Applications of transition metal doped zeolites

259 Pages·1994·9.2 MB·English

by  Hage, John Phillip, 1966-

APPLICATIONSOFTRANSITIONMETALDOPEDZEOLITES
By
JOHNPHILLIPHAGE
ADISSERTATIONPRESENTEDTOTHEGRADUATESCHOOL
OFTHEUNIVERSITYOFFLORIDAINPARTIALFULFILLMENT
OFTHEREQUIREMENTSFORTHEDEGREEOF
DOCTOROFPHILOSOPHY
UNIVERSITYOFFLORIDA
1994
ACKNOWLEDGEMENTS
Iwouldliketothankthemanypeoplewhohavehelpedmethroughoutmy
careerhereattheUniversityofFlorida. IwouldfirstliketothankDr.RussellS.
Dragoforhisencouragement,hisguidance,andsupportthroughouttheyears. I
wouldalsoliketothankhiswife,Ruth,forherkindnessandhospitalitythesemany
years.
Iwouldalsoliketothankthepeoplewhoweremyco-workers. Pastgroup
membersDr.MikeNaughton,Dr.StevenPetrosiusandDr.DouglasPattonwere
always there as good friends. Present group members Dr. Doug Burns (and
ImogeneBurns),Dr.DavidSingh,Dr.PhillipKaufman,MikeMcGilvray,Donald
Ferris,ChrisChronister,JonStack,KenLo,MikeGonzalez, MikeRobbins, and
AndyDadmunhavebeenavaluablesourceofknowledgeandadvicethroughout
theseyears. Iamproudtocallthemmyfriends.
Iwouldliketoacknowledgepeoplewithinthedepartmentwhohelpedmake
thingseasier. CharlieCromwell,GlennisBryant,andJeanneZacharyhelpedease
alotofbureaucraticredtape. MaureenAbdalla,KimMaxwell,andKaleeGregory
wereverysupportiveofmyeffortsandhelpedmetogetthroughwhatweresome
verydifficultmoments.
11
Mostimportantly, Iwouldliketoacknowledgeandthankmyfamily. My
motherandfather,RoxannandThomasHage,neverfalteredintheirsupport. They
gaveupanddidwithoutsomuchsothatIcouldhaveandattainthebest. They
taughtmebyexamplethatIcoulddoanythingwithhardwork,determinationand
confidence. Mostofalltheytaughtmetonevergiveuptrying.
IwouldliketoacknowledgeAirProductsforthreeyearsoffinancialsupport
forthisresearch.
in
TABLEOFCONTENTS
ACKNOWLEDGEMENTS
ii
TABLEOFCONTENTS iv
LISTOFTABLES vii
LISTOFFIGURES ix
ABSTRACT xii
CHAPTER1INTRODUCTIONTOZEOLITES 1
CHAPTER2REVERSIBLEOXYGENBINDERINSIDEZEOLITEY ... 17
Background 17
Introduction 17
UsesofOxygen 18
ProductionofOxygenandOxygen-RichAir 24
TransitionMetalComplexesinsideZeolites 36
CobaltCyanideComplexes 42
Experimental 45
SolventsandReagents 45
PretreatmentoftheZeolitePriortoMetalExchange 46
NomenclatureforMetalExchangedZeoliteY 47
MetalExchangedZeoliteY 47
CobaltexchangeintosodiumzeoliteY 47
CesiumexchangeintocobaltzeoliteY 48
Syntheticvariationsforadditionofcobaltandcesium... 48
CalciumexchangeintosodiumzeoliteY 49
CobaltexchangeintocalciumzeoliteY 49
LithiumexchangeintosodiumzeoliteY 49
CobaltexchangeintolithiumzeoliteY 50
Simultaneouscobaltandcesiumexchangeintocalcium
zeoliteY 50
iv
AproticSolvent/AzeotropeDryingProcedure 50
CyanideReactionConditions 51
CesiumcobaltcyanideinzeoliteY 51
LithiumcobaltcyanideinzeoliteY 52
Porefillingadditionofcyanide 52
SynthesisofCsCo(CN)-YunderDry,AproticConditions 53
SpectralMeasurements 54
AdsorptionMeasurements 55
ConcentrationofActiveComplex 60
EquilibriumConstantDetermination 60
MolecularWeightCalculations 61
ResultsandDiscussion 63
EPRCharacterizationofCsCo(CN)-Y 64
QuantitativeGasUptakeMeasurements 69
CyanideAdditioninProticSolvents 71
Cyanideadditioninmethanol 71
PretreatedCsCoYreactionswithcyanideinmethanol .. 79
Porefillingwithproticsolvents 92
ANovelDryingProcedureforCsCoY 98
SyntheticVariationsinAproticSolvents 99
FormationofCobaltCyanideComplexesinAproticSolvents .. 101
CyanideAdditioninMethanoltoAproticDriedCsCoY 103
CyanideAdditioninDMFtoAproticDriedCsCoY 106
CharacterizationofCsCo(CN)-Y 106
Deoxygenationtimeandtemperaturevariation 110
SynthesisinDMFwithNaCNversusKCN 118
CyanideAdditioninAcetonitriletoAproticDriedCsCoY .... 119
CharacterizationofCsCo(CN)-Y 120
AnotherSyntheticVariationinAcetonitrile:Preparation
ofCsCoY 121
Deoxygenationtimeandtemperaturevariation 124
SynthesisinAcetonitrilewithNaCNversusKCN 130
HydrogenationPretreatmentofCsCo(CN)-Y 131
CharacterizationofhydrogenatedCsCo(CN)-Y 131
Syntheticvariationandtheeffectsofhydrogenation .... 143
Hydrogenationreversibility 147
Hydrogenationmechanism 156
ZeoliteUnitCellCompositionandtheConcentrationofActive
Cobalt(II)Complex 158
OptimalSynthesisConditions 170
SSyynntthheessiissooffCLio3(CCoN()C4N2)'5u•sinnDgMApFroitniZceDolriiteedYCoYandCyanide 174
inAproticSolvents 175
ApplicationsofCsCo(CN)-Y 176
v
CHAPTER3HYDROCARBONOXIDATIONUSINGZEOLITEBASED
CATALYSTS 179
Background 179
Introduction 179
HydrocarbonOxidationUsingZeoliteCatalysts 188
Experimental 192
ReagentsandEquipment 192
TransitionMetalExchangedZeolites 194
Metal-2,9-Dimethyl-l,10-Phenanthroline Complexes Inside
ZeoliteY 194
HydrocarbonOxidationUsingPeroxide 195
HydrocarbonAutoxidationatElevatedPressures 196
ResultsandDiscussion 197
CyclohexaneOxidationatRoomTemperature 197
OOxxiiddaattiioonnooffCCyycclloohheexxaanneeUussiinnggVMarni+o(udsmFpe)x3-+Y-Daonpdetd-ZBeuotliOtOeHs . 200
at50°C 206
AnalysisforCleavageProducts 221
AutoxidationReactions 224
CHAPTER4CONCLUSIONS 231
BIBLIOGRAPHY 234
BIOGRAPHICALSKETCH 244
vi
LISTOFTABLES
T1-able page
2-
1-1. ImportantAchievementsinZeoliteTechnology 2
1-2. ZeolitePoreStructuresandDimensionalities 6
3. ZeoliteSecondarySub-UnitComposition 10
1. UsesofOxygen 19
2-2. EPRParametersforLow-spinCobalt(II)Complexes 67
2-3. CyanideAdditioninMethanol 74
2-4. NaYPretreatedReactions 81
2-5. DimethylglyoximePretreatedCsCoY 85
2-6. SodiumHydroxidePretreatedCsCoY/CsCoUSY 90
2-7. CalciumHydroxidePre-treatedCsCoY/CsCoUSY 93
2-8. CyanidePoreFillingReactionsusingProticSolvents 95
2-9. SynthesisusingAproticDriedCsCoYandKCNinMethanol 104
2-10.InfraredFrequenciesforCobaltCyanideCompounds 107
2-11.TemperatureStudiesonSamplePreparedinDMF Ill
2-12.TemperatureStudiesonSamplePreparedinDMF 113
2-13.TemperatureStudiesonSamplePreparedinAcetonitrile 126
2-14.HydrogenationStudyonSamplePreparedinAcetonitrile 134
vii
Table page
2-15.MagneticSusceptibilityResultsforCoY,CsCoYandCsCo(CN)-Y 140
2-16.SyntheticVariationinAcetonitrileandEffectsofHydrogenPre-
Treatment 144
22--17.HydrogenPretreatmentatVariousTemperatures 148
23--18.QuantitativeEPRResultsforHydrogenatedCsCo(CN)-Y 155
2-19.UnitCellCompositionandPercentActiveCobalt 160
20.P^ValuesforCo-02Adducts 177
1. CyclohexaneOxidationusingPeroxidesatRoomTemperature 198
3-2. CyclohexaneOxidationUsingFe3+-DopedYZeolites 201
3-3. ComparisonofZSM-5,Mordenite,andYZeolites 204
3-4. CyclohexaneOxidationUsingFe3+DopedZSM-5andMordenite 205
3-5. VariationinPeroxideConcentrationforOxidationofCyclohexane 207
3-6. ReactionTimeVariationinCyclohexaneOxidationat50°C 210
3-7. n-HexaneOxidationUsingt-ButOOHat50°C 212
3-8. CatalystVariationforCyclohexaneOxidation 215
3-9. CyclohexaneOxidationUsingMetalDopedMordenite 220
3-10.PercentConversiontoAdipicAcidandCyclohexylHydroperoxide 223
3-11.AutoxidationofCyclohexane 226
3-12.AutoxidationofCumene 227
vm
LISTOFFIGURES
Figure page
1-
21--1.ZeoliteSecondaryBuildingUnits 9
1-2.StructuralRepresentationofZeolites(a)SiliconorAluminumTetrahedralunits;
(b)BallandStickRepresentationofSodaliteUnit;(c)LinedrawingofSodalite
Unit;(d)LineDrawingofFaujasite 12
3.CationSitesAvailableinZeoliteY 14
1.ContemporaryDoubleColumnGas-SeparationSystem 27
2-2.SkarstromProcess 30
2-3.UnionCarbidePSA-OxygenProcess 33
2-4.AirProductsPSA-OxygenProcess 35
2-5.Co(en)22+inZeoliteY 39
2-6.CoSALENinZeoliteY 41
2-7.EPRSpectraofCo(CN)42'(a)Experimental;(b)Simulated 44
2-8.VacuumLineApparatus 57
2-9.REoPoRmSTpeemctprearaotfurCes;Co((b)CNS)p-ecYt(rau)mSaptec1t1r0uKmoafftCero(EvCaNc)u5a0ti2o3n'iTneZneoMliintuetYesaatt
RoomTemperature 65
2-10.EPRSpectrumofCo(CN)53‘inCsCo(CN)-Y 66
2-11.SpinPairingModel 68
2-12.GasAdsorptionIsothermsforCsCo(CN)-Y(SampleE) 76
IX
Figure page
2-13.Determinationof[Co] andKq^ofCsCo(CN)-Y(SampleE) 77
t
2-14. and[Co] DeterminationforDMGHSamples 86
t
2-15.StructureofCoSMDPT 88
2-16.Ultraviolet/VisibleSpectrumforCsCo(CN)-YPreparedinDMF 109
2-17.Kq and[Co] PlotforCsCo(CN)-YDeoxygenatedSevenHours
2 at300°Ct 115
2-18.Kq and[Co] PlotforCsCo(CN)-YDeoxygenatedSevenHours
2 at325°Ct 116
2-19.UltravioletVisibleSpectrumforCsCo(CN)-YPreparedinCH3CN. ... 122
2-20.GasAdsorptionIsothermsforCsCo(CN)-YPreparedinCH3CN 128
2-21.Kq2and[Co]tPlotforCsCo(CN)-YPreparedinCH3CN 129
2-22.GasAdsorptionIsothermforHydrogenatedCsCoY 132
2-23.ExperimentalCurvesafterHydrogenationofCsCo(CN)-Y(a)GasAdsorption
Isotherms;(b)Kq^and[Co] Curve 135
t
2-24.In(fbr)arAefdteSrpeHct2rTaroefatamHeyndtro#g2e;n(act)eAdfStearmpHl2eT(ra)eaPtrmioerntto#H52Treatment; 138
2-25.IsothermsforCsCo(CN)-YafterHydrogenationatRoomTemperature. 150
2-26.IsothermsforCsCo(CN)-YafterHydrogenationat250°C 152
2-27.IsothermsforCsCo(CN)-YafterHydrogenationat300°C 153
2-28.HydrogenationMechanism 157
2-29.CobaltContentVersusOxygenChemisorption 165
2-30.CesiumContentVersusOxygenChemisorption 167
2-31.CesiumtoCobaltRatioVersusOxygenChemisorption 168
x