Characterization and Design of Zeolite Catalysts: Solid Acidity, Shape Selectivity and Loading Properties

196 Pages·2010·5.88 MB·English

by  Miki Niwa

SpringerSeriesin
materials science
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Editors: R.Hull C.Jagadish R.M.Osgood,Jr. J.Parisi Z.Wang H.Warlimont
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Miki Niwa
Naonobu Katada
Kazu Okumura
Characterization
and Design
of Zeolite Catalysts
Solid Acidity, Shape Selectivity
and Loading Properties
With135Figures
123
Prof.MikiNiwa Prof.NaonobuKatada
TottoriUniversity TottoriUniversity
GraduateSchoolofEngineering GraduateSchoolofEngineering
Dept.Chemistry&Biotechnology Dept.Chemistry&Biotechnology
Koyama-Minami4-101 Koyama-Minami4-101
680-8552Tottori,Japan 680-8552Tottori,Japan
[email protected] [email protected]
Prof.KazuOkumura
TottoriUniversity
GraduateSchoolofEngineering
Dept.Chemistry&Biotechnology
Koyama-Minami4-101
680-8552Tottori,Japan
[email protected]
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UniversityofVirginia UniversitätOldenburg,FachbereichPhysik
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AustralianNationalUniversity UniversityofArkansas
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MicroelectronicsScienceLaboratory DSLDresdenMaterial-InnovationGmbH
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Preface
Catalysis and catalyst is a key technology to solve the problems in energy and
environment issues to sustain our human society. We believe that comprehensive
understandingof the catalysis and catalystprovidesus a chance to developa new
catalystandcontributesgreatlytooursociety.However,thefieldofheterogeneous
catalystisdifficulttostudyandstillstaysbehindmoredevelopedfieldsofchemistry
such as organic and physical chemistries. This is a dilemma to the chemists who
study the catalysis and catalyst. While we can accomplish the progress in the in-
dustrialapplication,thescientificunderstandingisnotcompleteyet.Agapbetween
the useful application and incomplete scientific understanding,however,becomes
smallerandsmallerinrecentyears.
Because zeolites are fine crystals, and the structure is clearly known,the study
onthecatalysisusingthezeolitesiseasierthanthoseencounteredinothercatalysts
such as metals and metal oxides. Very fortunately, zeolites provide us the strong
acidity with the fine distribution which enables various useful catalytic reactions.
Whensomemetalsandcationsareloadedinclosetotheacidsites,theseloadedele-
mentsshowextraordinarycharacters,andmanycatalyticreactionsproceedthereon.
Microporosityprovidesusauniquepropertyoftheshapeselectivity,andtheexcel-
lentselectivityisobserved.Thesevariousbeneficialpropertiesofzeolitesleadusto
studythefundamentalchemistrywhichisrelatedtothecatalyticproperties.Inthis
book, we want to summarize three important properties of zeolites: solid acidity,
shapeselectivity,andloadingproperty.Toaccomplishthestudyonthem,threekinds
ofimportanttechniquesareexplainedindetail,i.e.,temperature-programmeddes-
orptionofammonia,chemicalvapordepositionofsilica,andEXAFSmeasurement.
Wewillfocusonourinterestsonthesecharacterizationtechniquesandintroducethe
readerofthisbooktoourcharacterizationschoolforzeolitecatalysts.
Three of us are staffs in Tottori University, Japan, and education and research
areourduty.Itisourpleasurethatwestudyandlearnthechemistryofcatalysisby
collaboratingwith manystudentsin this laboratory.Our study dependsgreatly on
thecollaborationwiththem.
We first proposed the publication of this book to Mr. Ippei Ohta belonging to
Tokyo Institute of Technology Press, but unfortunately this publication was not
related to his recent job. However, he introduced to us Dr. Claus E. Ascheron,
v
vi Preface
SpringerScience andBusiness Media,Heidelberg,Germany;and heacceptedour
proposal.Withouthisstrongsupporttoouractivity,thisbookwouldneverbepub-
lished.WewanttoexpressoursincerethankstoMr.OhtaandDr.Ascheron.
Tottori,Japan MikiNiwa
May2010 NaonobuKatada
KazuOkumura
Contents
Preface............................................................................... v
1 IntroductiontoZeoliteScienceandCatalysis .............................. 1
1.1 GeneralTrendoftheZeoliteAcidCatalyst:Species,
Structure,andIndustrialApplication..................................... 1
1.2 PropertyofZeoliteCatalyst:Acidity,ShapeSelectivity,
andLoadingProperty..................................................... 5
1.3 Intention of the Publication with the Background
oftheZeoliteChemistry.................................................. 6
References....................................................................... 8
2 SolidAcidityofZeolites....................................................... 9
2.1 MultipleCharacterizationTechniques ................................... 9
2.1.1 PhysicalProperties................................................ 9
2.1.2 ChemicalProperties .............................................. 10
2.2 FundamentalsfortheTPDofAmmonia................................. 11
2.2.1 ExperimentalApparatusoftheTPDMethod.................... 11
2.2.2 IdentificationoftheDesorption,l-andh-Peaks ................ 13
2.2.3 IdentificationofAmmoniaDesorbedfromYZeolite........... 14
2.3 TheoryfortheTPDofAmmonia ........................................ 15
2.3.1 ConditionsoftheEquilibrium ................................... 15
2.3.2 DerivationofaFundamentalEquation .......................... 17
2.3.3 Determinationof(cid:2)H andConstancyof(cid:2)S (Desorption)..... 19
2.4 PracticalMeasurementsofAmmoniaTPD.............................. 20
2.4.1 CurveFittingMethodtoMeasuretheStrengthofAcidSite ... 20
2.4.2 (cid:2)H on Various Zeolites with Different
ConcentrationsofAcidSite...................................... 21
2.5 NumberofAcidSitesonVariousZeolites............................... 24
2.5.1 NumberofAcidSitesCorrelatedwithAlConcentration....... 24
2.5.2 InSituandExSituPreparedH-typeZeolites ................... 26
References....................................................................... 27
vii
viii Contents
3 IRMS-TPDMeasurementsofAcidSites.................................... 29
3.1 MeasurementMethod..................................................... 29
3.1.1 WhatIsObtainedfromtheTPDMeasurement ................. 29
3.1.2 ExperimentalMethods............................................ 29
3.1.3 RequiredCorrections,IRBandPositionand(cid:2)S ............... 31
3.2 ProtonFormZeolite....................................................... 32
3.2.1 H-Mordenite ...................................................... 32
3.2.2 H-YandH-Chabazite............................................. 34
3.3 ModifiedZeolites ......................................................... 39
3.3.1 MultivalentCation-ModifiedZeolite ............................ 39
3.3.2 UltrastableY(USY)Zeolite ..................................... 41
3.4 DistributionofBrønstedAcidSitesDependentontheConcentration . 43
3.5 Relationship Between Stretching Frequency
andAmmoniaDesorptionHeatofOHGroup........................... 45
3.6 DistortedStructureofZeoliteandRelatedMaterialwith
LewisAcidityandBroadDistributionofAcidStrength................ 47
3.7 MeasurementsofMetalOxideOverlayer................................ 52
3.8 ExtinctionCoefficientsofNH4C andNH3 Adsorbed
onBrønstedandLewisAcidSites,Respectively........................ 55
References....................................................................... 59
4 DFTCalculationoftheSolidAcidity........................................ 61
4.1 DFTCalculation .......................................................... 61
4.1.1 DFT Calculation Applied to the Study
onBrønstedAcidity .............................................. 61
4.1.2 EmbeddedClusterandPeriodicBoundaryConditions......... 62
4.2 ApplicationtoChabazite,aSimpleZeolite.............................. 63
4.2.1 BrønstedAcidSitesinChabaziteBasedonthe
ModelsWithinthePeriodicBoundaryConditions.............. 63
4.2.2 BrønstedAcidSiteinanEmbeddedClusterModel ............ 65
4.3 ApplicationtoOtherZeolites............................................. 65
4.3.1 FAU,MOR,andBEACalculatedUndertheConditions
oftheEmbeddedClusterandthePeriodicBoundary........... 65
4.3.2 MFI, FER, and MWW Calculated Under
theEmbeddedClusterModel .................................... 67
4.4 ModifiedZeolites ......................................................... 69
4.4.1 DivalentCation-ExchangedYZeolitesBased
ontheEmbeddedClusterModel................................. 69
4.4.2 Modified Brønsted OH in Y Zeolite Based
onthePeriodicBoundaryConditions............................ 71
4.5 DependenceofBrønstedAcidStrengthonLocalGeometry ........... 72
References....................................................................... 78
Contents ix
5 CatalyticActivityandAdsorptionProperty................................ 79
5.1 ParaffinCracking.......................................................... 79
5.1.1 EvaluationofIntrinsicActivityofAcidSite .................... 79
5.1.2 DependenceofActivityonAcidStrength....................... 81
5.1.3 ThermodynamicDescriptiononCorrelation
Between Activation Energyand Ammonia
DesorptionHeat................................................... 86
5.1.4 BehaviorofAcidSitesin8-and12-RingsofMordenite....... 88
5.2 AdsorptionofAromaticHydrocarbons.................................. 89
5.3 Friedel–CraftsAlkylationonGa-MCM-41.............................. 93
5.4 AminationofPhenolintoAnilineonGa/ZSM-5........................ 97
References.......................................................................100
6 CVDofSilicafortheShapeSelectiveReaction.............................103
6.1 ReactantsandProductsShapeSelectivity,ConceptandDefinition ....103
6.2 ChemicalVaporDepositionofSilicaandtheProcedure................104
6.3 FormationofSilicaOverlayerontheExternalSurface.................108
6.3.1 Method of Benzene-Filled Pore for the
MeasurementofExternalSurfaceArea .........................108
6.3.2 MechanismofCVDtoformtheSilicaOverlayer...............109
6.3.3 Formation of Silica Overlayer on Zeolite
andMetalOxide,andItsFunction...............................110
6.4 FineControlofPore-OpeningSize ......................................111
6.4.1 Mordenite .........................................................112
6.4.2 MFIZeolite .......................................................113
6.4.3 AZeolite ..........................................................114
6.4.4 YZeolite ..........................................................119
6.5 CharacterizationofDepositedOxide ....................................120
6.5.1 XPSMeasurements...............................................120
6.5.2 EXAFSoftheDepositedGermanium...........................121
6.5.3 TEMObservation.................................................123
6.6 ExternalSurfaceAcidity:MeasurementsandInactivation..............124
References.......................................................................127
7 ApplicationoftheCVDofSilicatotheShapeSelectiveReaction........129
7.1 SelectiveFormationofPara-Dialkylbenzene............................129
7.1.1 PrincipleoftheShapeSelectivity................................129
7.1.2 CVDZeolitetoProducethePara-Dialkylbenzene..............131
7.1.3 InSituProductionofCVDZeolites .............................135
7.1.4 HZSM-5 In Situ and Ex Situ Prepared
fortheCVDofSiliconAlkoxide ................................136
7.1.5 CLDofSilicafortheShapeSelectiveAdsorption..............136
7.2 SelectiveCrackingofLinearAlkane(Dewaxing).......................139