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Chemical Engineering Research and Design
jo u r n al ho m e p a g e :w w w . e l s e v i e r . c o m / l o c a t e / c h e r d
Kinetic modelling of methanol conversion to light olefins process over silicoaluminophosphate
(SAPO-34) catalyst
Reza Bagherian Rostami
∗, Alireza Samadi Lemraski, Mohammad Ghavipour, Reza Mosayyebi Behbahani, Bahram Hashemi Shahraki, Tuba Hamule
CatalystResearchGroup,GasResearchCenter,GasEngineeringDepartment,PetroleumUniversityofTechnology, Ahwaz63431,Iran
a r t i c l e i n f o
Articlehistory:
Received8July2015
Receivedinrevisedform8October 2015
Accepted13October2015 Availableonline21October2015
Keywords:
MTO SAPO34
Kineticmodelling Lightolefins PSOoptimization
a bs t r a c t
TheMTOprocessoverSAPO34catalystwasmodelledwiththeconsiderationoffunctional- ityagainstcokedepositionforproductsdistribution,consistingof11reactionsinvolving13 reactionspeciesandusedintheassessmentofexperimentaldataacquiredinafixedbed reactorinatemperaturerangefrom400to460◦Cusingweighthourspacevelocity(WHSV) of1,2and4gMeOHgcatalyst−1h−1andatatmosphericpressure.Theresultsshowedthat olefinscarbonselectivityincreaseswithspacevelocity,suggestingthatthesecondaryreac- tionswhichtakepartintheMTOreactionfortheparaffiniccomponentsproductionare reducedbydecreasingcontacttime.Calculationofthekineticmodelparametersofbestfit wasperformedbyparticleswarmoptimizationalgorithmthroughsolvingthemasscon- servationequationsofthereactionproductsofthekineticscheme.Pre-exponentialfactors andapparentactivationenergieswerethencalculatedbasedontheArrheniusequation usingtheoptimizedrateconstants.ThekineticmodelgaveagoodrepresentationofMTO experimentaldataatconditionsclosetoindustrialpractice.
©2015TheInstitutionofChemicalEngineers.PublishedbyElsevierB.V.Allrightsreserved.
1. Introduction
Todays,theshortageofoilresourceshasattractedtheatten- tionofthescientiststodevelopatechnologyforlightolefins productionfromtheabundantandrelativelycheapresources ofnaturalgas,coalandbiomass(Sunetal.,2014).Amongthe alternativeroutes,thezeolitecatalysedmethanoltoolefins (MTO)hasshowntobeapromisingprocess,becausemethanol canbeefficientlyproducedfromsyngasobtainedthroughnat- uralgasreformingorcarbongasification(Álvaro-Mu ˜nozetal., 2014).AmongmolecularsievecatalystsappliedinMTOreac- tion(Bhaweetal.,2012;Castroetal.,2009;Leeetal.,2010;
Parketal.,2008;Svelleetal.,2007;Teketeletal.,2011;Wang etal.,2011),thesmallporesilicoalomonophosphatemolecular
∗ Correspondingauthor.Tel.:+989119508688;fax:+986115550868.
E-mailaddress:[email protected](R.B.Rostami).
sieveSAPO34,withmildacidstrengthhasshowntohavethe bestcatalyticperformance(Chenetal.,2005;Wangetal.,2015;
Yang etal., 2013). Thesuccessfuldevelopmentofcommer- ciallyapplicableMTOtechnologyhasbeenprovidedinChina usingtheDMTOtechnologydevelopedbytheDalianInstitute ofChemicalPhysics(DICP)(Tianetal.,2015).
Althoughthecommercializationandtechnologicaldevel- opment of this process has been considerable, kinetic modeling ofthis complex reaction networkwith heteroge- neous reactionstepshasyetneededtobemoredeveloped (Gayuboetal.,2005).Kineticstudiesareimportantmeansto gainabetterinsightoftheoverallprocesssothatitcanbe modifiedforoptimumoperatingconditionsandbetteryields.
For reactordesign,simulationofprocessesthatare carried
http://dx.doi.org/10.1016/j.cherd.2015.10.019
0263-8762/©2015TheInstitutionofChemicalEngineers.PublishedbyElsevierB.V.Allrightsreserved.
mixtureistoapplylumping,inreactionnetworkandspecies.
Intheseglobalkineticmodels,themechanisticaspectsare considered inageneric way,and astheyare simpler, they benefitfromlesscomplicatedkineticparametersestimation andsimpleuseinreactordesign(Olsbyeetal.,2012).Several kineticmodelingeffortshavebeenreportedintheliterature forMTO.
Mihail et al. (1983) proposed a kinetic model based on carbenoidintermediates,involving27reactionsand18molec- ularspecies.Accordingtotheproposedmechanism,dimethyl ether(DME)generatesacarbenespecieswhichreacts with oxygenatesto form the first C C bond, that subsequently furtherreactstoformhigherolefins.Bosetal.(1995)devel- opeda modelwith6 lumpsplus cokereacting through12 reactions. The Bos et al. (1995) reaction network was fur- ther simplified by eliminating slower steps, and a kinetic modelwasdevelopedonSAPO34,whichtakesintoaccount fourindividualstepsfortheproductionofethene,propene, butenes,and remaininghydrocarbons (pentenes+paraffins) (Gayuboetal.,2000).Singleeventkinetic modelingofMTO onSAPO 34wasdevelopedbasedonthesurface-bondedoxo- niummethylidemechanismbyAlwahabiandFroment(2004).
Chenetal.(2007)havedistinguishedthetypeofproduct(stable or unstable,primaryor secondary) and thetype ofdeacti- vation(selectiveornonselective)usingtheyield-conversion plot.Basedontheobtainedresults,thekineticofMTOreac- tionwasmodelledwith7reactionsinvolving7lumps[ethene, propene,butenes(C4),C5,C6,oxygenates,ethane+propane].
Langmuir–HinshelwoodmechanismwasalsoappliedinMTO kinetic modeling and methanol, DME, ethylene, propylene andparaffinweretakenintoaccountasthereactionspecies (Fatourehchietal.,2011).
Althoughconsiderable studies have been performed on MTOreactionoverSAPO34,thereisnouserfriendlykinetic modelintermsofreactionmechanism,takingintoaccount theeffectsofcokedepositiononproductsdistributionaswell astheinitialreactionconditions(i.e.temperature,WHSV...).
Inthe present work,alumped (in terms ofreaction steps) kineticmodelwasestablishedbasedonthesimpleandreli- ablereactionnetworkwiththeconsiderationoffunctionality againstcokedepositionforproductsdistribution,consisting of11reactionsinvolving13reactionspecies.
2. Experimental
Thedetailsofexperimentalreactionsetupandthecatalystare identicaltothosedescribedinourpreviousworks(Behbahani et al., 2014; Rostami et al., 2014). The experimental data wascarriedoutinastainlesssteeltubular,fixed-bedreactor (12mmI.D.,20cmlength).2gofSAPO-34catalystinpowder
3. Product distribution analysis
Theevolutionofdifferenthydrocarbonsmolefractionswith the timeon streamatdifferent industrialoperating condi- tions (different temperatureand contacttime)is shownin Figs. 1–4. The results clearly show that the ethylene and methanemoleratioincreaseinthewholetimeduringreac- tionasTOSincreases.Asitcanbeseenin,highertemperature favoursethyleneandmethaneproduction.Propylenemolar fractionhasnoconsiderablechangebyTOS,butaccordingto Fig.1decreasingtemperatureresultsinmorepropylenefor- mation.Thepropanemoleratiowashighatthebeginning,but itcamedownwithintensiveslope.Ethanealsohadasimilar trendwithlessintensity. Thisshowsthathydridetransfer- ringreactioninMTOleadingethaneandpropaneformation fromethyleneandpropylene,respectively,decreasesbycoke deposition.Thiscouldbeduetothefactthatacidsitesare responsibleforhydridetransferringreactionandincreasing cokecontentresultsinlowercontributionoftheseacidsites
Fig.1–Effectsoftemperatureonethylene(A)and propylene(B)molepercentatWHSV=2h−1.
Fig.2–EffectsoftemperatureonMTOproductsdistribution atWHSV=2h−1.
tothisreaction(Aguayoetal.,1994;Gayuboetal.,2011;Guisnet etal.,2009;GuisnetandMagnoux,2001).
It is also observed that heavier fraction (C4= and C5+) decreaseswithTOS.Thistrendcanbeexplainedbyconsider- ationofcokeshapeselectivityeffects,favouringtheformation ofsmallermoleculeswhenthevoidvolumeinthecavitiesis
Fig.3–Shortchainolefinscarbonselectivityat WHSV=2h−1anddifferenttemperature.
Fig.4–Effectsofspacetimeonshortchainolefinscarbon selectivityatT=730K.
reducedbycokeandtheproductdiffusionlimitationoutofthe catalystcrystalsresultingfromthecokemoleculesformation.
85% selectivityto lightolefins (C2=, C3=) and about 92%
selectivitytoolefins(C2=,C3=,C4=)wereobservedunderMTO conditionsstudiedinthepresentwork,asitreportedinUOP MTOprocess(Chenetal.,2005).Itisalsofoundthat,olefins carbon selectivitynot changed significantly by rising tem- peratureinaconstantWHSV(Fig.3);whileincreasingspace velocityleadstheolefinsselectivitytobeincreased(Fig.4), suggestingthatsecondaryreactionwhichtakepartinMTO reactionforparaffiniccomponentsproductionarereducedby decreasingcontacttime.
Generally large crystal sizeleads todiffusion limitation inwhich the reactionsare controlledbylimitation ofboth methanol (MeOH)and dimethyl ether (DME).On too small crystalsizearelativelylargequantityofMeOHandDMEscape theSAPO34poresbeforebeingtransformed,henceresulting inlowerolefinsselectivity.Thepresenceoflightolefinswith longresidencetimeinsidetheSAPO34poresandcagesleads toanacceleratedformationofoligomerizationandhydrogen transferreactionproducts(Rostamietal.,2015).Besides,com- paringabsoluteself-diffusivitiesofC2= andC3= hasshown asignificanthigherself-diffusivity valuesforethylenethan forpropylenewhicheffectsolefinsdistributionduringMTO reaction(Daietal.,2012).Moreover,increasingspacevelocity leadstofastercokedepositiononSAPO34catalyst.Ithasbeen well-establishedthatstrongacidsiteshavesignificanteffects oncyclizationandhydrogentransferreactionsandpreferen- tiallythesesitesaredeactivatedbycokemolecules(Chenetal., 2012).AccordingtotheDensityFunctionalTheory(DFT)calcu- lation,thecyclizationandthesubsequenthydridetransferare calculatedtobetherate-determiningstepfortheformation ofthepolymethylcyclopentenylandpolymethylcyclohexenyl cations,whichserveasbridgesconnectingthetwopartsof thedual-cyclereactionmechanism(Daietal.,2014).
4. Methanol to olefins kinetic modelling
4.1. MTOreactionnetworkIn thepresent Vera-Castaneda(1985) proposed mechanism formethanoltoolefinhasbeenused.Thereactionnetwork issummarizedinTable1.
Themainfeaturesoftheappliedmechanismareasfollows, 1. Thefirststepintheoverallsequenceoftheconversionof methanoltohydrocarbonsistheconversionofmethanol
C3H6+H2⇒C3H8
toDME(Experimentalstudiesshowthatdimethyletheris formedintheinitialstagesofthereactionpriortothepro- ductionofanyhydrocarbonproducts).Dimethyletherand methanolrapidlyreachequilibriumoverthecatalystsur- face,andsoeithercancontributeasafeedstocktoproduce hydrocarbonproducts.
2. Ethyleneisprimaryproductformedfrom methanoland dimethylether.Basedonthemostacceptedmechanism, thereactantsmethanolandDMEasthemethylationagents arerepeatedlyaddedtotheorganicreactioncenters(poly- methylbenzenesandmethylbenzene-derivedcations)for theassemblyoflightolefins.Theseorganicspeciesactas catalytichosts(co-catalyst)inMTOreaction.
3. Thesignificantlyhigher13CcontentintheC3–C6 alkenes thanethyleneand aromaticsinisotopiccompositionsof theeffluentcompounds(Bjørgenetal.,2007)suggestsadif- ferentoradditionalrouteformethanolincorporationinto C3–C6alkenes.Higher alkeneareformedfromthelower alkenesthroughsequentialmethylation. Theconversion ofthelightolefinsintohighermolecularweightproducts throughsequential methylation byreactive C1 interme- diate.Propylene would beformed in this manner from ethylene,butenefrompropylene,etc.byachainmecha- nism.
4. Methaneisabyproductofmethanoldecomposition.
5. Hydrogentransferreactionofolefinstoproduceparaffins.
6. Decomposition of methanol to carbon monoxide and hydrogen.
Thereactionofcarbonmonoxideandwatervapourtoform carbondioxideandhydrogen.(Watergasshiftreaction).Itpro- videsasourceofhydrogenattheexpenseofcarbonmonoxide.
Itisnecessarytobementioned that, Table1showsthe global pathway for methanol to olefins reaction while in molecularscaleMTOreactioninvolveshundredsofelemen- tarysteps.
4.2. Developingrateequations
An11elementaryreactionrateequationwasdevelopedbased onreactionnetworkpresentedinTable2.Allrateconstants areassumedtodependonthecatalystcokecontent,whichis takenintoaccountbythedeactivationfunctions,ϕi.
Forthereaction 2CH3OH⇔k1CH3OCH3+H2O
Theequilibriumconstant(kE)hasbeenreportedasafunc- tionoftemperaturethroughthefollowingequationbyMoffatt
andHayashi(Spivey,1991):
RlnkE= G
T =−6836
T +3.32lnT−0.475×10−3T
−0.11×10−6T2−10.92 (1)
Inordertodescribethechangeinreactionrateswithcoke contentdifferentdeactivationfunctions(Table3)havebeen tried.Thelinearfunctionhasshownthebestfittotheexper- imentaldata.
C is the weight percent of coke on the catalyst (gcokegcatalyst−1). Note that ˛i (empirical constants) are obtainedfromexperimentaldata,showingthereactionssen- sitivitytodepositionofcokeduringMTOreaction.Thelarger thevaluefor˛ishowsthestrongereffectofincreasingcoke contentonreactioni.
4.3. Reactormodel
Aone-dimensional,idealplugflowreactormodelisusedto simulatetheexperimentaldataacquiredontheSAPO34cat- alyst.Accordingly,thetheoreticalresponses,yj,forcomponent jofgasphasearecalculatedbaseduponthefollowingconti- nuityequations
dyj
d
W/F0MeOH
=rj (2)Thenetrateofformationofevery speciesrj isobtained by summationof the rateof thereactions participating in theproductionorconsumptionofspeciej.Amassbalance, resultinginasetofdifferentialequations,isconstructedfor allspecies,whichconsistofmethane,ethylene,ethane,pro- pylene,propane,butyleneandC5+aswellasDME,methanol, carbonmonoxide,carbondioxide,hydrogenandwater.
rCH4=k8ϕ8PCH3OHPH2 (3)
rC2H4 = 1
2k2ϕ2P2CH3OCH3+1
2k3ϕ3P2CH3OH−k4ϕ4PC2H4PCH3OCH3
−k10ϕ10PC2H4PH2 (4)
Table3–Deactivationfunctions.
i=(1−˛iC) i=(1/(1−˛iC)) i=e−˛iC
Fig.5–FlowchartdiagramofbestparametersestimationprocedurebyPSOoptimization.
Fig.6–Arrheniusplotforreactions1to3rateconstants.
Fig.7–Arrheniusplotforreactions4to6rateconstants.
Fig.8–Arrheniusplotforreactions7to9rateconstants.
Fig.9–Arrheniusplotforreactions10and11rate constants.
rCH3OCH3=k1ϕ1P2CH3OH−k1
kEPCH3OH3PH2O−k2ϕ2P2CHO3OCH3
−k4ϕ4PC2H4PCH2OCH3−k5ϕ5PC3H6PCH3OCH3
−k6ϕ6PC4H8PCH3OCH3
(10)
rCH3OH=−k1ϕ1P2CH3OH+k1
kEPCH3OH3PH2O−k2ϕ2P2CH3OCH3−k3ϕ3P2CH3OH +k4ϕ4PC2H4PCH3OCH3+k5ϕ5PC3H6PCH3OCH3+k6ϕ6PC4H8PCH3OCH3
−k7ϕ7PCH3OH−k8ϕ8PCH3OHPH2
(11)
Fig.10–Parityplotforcomparisonofexperimentalandcalculatedmolefractionofethylene,propylene,butaneandC5+at differenttemperature.
Thecontinuityequationsarenumericallyintegratedupto thespacevelocity
WHSV−1
foreachexperimentbyMATLAB ODEsolver.
4.4. Kineticmodel’sparametersestimationand validation
ThekineticmodelParametersofbestfithavebeendetermined separatelyatdifferenttemperaturesbyparticleswarmopti- mizationusingMATLAB(2014a,theMathWorks).Optimization hasbeencarriedoutbyminimizinganobjectivefunction,˚,
Fig.11–Parityplotforcomparisonofexperimentalandcalculatedmolefractionofmethane,ethane,propane,methanolat differenttemperature.
whichisknownastheRootMeanSquareError(RMSE)which isdefinedin
RMSE=
1
N−1
Ni=1
yexpi −ycali 2(16)
FlowchartdescriptionofparametersestimationofthePSO optimizationalgorithmispresentedFig.5.
In order to estimate the activation energy and pre- exponential factor for each reaction, natural logarithm of theratesconstantswereplottedagainst1/T.Figs.6–9show anArrheniusplotofthekinetic ratesconstants.Thefigure
Table4–Activationenergiesandpre-exponential factorsofMTOreactions.
Reaction no.
k0i
molgCatalyst−1atm−1h−1
Ei
kJmol−11 17.322 52.51
2 14.076 50.977
3 11.837 32.13
4 13.068 23.36
5 15.622 44.05
6 15.427 40.25
7 6.161 14.45
8 15.349 40.41
9 23.389 87.91
10 12.737 27.42
11 10.684 12.53
demonstrates that the rate constants fitted Arrhenius law well.
The estimated apparent activation energies and pre- exponential factorsare presentedin Table4, theempirical constants of deactivation functions are also presented in Table5.
ThegoodnessofthefitisshowninFigs.10and11,where theexperimentalresultsarecomparedwiththosecalculated using thekinetic modelfordifferentinitialreactioncondi- tions.Eachgraphcorrespondstoadifferentcomponents.As showninthesefigures,almostsymmetricaldistributionofthe data pointsonbothsides oftheparityplot’s diagonal was obtained.InsomecasessuchasethaneandC5+olefinsmole
Table5–Estimatedconstantsofdeactivationfunctions.
Temperature
T=673K T=703K T=733K
˛1 3.180021 2.94084 2.637843
˛2 2.464574 1.835211 1.802814
˛3 0.731919 0.895742 2.050251
˛4 1.622352 2.907193 3.001011
˛5 2.997174 2.24347 1.646499
˛6 0.228976 1.926216 2.300051
˛7 3.161159 2.653282 2.33734
˛8 1.860715 0.745094 1.266358
˛9 3.12245 1.684573 1.805259
˛10 2.488949 2.047843 2.003289
˛11 2.553945 2.063543 0.978486
whichconsistsof11 reactionsinvolving13 species.Kinetic modelparametersofbestfitwerecalculatedbyparticleswarm optimizationalgorithmthroughsolvingthemassconserva- tionequationsofthereactionproductsofthekineticscheme.
ThecalculatedrateconstantsfollowtheArrheniusequation againsttemperaturewell.Pre-exponentialfactorsandappar- ent activation energies were then calculated based on the Arrheniusequationusingtheoptimizedrateconstants.
Olefinscarbonselectivitywasnotchangedsignificantlyby risingtemperatureinaconstantWHSV,whileincreasingspace velocityleadstheolefinsselectivitytobeincreased,suggest- ingthatthesecondaryreactionswhichtakepartintheMTO reactionforparaffiniccomponentsproductionarereducedby decreasingcontacttime.
Acknowledgements
TheauthorsaregratefultoDr.YaoWangandDr.ZuoxingDi forquantitativeanalysisofcokedcatalystsamplesinBeijing KeyLaboratoryofGreenChemicalReactionEngineeringand TechnologyatTsinghuaUniversity.
References
Aguayo,A.,Benito,P.,Gayubo,A.,Olazar,M.,Bilbao,J.,1994.
AciditydeteriorationandcokedepositioninaHZSM5zeolite intheMTGprocess.Stud.Surf.Sci.Catal.88,567–572.
Álvaro-Mu ˜noz,T.,Sastre,E.,Marquez-Alvarez,C.,2014.
Microwave-assistedsynthesisofplate-likeSAPO-34 nanocrystalswithincreasedcatalystlifetimeinthe methanol-to-olefinreaction.Catal.Sci.Technol.
Alwahabi,S.M.,Froment,G.F.,2004.Singleeventkineticmodeling ofthemethanol-to-olefinsprocessonSAPO-34.Ind.Eng.
Chem.Res.43,5098–5111.
Behbahani,R.M.,Rostami,R.B.,Lemraski,A.S.,2014.
Methanol/dimethylethertolightolefinsoverSAPO-34:
comprehensivecomparisonoftheproductsdistributionand catalystperformance.J.Nat.GasSci.Eng.21,532–539.
Bhawe,Y.,Moliner-Marin,M.,Lunn,J.D.,Liu,Y.,Malek,A.,Davis, M.,2012.Effectofcagesizeontheselectiveconversionof methanoltolightolefins.ACSCatal.2,2490–2495.
Bjørgen,M.,Svelle,S.,Joensen,F.,Nerlov,J.,Kolboe,S.,Bonino,F., Palumbo,L.,Bordiga,S.,Olsbye,U.,2007.Conversionof methanoltohydrocarbonsoverzeoliteH-ZSM-5:ontheorigin oftheolefinicspecies.J.Catal.249,195–207.
Bos,A.R.,Tromp,P.J.,Akse,H.N.,1995.Conversionofmethanolto lowerolefins.Kineticmodeling,reactorsimulation,and selection.Ind.Eng.Chem.Res.34,3808–3816.
Castro,M.,Warrender,S.J.,Wright,P.A.,Apperley,D.C., Belmabkhout,Y.,Pirngruber,G.,Min,H.-K.,Park,M.B.,Hong, S.B.,2009.SilicoaluminophosphatemolecularsievesSTA-7 andSTA-14andtheirstructure-dependentcatalytic
performanceintheconversionofmethanoltoolefins.J.Phys.
Chem.C113,15731–15741.
103–107.
Dai,W.,Scheibe,M.,Li,L.,Guan,N.,Hunger,M.,2012.Effectofthe methanol-to-olefinconversiononthePFGNMR
self-diffusivitiesofethaneandetheneinlarge-crystalline SAPO-34.J.Phys.Chem.C116,2469–2476.
Dai,W.,Wang,C.,Dyballa,M.,Wu,G.,Guan,N.,Li,L.,Xie,Z., Hunger,M.,2014.Understandingtheearlystagesofthe methanol-to-olefinconversiononH-SAPO-34.ACSCatal.5, 317–326.
Fatourehchi,N.,Sohrabi,M.,Royaee,S.J.,Mirarefin,S.M.,2011.
PreparationofSAPO-34catalystandpresentationofakinetic modelformethanoltoolefinprocess(MTO).Chem.Eng.Res.
Des.89,811–816.
Gayubo,A.,Aguayo,A.,Alonso,A.,Atutxa,A.,Bilbao,J.,2005.
ReactionschemeandkineticmodellingfortheMTOprocess overaSAPO-18catalyst.Catal.Today106,112–117.
Gayubo,A.G.,Aguayo,A.T.,SánchezdelCampo,A.E.,Tarrío,A.M., Bilbao,J.,2000.Kineticmodelingofmethanoltransformation intoolefinsonaSAPO-34catalyst.Ind.Eng.Chem.Res.39, 292–300.
Gayubo,A.G.,Alonso,A.,Valle,B.,Aguayo,A.T.,Olazar,M.,Bilbao, J.,2011.Kineticmodellingforthetransformationof
bioethanolintoolefinsonahydrothermallystableNi–HZSM-5 catalystconsideringthedeactivationbycoke.Chem.Eng.J.
167,262–277.
Guisnet,M.,Costa,L.,Ribeiro,F.R.,2009.Preventionofzeolite deactivationbycoking.J.Mol.Catal.A:Chem.305,69–83.
Guisnet,M.,Magnoux,P.,2001.Organicchemistryofcoke formation.Appl.Catal.,A:Gen.212,83–96.
Lee,J.H.,Park,M.B.,Lee,J.K.,Min,H.-K.,Song,M.K.,Hong,S.B., 2010.SynthesisandcharacterizationofERI-typeUZM-12 zeolitesandtheirmethanol-to-olefinperformance.J.Am.
Chem.Soc.132,12971–12982.
Mihail,R.,Straja,S.,Maria,G.,Musca,G.,Pop,G.,1983.Kinetic modelformethanolconversiontoolefins.Ind.Eng.Chem.
ProcessDes.Dev.22,532–538.
Olsbye,U.,Svelle,S.,Bjørgen,M.,Beato,P.,Janssens,T.V.,Joensen, F.,Bordiga,S.,Lillerud,K.P.,2012.Conversionofmethanolto hydrocarbons:howzeolitecavityandporesizecontrols productselectivity.Angew.Chem.Int.Ed.51,5810–5831.
Park,J.W.,Kim,S.J.,Seo,M.,Kim,S.Y.,Sugi,Y.,Seo,G.,2008.
ProductselectivityandcatalyticdeactivationofMORzeolites withdifferentacidsitedensitiesinmethanol-to-olefin(MTO) reactions.Appl.Catal.,A:Gen.349,76–85.
Rostami,R.B.,Ghavipour,M.,Behbahani,R.M.,Aghajafari,A., 2014.ImprovementofSAPO-34performanceinMTOreaction byutilizingmixed-templatecatalystsynthesismethod.J.Nat.
GasSci.Eng.20,312–318.
Rostami,R.B.,Ghavipour,M.,Di,Z.,Wang,Y.,Behbahani,R.M., 2015.StudyofcokedepositionphenomenaontheSAPO34 catalystanditseffectsonlightolefinselectivityduringthe methanoltoolefinreaction.RSCAdv.5,81965–81980.
Spivey,J.J.,1991.Review:dehydrationcatalystsforthe
methanol/dimethyletherreaction.Chem.Eng.Commun.110, 123–142.
Sun,Q.,Ma,Y.,Wang,N.,Li,X.,Xi,D.,Xu,J.,Deng,F.,Yoon,K.B., Oleynikov,P.,Terasaki,O.,2014.Highperformance
nanosheet-likesilicoaluminophosphatemolecularsieves:
synthesis,3DEDTstructuralanalysisandMTOcatalytic studies.J.Mater.Chem.A2,17828–17839.
Svelle,S.,Olsbye,U.,Joensen,F.,Bjørgen,M.,2007.Conversionof methanoltoalkenesovermedium-andlarge-poreacidic zeolites:stericmanipulationofthereactionintermediates governstheethene/propeneproductselectivity.J.Phys.Chem.
C111,17981–17984.
Teketel,S.,Skistad,W.,Benard,S.,Olsbye,U.,Lillerud,K.P.,Beato, P.,Svelle,S.,2011.Shapeselectivityintheconversionof methanoltohydrocarbons:thecatalyticperformanceof one-dimensional10-ringzeolites:ZSM-22,ZSM-23,ZSM-48, andEU-1.ACSCatal.2,26–37.
Tian,P.,Wei,Y.,Ye,M.,Liu,Z.M.,2015.Methanoltoolefins(MTO):
fromfundamentalstocommercialization.ACSCatal.5, 1922–1938.
VanSpeybroeck,V.,DeWispelaere,K.,VanderMynsbrugge,J., Vandichel,M.,Hemelsoet,K.,Waroquier,M.,2014.First
principlechemicalkineticsinzeolites:themethanol-to-olefin processasacasestudy.Chem.Soc.Rev.43,7326–7357.
Vera-Castaneda,E.,1985.TheStudyoftheMethanolConversion toEthyleneandPropyleneUsingSmallPoreSizeZeolites.
TexasA&MUniversity,TX,USA.
Wang,C.,Yang,M.,Tian,P.,Xu,S.,Yang,Y.,Wang,D.,Yuan,Y., Liu,Z.,2015.Dualtemplate-directedsynthesisofSAPO-34 nanosheetassemblieswithimprovedstabilityinthe methanoltoolefinsreaction.J.Mater.Chem.A,5608–5616.
Wang,Q.,Cui,Z.-M.,Cao,C.-Y.,Song,W.-G.,2011.0.3 ˚Amakesthe difference:dramaticchangesinmethanol-to-olefinactivities betweenH-ZSM-12andH-ZSM-22zeolites.J.Phys.Chem.C 115,24987–24992.
Yang,G.,Wei,Y.,Xu,S.,Chen,J.,Li,J.,Liu,Z.,Yu,J.,Xu,R.,2013.
Nanosize-enhancedlifetimeofSAPO-34catalystsin methanol-to-olefinreactions.J.Phys.Chem.C117, 8214–8222.
