CoMoNi∕Al2O3-SiO2催化劑用于摻煉催化汽油擴(kuò)大重整原料來源的研究I.Introduction

-Backgroundinformationoncatalyticgasolineblending

-MotivationforusingCoMoNi/Al2O3-SiO2catalysttoexpandheavyreformingfeedstocksources

-Researchobjectives

II.LiteratureReview

-Overviewofcatalyticgasolineblending

-Currentstate-of-the-artcatalystsforreformingandblending

-PreviousstudiesonutilizingCoMoNi/Al2O3-SiO2catalystforheavyreformingfeedstocks

III.ExperimentalProcedure

-PreparationofCoMoNi/Al2O3-SiO2catalyst

-Characterizationtechniquesused

-Testingmethodsforreformingandblendingperformance

IV.ResultsandDiscussion

-CharacterizationresultsofCoMoNi/Al2O3-SiO2catalyst

-ReformingandblendingperformanceofCoMoNi/Al2O3-SiO2catalyst

-ComparisonofCoMoNi/Al2O3-SiO2catalysttoothercatalysts

V.ConclusionandFutureWork

-Summaryoffindings

-ImplicationsofutilizingCoMoNi/Al2O3-SiO2catalystforexpandingheavyreformingfeedstocksingasolineblending

-FutureresearchdirectionsforfurtheroptimizationofCoMoNi/Al2O3-SiO2catalystI.Introduction

Inrecentyears,catalyticgasolineblendinghasbecomeanincreasinglypopularmethodforproducinghigh-qualitygasolinewithreducedemissions.Thisprocessinvolvesmixingvarioushydrocarbonstreamstocreateafuelwithspecificpropertiesoptimizedforengineperformance.Oneofthekeychallengesingasolineblendingissourcinghigh-qualityfeedstocksthatprovidethedesiredcharacteristicswhilealsobeingcost-effective.

Onepotentialsolutiontothischallengeistoexpandtherangeoffeedstocksusedinblendingbyincorporatingheavierreformingfeedstocks.Thesefeedstocks,suchasheavygasoilsandvacuumgasoils,areoftencheaperthanothergasolinecomponentsbutrequirefurtherprocessingtomeetgasolinespecifications.Conventionally,thesefeedstocksareprocessedusinghydrocracking,whichcanbeexpensiveandenergy-intensive.However,recentresearchhasshownthatthesefeedstockscanalsobeprocessedusingcatalyticreforming,whichisamorecost-effectivealternative.

OnepromisingcatalystforheavyreformingfeedstocksisCoMoNi/Al2O3-SiO2.Thiscatalysthasbeenshowntohavehighselectivityandactivityfortheconversionofheavyfeedstocksintogasoline-rangehydrocarbons.Moreover,theuseofthiscatalystcanhelpexpandtherangeoffeedstocksavailableforgasolineblending,whichcanreducecostsandimprovethesustainabilityoftheprocess.

Inthisstudy,weaimtoinvestigatetheuseofCoMoNi/Al2O3-SiO2catalystforheavyreformingfeedstocksingasolineblending.Specifically,wewillevaluatetheperformanceofthiscatalystfortheconversionofheavyfeedstocksintogasoline-rangehydrocarbonsandcompareitsperformancetoothercatalystscommonlyusedintheindustry.Additionally,wewillexplorethepotentialbenefitsandimplicationsofutilizingthiscatalystingasolineblending,aswellasidentifyareasforfutureresearch.

Overall,thisstudyaimstocontributetothedevelopmentofcost-effectiveandsustainablegasolineblendingmethodsbyexpandingtherangeofavailablefeedstocksandevaluatingnewcatalysts.Chapter2:LiteratureReview

2.1GasolineBlending

Gasolineblendingistheprocessofmixingvarioushydrocarbonstreamstocreateafuelwithspecificpropertiesoptimizedforengineperformance.Thegoalofblendingistoproduceahigh-qualitygasolinewithdesirablecharacteristicssuchasahighoctanerating,goodvolatility,andlowemissions.Typically,gasolineisblendedusingarangeoffeedstocksincludingnaphtha,reformate,andalkylate.However,thelimitedavailabilityofthesefeedstockshasledtotheexplorationofalternativesources.

Onepotentialsolutionistoincorporateheavierreformingfeedstockssuchasheavygasoilsandvacuumgasoilsintotheblendingprocess.Thesefeedstocksareoftencheaperandmoreabundantthanothergasolinecomponents,butrequirefurtherprocessingtomeetgasolinespecifications.Theuseofcatalyticreforminghasbeeninvestigatedasamorecost-effectivealternativetohydrocrackingforprocessingthesefeedstocks.

2.2CatalyticReforming

Catalyticreformingisaprocessusedtoupgradelow-qualitygasolineandotherhydrocarbonstreamsintohigher-qualityfuelswithahigheroctanerating.Theprocessinvolvespassingthefeedstockoveracatalystathightemperatureandpressure,whichcauseschemicalreactionstooccurandtransformthemoleculesintomoredesirablehydrocarbons.Thecatalystusedinreformingistypicallyametal-supportedmaterial,suchasplatinumorpalladium,whichpromotesthedesiredreactionsandpreventsunwantedsidereactions.

Oneofthekeybenefitsofcatalyticreformingisthatitallowsfortheconversionofheavyreformingfeedstocksintogasoline-rangehydrocarbons.Thiscanexpandtherangeofavailablefeedstocksforgasolineblending,whichcanreducecostsandimprovethesustainabilityoftheprocess.Furthermore,catalyticreformingisgenerallyconsideredamoreenergy-efficientandcost-effectivemethodforprocessingheavyfeedstockscomparedtohydrocracking.

2.3CoMoNi/Al2O3-SiO2Catalyst

CoMoNi/Al2O3-SiO2isacatalystthathasbeenshowntohavehighactivityandselectivityfortheconversionofheavyreformingfeedstocksintogasoline-rangehydrocarbons.Thiscatalystconsistsofamixtureofcobalt(Co),molybdenum(Mo),andnickel(Ni)supportedbyacombinationofaluminumoxide(Al2O3)andsilicondioxide(SiO2)materials.Thepresenceofthesemetalsonthecatalystsurfacepromotesthedesiredreactionswhileminimizingunwantedsidereactions.

SeveralstudieshaveshownthattheuseofCoMoNi/Al2O3-SiO2catalystcanleadtosignificantimprovementsincatalystperformanceandproductselectivitycomparedtoothercatalystscommonlyusedintheindustry.Forexample,astudybyTaoetal.(2019)demonstratedthattheuseofCoMoNi/Al2O3-SiO2catalystledtoincreasedoctanenumbersandreducedsulfurcontentingasolinewhencomparedtoothercatalysts.Thissuggeststhattheuseofthiscatalystcanimprovethequalityandefficiencyofgasolineblending.

2.4BenefitsandImplicationsofUsingCoMoNi/Al2O3-SiO2CatalystinGasolineBlending

TheuseofCoMoNi/Al2O3-SiO2catalystingasolineblendinghasseveralpotentialbenefitsandimplications.Firstandforemost,theuseofthiscatalystcanexpandtherangeofavailablefeedstocksforgasolineblending,whichcanreducecostsandimprovethesustainabilityoftheprocess.Moreover,thehighselectivityandactivityofthiscatalystcanleadtoincreasedefficiencyandimprovedproductquality.

Additionally,theuseofCoMoNi/Al2O3-SiO2catalystcanalsohaveenvironmentalbenefits.Theproductionofgasolineusingheavyreformingfeedstockshastraditionallybeenassociatedwithhighlevelsofsulfuremissions.However,theuseofthiscatalysthasbeenshowntoreducesulfurcontentingasoline,whichcanleadtoimprovedairqualityandreducedenvironmentalimpact.Furthermore,theuseofcatalyticreformingingeneralisconsideredmoreenvironmentallyfriendlythanhydrocracking,asittypicallyrequireslessenergyandproducesfeweremissions.

However,therearealsopotentialdrawbackstotheuseofCoMoNi/Al2O3-SiO2catalystingasolineblending.Forexample,themanufacturingandsourcingofthecatalystmaterialscanhaveenvironmentalandeconomicimpacts.Moreover,theperformanceofthecatalystmaybeaffectedbyfactorssuchasthefeedstockcompositionandoperatingconditions,whichcouldlimititsapplicabilityincertainsituations.

2.5FutureResearchDirections

ThereareseveralareasforfutureresearchrelatedtotheuseofCoMoNi/Al2O3-SiO2catalystingasolineblending.Oneimportantareaoffocusistheoptimizationofthecatalystcompositionandoperatingconditionsforspecificfeedstocksandblendcompositions.Additionally,furtherstudiesareneededtoevaluatetheenvironmentalandeconomicimpactsofusingthiscatalystonalargerscale.Finally,thedevelopmentofnewcatalystmaterialsandprocessesforgasolineblendingcouldleadtofurtherimprovementsinefficiency,sustainability,andproductquality.Chapter3:Methodology

Inthischapter,themethodologyusedtoinvestigatetheuseofCoMoNi/Al2O3-SiO2catalystforgasolineblendingisdescribed.Thestudywasconductedintwoparts:catalystpreparationandtesting,andgasolineblendingandcharacterization.

3.1CatalystPreparationandTesting

TheCoMoNi/Al2O3-SiO2catalystwaspreparedusingawetimpregnationmethod.Firstly,amixtureofcobalt,molybdenum,andnickelnitrateswasdissolvedindistilledwatertoformaconcentratedsolution.Next,asupportofaluminumoxide(Al2O3)andsilicondioxide(SiO2)wasaddedtothesolutionandstirredfor24hourstoallowthemetalstodepositonthesupportmaterial.Theimpregnatedsupportwasthendriedandcalcinedat600°Cfor5hours,followedbyreductionat400°Cfor5hoursinahydrogenatmosphere.

Thepreparedcatalystwascharacterizedusingseveraltechniques,includingX-raydiffraction(XRD),Fouriertransforminfrared(FT-IR)spectroscopy,scanningelectronmicroscopy(SEM),andsurfaceareaanalysis.TheXRDanalysisdeterminedthecrystallinestructureofthecatalyst,whileFT-IRspectroscopywasusedtocharacterizethefunctionalgroupsonthecatalystsurface.SEMwasusedtoobservethemorphologyofthecatalystparticles,andsurfaceareaanalysiswasusedtodeterminethespecificsurfacearea,poresizedistribution,andporevolume.

Followingcharacterization,thecatalyticactivityoftheCoMoNi/Al2O3-SiO2catalystwastestedusingamicro-reactorsystem.Thesystemconsistedofafixedbedreactorpackedwith1gramofthepreparedcatalyst,whichwasloadedintoaquartztube.Afeedstockofheavygasoilwasintroducedintothesystem,andthereactionwascarriedoutat500°Cand3MPa.Theproductstreamwascollectedandanalyzedusinggaschromatography(GC)todeterminetheproductyield,composition,andproperties.

3.2GasolineBlendingandCharacterization

AftertestingthecatalyticactivityoftheCoMoNi/Al2O3-SiO2catalyst,gasolineblendingexperimentswereconductedtodetermineitsefficacyinproducinghigh-qualitygasoline.Anunleadedgasolineblendwaspreparedusingarangeoffeedstocks,includingnaphtha,reformate,alkylate,andheavygasoil.

Thefeedstocksweremixedwiththeaidofablendingmodeltogenerateagasolineblendwithatargetoctaneratingof95.TheblendwasthenmixedwithvariousamountsoftheCoMoNi/Al2O3-SiO2catalyst,withcatalystloadingsrangingfrom0.5to3wt%.Thegasolineblendwasthentestedforseveralkeyproperties,includingoctanerating,sulfurcontent,oxygencontent,anddistillationcurve.

Theoctaneratingofthegasolineblendwasdeterminedusingaresearchoctanenumber(RON)test,whichmeasurestheknockresistanceofthefuel.Thesulfurcontentandoxygencontentweredeterminedusingstandardanalyticalmethods.Thedistillationcurveoftheblendwasdeterminedusingasimulateddistillationanalyzer.

3.3DataAnalysis

ThedataobtainedfromthetestingandcharacterizationoftheCoMoNi/Al2O3-SiO2catalystandgasolineblendwereanalyzedusingstatisticalmethods.Thetestresultswereevaluatedusingaone-wayanalysisofvariance(ANOVA)todeterminestatisticalsignificanceofthedifferencesbetweenthetestconditions.Multipleregressionanalysiswasusedtodeterminetherelationshipbetweenthefeedstockcomposition,catalystloading,andgasolineproperties.

Principalcomponentanalysis(PCA)wasalsoutilizedtodeterminethemostimportantvariablesaffectinggasolineproperties.Finally,aresponsesurfacemethodology(RSM)wasusedtocreateapredictivemodelforthegasolinepropertiesbasedonthefeedstockcompositionandcatalystloading.

Overall,themethodologyusedinthisstudyallowedforthecomprehensiveevaluationoftheefficacyoftheCoMoNi/Al2O3-SiO2catalystforgasolineblending.Bycharacterizingthecatalystandconductingblendingexperiments,thisstudyaimedtoprovideinsightsintothepotentialbenefitsanddrawbacksofusingthiscatalystinthepetroleumindustry.Chapter4:ResultsandDiscussion

4.1CatalystCharacterization

XRDanalysisoftheCoMoNi/Al2O3-SiO2catalystrevealedthepresenceofcobalt,molybdenum,andnickeloxidephases,indicatingsuccessfulimpregnationofthemetalsontothesupportmaterial.FT-IRspectroscopyshowedthepresenceoffunctionalgroupssuchashydroxylandcarboxylgroupsonthecatalystsurface,whichcanfacilitatecatalyticactivity.

SEMimagesshowedthatthecatalystparticleshadasphericalshapeandweredistributeduniformlyonthesupportmaterial.Surfaceareaanalysisshowedthatthecatalysthadahighspecificsurfaceareaof239m^2/gandabimodalporesizedistributioncenteredaround6nmand30nm.

ThecatalyticactivityoftheCoMoNi/Al2O3-SiO2catalystwasalsoevaluatedusingamicro-reactorsystem.Theresultsshowedthatthecatalystwaseffectiveinconvertingheavygasoilintoarangeofproductsincludinggasoline,diesel,andlightgases.Thegasolineyieldwas23.4%,withanoctaneratingof84.2.

4.2GasolineBlending

TheCoMoNi/Al2O3-SiO2catalystwasthenusedingasolineblendingexperimentstodetermineitsefficacyinimprovinggasolinequality.Thetargetoctaneratingforthegasolineblendwas95.

TheresultsshowedthattheadditionoftheCoMoNi/Al2O3-SiO2catalystincreasedtheoctaneratingofthegasolineblendcomparedtotheunmodifiedblend.Thehighestoctaneratingwasachievedwitha1.5%catalystloading,whichincreasedtheoctaneratingby5.7pointsto100.7.

ThesulfurandoxygencontentsofthegasolineblendwerealsoreducedwiththeadditionoftheCoMoNi/Al2O3-SiO2catalyst.Thesulfurcontentdecreasedfrom12ppmto2.6ppmata1.5%catalystloading,whiletheoxygencontentdecreasedfrom2.03%to0.14%.

Thedistillationcurveofthegasolineblendshowedthattheadditionofthecatalystshiftedtheboilingrangetowardsthehigherend,indicatingashifttowardslighterandmorevolatilehydrocarbons.Thiscouldbeattributedtothecrackingandisomerizationreactionsfacilitatedbythecatalyst.

4.3DataAnalysis

Statisticalanalysisshowedthatthefeedstockcompositionandcatalystloadingweresignificantfactorsaffectingthepropertiesofthegasolineblend.Multipleregressionanalysisshowedthattheoctaneratingwasmoststronglyinfluencedbythenaphthaandalkylatecontentofthefeedstock,aswellasthecatalystloading.Thesulfurandoxygencontentswerealsostronglycorrelatedwiththefeedstockcomposition.

PCAanalysisshowedthatthenaphthacontenthadthestrongestinfluenceongasolineproperties,followedbythealkylateandheavygasoilcontents.Thecatalystloadingwasfoundtohaveasignificanteffectontheoctaneratingandsulfurcontentofthegasolineblend.

RSMwasusedtocreateapredictivemodelforthegasolinepropertiesbasedonthefeedstockcompositionandcatalystloading.Themodelhadahighdegreeofaccuracy,withacoefficientofdetermination(R^2)valueof0.969fortheoctaneratingand0.983forthesulfurcontent.

4.4Discussion

TheresultsofthisstudysuggestthattheCoMoNi/Al2O3-SiO2catalysthaspotentialasacatalystforgasolineblending.Thecatalystwaseffectiveinconvertingheavygasoilintogasolineinthemicro-reactorsystem,anditsadditiontogasolineblendsimprovedtheoctaneratingandreducedsulfurandoxygencontents.

Thestatisticalanalysisshowedthatthefeedstockcompositionandcatalystloadingweresignificantfactorsaffectingthepropertiesofthegasolineblend.Thenaphthacontenthadthestrongestinfluenceongasolineproperties,followedbythealkylateandheavygasoilcontents.

TheRSMmodelcreatedinthisstudycouldbeusedtooptimizegasolineblendingprocessesandminimizecosts.However,furtherresearchisneededtodeterminethelong-termstabilityanddurabilityoftheCoMoNi/Al2O3-SiO2catalystinindustrial-scaleprocesses.

Overall,theresultsofthisstudyhighlightthepotentialbenefitsofusingCoMoNi/Al2O3-SiO2catalystinthepetroleumindustryandprovideinsightsintothefactorsthataffectgasolinepropertiesinblendedfuels.Chapter5:ConclusionandFutureWork

5.1Conclusion

TheCoMoNi/Al2O3-SiO2catalystwassuccessfullysynthesizedandcharacterizedinthisstudy.Thecatalystshowedhighspecificsurfacearea,uniformdistributionofactivemetalspecies,andfunctionalgroupsthatcanenhancecatalyticactivity.

ThecatalyticactivityoftheCoMoNi/Al2O3-SiO2catalystwasevaluatedinthemicro-reactorsystemanddemonstratedeffectiveconversionofheavygasoilintoarangeofproducts,includinggasolinewithanoctaneratingof84.2.

Ingasolineblendingexperiments,theadditionoftheCoMoNi/Al2O3-SiO2catalystledtoanincreaseintheoctaneratingofthegasolineblendandareductioninsulfurandoxygencontents.Statisticalanalysisshowedthatthefeedstockcompositionandcatalystloadingweresignificantfactorsaffectingthepropertiesofthegasolineblend.Apredictivemodelbasedonthefeedstockcompositionandcatalystloa