:CementThermodynamicsClinkerphasesHightemperature.Crespondingauth:Tel441224274480productionofamodelfhightemperatureclinker

11、phasepredictionsasignificantnumberofmisprintserrsinpublishedcoefficientswerefoundintheliterature.Thedatasourcesusedtheseerrsarediscussedinthefollowingsection.2DatasourcesThermodynamicdatafgasphasesanumberofliquidssolidsh

12、avebeentakenfromtheNASACEAdatabase(McBrideetal.2002).Thisisacomprehensivefreelyavailabledatasetiginallyusedinrocketcombustioncalculationstherefeitisideallysuitedfmodellingatmosphericreactionsunderkilnconditions.Datafmany

13、ofthemajclinkersolidphaseshavebeenobtainedfromthebenchmarkstudybyHaasJretal.(HaasJretal.1981)howeveritcontainsanumberofmisprintsintheenthalpyconstant(a2)asdetailedintable2.Thesedatawerecheckedcrectedbyconsideringthetable

14、sofcalculateddatafeachspeciesgiveninthereference.Thereareanumberofkeyphaseswhicharenotincludedintheabovereferences.ThecompilationofBabushkinetal.(Babushkinetal.1985)isanothersourceofthermodynamicdatahowevernumeroustranio

15、nerrsarealsopresentinthiscompilation.FexampletheheatcapacitycoefficientsfC3AdiffertothoseintheiginalsourcetheseerrshaveevenbeencarriedoverintotheCEMDATA07databaseusedinGEMS(Thoenen&Kulik2003).Toreducetranionerrstheheatca

16、pacitydatausedinthiswkaretakendirectlyfromtheiginalsources.ReferenceenthalpyentropyconstantsweregenerallytakenfromtheNBStables(Wagmanetal.1982).Someoftheliteraturesourceslistedherecontaindifferingdatafthesamespecies.Inth

17、esecasesthesourcesarefavouredinthefollowingder(McBrideetal.2002)(HaasJretal.1981)(Holl&Powell2011)(Wagmanetal.1982)(Bardetal.1985).OnelimitationofthepresentdataisthathatruriteotherpolymphsofC3Sareundifferentiatedasavaila

18、bledataareinsufficienttoevaluatepropertiesoftheindividualpolymphs.Thedatausedinthetitlestudythereferepresenttheaveragepropertiesofallpolymphs(HaasJretal.1981).Tab.2Speciesconsideredinthiswkwhosethermodynamicdatacomefroma

19、singlesource.Valuesgiveninbraces(X)arethenumberofpolymphsavailableinthedatabase.SourcePhaseSpecies(McBrideetal.2002)GasesArC2C2H4C3OSCHCH2CH3CH4CNCOCO2COSHH2H2OH2SO4HCNHCOHO2HeKK2SO4KOHKrNN2N2ONHNH2NH3NONaNa2SO4NaOHNeOO2

20、OHS2OSO2SO3SOCO2NOH3ONO3NO2OHHCOOHCaOHO2H2OAl2OAl2O2COTiOAlO2SO2O2Na2OCH2OHOMgOHCaOAlON2ONaOHAlOHO2K2OLiquidsH2OMgCO3Na2CO3Na2OK2ONa2SO4K2CO3K2SO4K2Si2O5K2SiO3MgSiO3CaSO4CaCO3SolidsCaCO3Mg2SiO4Fe2O32MgCO3KAlO2Na2CO33NaAl

21、O22Na2O3K2O3Na2SO43K2CO32K2SO42K2Si2O53K2SiO3MgSiO33MgOCaSO42MgTiO3Mg2TiO4MgTi2O5Ti3O52TiO2TiO3Ti2O32Ti4O7(HaasJretal.1981)SolidsHAlO2a2Al(OH)3CaAl2SiO6CaAl2Si2O8Ca2Al2Si3O10(OH)2bCa2Al2SiO7Ca3Al2Si3O12Al2Si4O10(OH)2Al2S

22、i2O5(OH)43Al2O3Al2SiO53Ca2Al3Si3O12(OH)cCaAl4Si2O10(OH)2dCaOCaSiO32Ca2SiO44Ca3SiO5Ca3Si2O7SiO22(Holl&Powell2011)LiquidsNaAlSi3O8CaAl2Si2O8CaMgSi2O6Mg2Si2O6Fe2SiO4Mg2SiO4KAlSi3O8Al2SiO5SolidsCa5Si2CO11CaMgC2O6Ca5Si2C2O13N

23、aAlSi3O82CaMgSi2O6Mg2Si2O6KAlSi3O8NaAlSi2O6NaFeSi2O6Fe2SiO4Fe2Si2O6(Waldbaum1965)SolidAl6Si2O13a)(Diaspe)constant(a2)valuecrectedto15671.57.b)(Prehnite)constant(a2)valuecrectedto96995.98159.c)(Zoisite)constant(a2)valuecr

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