THÔNG TIN TÀI LIỆU
MIISTRYOFE D U C A T I O N A N D T R A I N I N G HANOIU N I V E R S I T Y O F S C I E N C E A N D T E C H N O L O G Y PHẠMTHỊMAIPHƢƠNG STUDY ON THE PROCEDURESOFTHE SUPPORT ON THESUBSTRATES TO PREPARE CATALYTIC COMPLEXES FORTHETREATMENTOFMOTORBIKE’SEXHAUSTEDGASES DOCTORO F PHILOSOPHYT H E S IS : C H E M I C A L E N G I N E ERING HANOI–2 MINISTRYOFEDUCATIONANDTRAINING HANOIUNIVERSITYOFSCIENCEANDTECHNOLOGY PHẠMT H Ị MAIP H Ƣ Ơ N G STUDY ON THE PROCEDURES OF THE SUPPORT ON THESUBSTRATES TO PREPARE CATALYTIC COMPLEXES FOR THETREATMENTOFMOTORBIKE’SEXHAUSTEDGASES Chuyênngành:Kỹthuật hóa họcMãsố:62520301 DOCTOROFPHILOSOPHYTHESIS:CHEMICAL ENGINEERING SUPERVISOR: 1.A s s o c Dr.LÊMINHTHẮNG HANOI–2014 Commitment I assure that this is my own research All the data and results in the thesis arecompletely true, was agreed to use in this paper by co-authors This research hasn‟t beenpublishedbyotherauthorsthanme PhạmThịMaiPhƣơng Acknowledgement This Ph.D thesis has been carried out at the Department of Organic Synthesis andPetrochemistry,SchoolofChemicalEngineering,HanoiUniversityofScienceandTechnolo gy during the period July 2010 to September 2013.The work has been completedunderthesupervisionofAssoc.Prof.Dr.LeMinhThang Firstly, Iwouldlike toexpressmy deepest andmost sinceregratitudetomypromotors: Assoc Prof Dr Le Minh Thang She has been helping me a lot not only in thescientific work but also in my private life Without her guidance, her encouragement, herenthusiastic and kind help, it would have been difficult to overcome the difficulties I metduringthepresentwork I wantto thankmy colleaguesin thelabEnvironmentfriendly Materials andTechnologiesfortheirfriendlyattitudetowardsmeandtheirhelpinmywork I would like to thank all members of the Department of Inorganic and PhysicalChemistry, especially the group of Solid State Chemistry for their support and guidanceduringtheperiodIwasinBelgium I am gratefultotheentirememberinthe AdvancedInstituteof Science andTechnologyfortheirhelp,andniceenvironmenttheycreatedforme I especially want to expressmy sinceregratitudeforthe cooperation programbetween Flemish Interuniversity Council (VLIR) andHanoi University ofTechnology(HUT) for the financial support for this study I acknowledge to Prof Isabel Van Driessche(Coordinatorofthecooperationprogram)fortheadministrativehelp Finally, I lovingly thank my family for their love and encouragements during thewholelongstudyperiod Contents LISTOFABREVIATES .8 CONTENTOFTABLES .9 CONTENTOFFIGURES 10 INTRODUCTION .13 CHAPTER1.LITERATUREREVIEW .14 1.1 Airpollutioncaused byvehiclesemission .14 1.1.1 Overtheworld andinVietnam 14 1.1.2 Airpollutantsf r o m emission 15 1.1.3 Solutionsforairpollution 16 1.2 Thecatalyticconverter 18 1.2.1 Substrates 19 1.2.2 Supports .22 1.2.3 Activephase 27 1.3 Kineticmodellingoftransientexperimentsofautomotiveexhaustgascatalyst 30 1.4 Synthesismethods 33 1.4.1 Principlesofsomesynthesismethods 33 1.4.2 Synthesismethodsofsubstratesand supports 34 1.5 Preparationthecatalyticconverters 37 1.5.1 Coatingamonolithwithacatalysissupportmaterial .37 1.5.2 Depositionofactivephaseonmonolithicsupport 39 Literaturereview‟sconclusion 40 1.6 Theaimofthethesis .41 CHAPTER2.EXPERIMENTS 43 2.1 Preparationthesubstrates 43 2.1.1 Preparationofthecordieritesubstrate .43 2.1.2 PreparationofCordieriteusing additives 44 2.1.3 Preparationofcordieritewiththeadditionofdolomite 44 2.1.4 Surfacetreatmentofprepared cordierite 44 2.1.5 SurfacetreatmentofFeCralloysubstrate 44 2.2 Preparationthesupports 47 2.2.1 γ-Al2O3 47 2.2.2 Ce0.2Zr0.8O2mixedoxides 47 2.2.3 AlCe0.2Zr0.05O2mixedoxide 47 2.3 Deposition methodsofsupportoncordierite substrate .49 2.3.1 Directcombustion 49 2.3.2 Hydriddeposition 49 2.3.3 Suspension 50 2.3.4 Secondarygrowth 50 2.3.5 Doubledepositions .50 2.4 Depositionofsupportonmetalsubstrates 52 2.5 Depositionofactivecatalyticphaseonsupport/substrate .52 2.6 Preparationoftherealcatalyticconverter 52 2.7 Catalystcharacterization 54 2.7.1 X-raydiffraction(XRD) 54 2.7.2 Characterizationofsurfacepropertiesbyphysicaladsorption 54 2.7.3 Scanningelectronmicroscopy(SEM) 56 2.7.4 ThermalAnalysis 56 2.7.5 X-rayphotoelectronSpectroscopy(XPS) 57 2.8 Catalyticactivitymeasurement 57 2.8.1 Measurementofcatalyticactivityinthemicro-reactorconnectedwithG C online 57 2.8.2 Measurementofexhaustedgases 58 CHAPTER3.RESULTSANDDISCUSSION .60 3.1 Synthesisofcordieritesubstrate 60 3.1.1 Influenceofsynthesismethodsonthepreparationofcordierite 60 3.1.2 Theinfluenceofburnableadditivesonthesynthesisofcordierite .62 3.1.3 Theinfluenceofdolomiteonsynthesisofcordierite 66 3.1.4 Influenceofacidtreatmentonsurfaceareaofcordierite .67 3.2 PreparationofFeCrmetalsubstrate 72 3.3 Synthesisofsupports 73 3.3.1 Synthesisofboehmiteandγ-Al2O3 73 3.3.2 SynthesisofCe0.2Zr0.8O2mixedoxide 75 3.3.3 AlCe0.2Zr0.05O2mixed oxides 77 3.4 Depositionofsupportonsubstrates 84 3.4.1 PreparationofCe0.2Zr0.8O2oncordierite 84 3.4.2 Preparationofγ-Al2O3supportoncordieritesubstrate 90 3.4.3 PreparationofAlCe0.2Zr0.05O2supportoncordieritesubstrate 91 3.5 Characterizationofcompletecatalysts 92 3.5.1 MnO2–NiO–Co3O4/Ce0.2Zr0.8O2/cordierite 92 3.5.2 MnO2-Co3O4-CeO2/AlCe 0.2Zr0.05O2/cordierite 95 3.5.3 MnO2-Co3O4-CeO2/support/FeCralloys .98 3.6 Catalyticactivitiesofthecompletecatalysts 101 3.6.1 MnO2–NiO–Co3O4/Ce0.2Zr0.8O2/cordierite 101 3.6.2 MnO2-Co3O4-CeO2/supports/cordierite .103 3.6.3 MnO2-Co3O4-CeO2/support/FeCralloys 105 3.7 Commercialcatalyst 106 3.8 CatalyticactivityofMnO2-Co3O4-CeO2/cordieritemonolith installedinmotorbike108CONCLUSION 111 REFERENCES 113 PUBLISHEDREPORTS 121 APPENDIX 122 LISTOFA B R E V I A T E S Symbols NOx THC NMHC CO PM NO2 O3 PM10 SO2 NO VOCs HC TWCs A/F OSC ACZ CZ XRD BET SEM TGA DTA XPS CTAB SDS PEG Meaning Nitrogenoxide Totalhydrocarbon Non-methanehydrocarbon Carbonmonoxide Particulatematter Nitrogendioxide Ozone Particulatematterlessthan10nmindiameter Sulfurdioxide Nitrogenoxide Volatileorganiccompounds Unburnedhydrocarbons Three-waycatalysts Airtofuel Oxygenstoragecapacity Al2O3–CeO2–ZrO2mixedoxides CeO2–ZrO2mixedoxides X-raydiffraction Brunauer,EmmettandTeller Scanningelectronmicroscopy Thermogravimetricanalysis Differentialthermalanalysis X-rayphotoelectronSpectroscopy Cetyltrimethylammoniumbromide Sodiumdodecylsulfate polyethyleneglycol CONTENTOFT A B L E S Table1.1.EuropeanEmissionStandard 15 Table 1.2.EmissionStandardsforin-usedvehiclesinVietnam 15 Table1.3:CharacteristicpropertiesofCordierite .20 Table1.4.TWCmicrokineticschemeusedinthemodel[66,67] .30 Table2.1.The content(weight%)ofmain metaloxidesinkaolin afteractivation 43 Table2.2.Synthesisconditionofsubstratessamples 45 Table2.3.Synthesisconditionsofsupportssamples 48 Table2.4 Synthesisconditionsofsupportsdeposited onsubstratessamples 51 Table2.5.Synthesisconditionsofc a t a l y s t samples 53 Table2.6.StandardXRDreflectionsofthes y n t h e s i z e d materials 54 Table3.1.Propertiesofcordieritesamplessynthesizedfromdifferentmethods 61 Table3.2.Propertiesofsynthesized Cordieriteusingadditive 64 Table 3.3 The BET surface areas of the cordierite prepared by conventional sintering fromkaolinwithdifferentadditionofcellulosebeforesintering .65 Table3.4.Compositionsofprecursorstopreparecordierite .66 Table3.5.Contentofcordieritephaseintheproductandimpuritiesintheprecursor .66 Table3.6 ContactangleofFeCrmetalsubstrates 73 Table3.7.Charaterizationofboehmiteandγ-Al2O3 74 Table3.8.BETspecificsurfaceareas,poresizes,porevolumesoftheCZsamples 76 Table3.9.BETsurfaceareaofACZsamplessynthesizedusing differentprecipitants 79 Table3.10.TheBETsurfaceareaofsamplessynthesizedwithandwithoutaging .82 Table3.11.TheBETresultsofmixedoxideswithdifferentsurfactants 83 Table3 S u r f a c e a r e a o f C e 0.2Zr0.8O2/ cordierites a m p l e s p r e p a r e d b y d i f f e r e n t depositionmethods 85 Table3.13 Characterizationofγ-Al2O3supportoncordieritesubstrate .90 Table3.14.Atomiccompositions(%)ofcomponentsinCa.2 and Ca.3 catalysts .93 Table 3.15 Atomic compositions(%) of components in Ca.2 and Ca.3 catalysts by XPS 95Table3.16.ResultsofBETsurfaceareaofMnO2-Co3O4-CeO2catalysts 97 Table3.17.A t o m i c composition(%)ofthecommercialcatalystCAT920basedonmetalsubstrate 108 Table3 T h e c o n t e n t of emis s ion g a s e s w i th a n d w i t h o u t catalytic c o m p l e x ( C a 1 - MnO2-Co3O4-CeO2/AlCe0.2Zr0.05O2/cordieritemonolith) .109 Table3.19.EmissionofmotorbikeVespai n s t a l l e d thecommercial catalystsf r o m Vesp a based onmetalsubstrates 110 CONTENTOFF I G U R E S Fig.1.1.Schemeofsuccessivetwoconvertermodel[20] 17 Fig.1.2.Structureofthree-wayscatalyst[23] 19 Fig.1.3:Theformationofvariousaluminaatdifferentcalcinationtemperature 22 Fig.1.4:Structure ofγ-Al2O3 23 Fig.1.5:Phase diagramoftheCeO2–ZrO 2system 24 Fig.2.1.Isothermadsorption 55 Fig.2.2.IUPACclassificationofhysteresisloops(revisedin1985) 56 Fig.2.3.Schemaofmicro-reactorsetup 58 Fig.2.4.Schemaofexhausttubewithafixed catalyticconverter 59 Fig.2.5.Schemaofmeasuringmotorbike‟sexhaust gases 59 Fig.3.1:XRDpatternsofCordieritesamplespreparedbyvariousmethods 56 Fig.3.2.S E M i m a g e o f Cordierite p r o d u c e d b y s o l - g e l p r o c e s s i n g : SG0( a ) a n d conventionalsinteringofkaolin:CV-0(b) 61 Fig.3.3.TGA-DSCofcordieritesamplespreparedfromsol-gelmethod 62 Fig.3.4.X R D patternofcordieritesamplepreparedbyconventionalsinteringcalcinedat 1400oC 62 Fig3.5.XRDpatternsofcordieritepreparedbyconventionalsinteringwithdifferentadditionof 63 activatedcarbon 63 Fig.3.6.XRDpatternsofcordieritepreparedbysol-gelwithdifferentadditionof .64 activatedcarbon 64 Fig.3.7.SEMimageofcordieriteproducedfromkaolinwithout .65 Fig.3.8.S EM i m a g e of cordieriteproduced by sol-gelprocessingwithout- S G (a) andwith-SG-5AC(b)theadditionofactivatedcarbonto thepreforms .65 Fig.3.9.XRDpatternsofcordieritesamplespreparedwithdifferentdolomitec o n t e n t (TX1,T D.1andTD.2) 67 Fig.3.10.BETsurfaceareaofHCltreatedcordieritepellets(CV-0)atdifferentperiodsoftime .67 Fig.3.11.SEMimagesofsubstratesbefore(a)andafterhydrochloricacidtreatmentfor8h(b),12 h(c) 68 Fig.3.12.XRDpatternsofsamplestreatedcordieritebyhydrochloricacid 69 Fig.3.13.EffectofHClacidtreatmentoncordierite‟scontent 69 Fig.3 X R D patternsofsamplesw i t h 8.69w t % ofdolomitebefore (T D ) andaf te r HCltreatment(TD1.1) 70 Fig.3.15.X R D patternsofcordieritesampleswith16.27wt %ofdolomitebefore( T D ) andafterHCltreatment(TD2.1) 70 Fig.3.16.Influenceofacidtreatmentoncordieritecontent(a)andBETsurface area(b)ofthecordieritesampleswithadditionofdolomite(8.69wt.%-TD1, 16.27wt.%TD2)7 Fig.3.17.T h e determinationo f c o n t a c t angleofuntreated(a)andtreated(b)metal sub stratesby B3procedure(calcinedat800oC, then immersedinNaOH10wt%) 72 Fig.3.18.XRDpatternofboehmite 73 Fig.3.19.XRDpatternofγ-Al2O3 74 Fig.3.20.Adsorption-desorptionisothermplotsofboehmiteandγ-Al 2O3 74
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