外文专利的说明书.docx

外文专利的说明书.docx

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外文专利的说明书

ISOPROPYLALCOHOLFROMPROPYLENEUSINGZIRCONIUMBASEDMIXEDMETALOXIDES

FIELDOFTHEINVENTION

[0001]Theinventionrelatestotheproductionofisopropylalcohol（IPA）bydirecthydrationofpropyleneovermixedmetaloxides.

BACKGROUNDOFTHEINVENTION

[0002]Hydrationofpropylenetomakeisopropylalcohol（IPA）hasbeenpracticedcommerciallyformanyyears.Commercialprocessesmaybeclassifiedasindirectordirecthydrationprocesses.Indirecthydrationprocessescontactpropylene（C3=）withstrongmineralacidssuchasulfuricacidorphosphoricacidtoformasulfate/phosphateesterwhichisthenhydrolyzedtoreformtheacidandproducetheIPAproduct.Directhydration（DH）processesfeedpropyleneandwateroverasolidacidcatalystthathydrolyzestheolefintoproduceIPA.

[0003]DHprocessestypicallyusesolidacidcatalystorheterogeneouscatalystforthehydrationofthepropylenedirectlytoIPA.Inthedirectprocess,thehydrationoftheolefinstoalcoholsiscarriedoutdirectlyandinasinglestep,bycontactingtheolefinwiththehydrationwaterinthepresenceofanacidiccatalyst.DHprocessestypicallyrequirechemicalgradepropyleneorbetterasfeedtodecreaseimpuritiesproducedandmaintaincatalystlife.DHmaybecarriedoutinvapor-phase,liquid-phaseormixedphase.IPEisthemajorby-productfromtheC3<">directhydrationprocesses.

[0004]SolidacidcatalyststhathavebeenutilizedforDHincludefunctionalizeddivinylbenzenepolymercatalystssuchassulfonicacidresins（i.e.Amberlysts（TM）,Dowexs（TM））,solidphosphoricacid（SPA）,varioustypesofzeolites,metalimpregnatedsilicaandaluminas.AlthoughthesecatalystsarecapableofDHchemistrytheyallaresubjecttovariouslimitationsthatimpacthowtheycanbeused.Resincatalystsareveryactivebutarenotintrinsicallyselectiveandchemicallydegradeover150<0>C.Tomanagethenon-selectivity,highwatertoC3=ratiosareusedtodrivetheequilibriumtowardsIPA.ThesehighwatersystemscreatemorecostlyprocessesforseparationandpurificationofIPA.Manyzeolites/molecularsievesandothersilica/aluminacatalystsareintrinsicallyselectivetoIPAduetomicroporousstructure,butthesehavehydrolyticstabilityproblems.[0005]Accordingly,thisveryimportantcommercialprocessisanareaofactiveresearchtoovercometheproblemswithpriorartprocesses.[0006]Onespecificareaofresearchinvolvescatalystsbasedonthemodificationonemetaloxidebyincorporationofothermetaloxides,generallyreferredtoasmixedmetaloxides（MMO's）.Typically,atleastoneofthemetalsisatransitionmetal（i.e.,Groups3-11accordingtothePeriodicTablefromChemicalandEngineeringNews,63（5）,27,1985）.Asusedherein,theterm"transitionmetal"includesthemembersoftheLanthanideandActinidefamiliesofsaidTable.

[0007]WorkbyHoeckerin1996（DE1012783）identifiedZrO2foruseasasubstrateforaphosphoricacidcoatedcatalyst.Theactivityfromthatcatalystisbelievedduetotheinclusionofphosphoricacid.

[0008]Krause（WO200234390）describedcatalystscomprisedsilicaplus5-50%oxidesofthetransitionmetals,includingZrO2.Thesemixedmetaloxidesarebasedprimarilyonthesilicasubstrate.

[0009]ChiyodaCorp（JP08224472）reportedawaterinsolublezirconiumhydroxidecoatedwithatungstencompound.

[0010]SeealsorecentworkdirectedtoIPAproductionasdisclosedinU.S.PatentNo.

7,173,158;U.S.PatentApplicationPublicationNo.20060269462and20060270883;and

PCTpublicationWO2006/135475.

[0011]Inpreviousworkdescribedbyoneormoreofthepresentinventors,aCeO/ZrO2mixedmetaloxidecatalystwasidentifiedasactiveforthedecompositionofisopropylether

（IPE）.SeeU.S.7,102,037,andU.S.ApplicationPublicationNo.2006-0281954.Highpurity

C3=wasproduced,alongwithsomeisopropylalcohol（IPA）wasproducedasasidereaction.

Sincethesereactionsarereversible,eitherIPEorIPAcanbeoptimizedasthemainproductbyselectionofthereactionconditions.

[0012]WhileithasbeenfoundthattheCeO/ZrO2catalystpreviouslydescribedpromotesdirecthydrationofpropylene,theactivityisinsufficientforcommercialproduction.

[0013]Thepresentinventorshavefound,however,thatbyproperincorporationofcertainothermetaloxidesbytheuseofco-precipitation,anMMOcatalystsbasedonZrO2forthedirecthydrationofpropylenemaybeachieved.

SUMMARYOFTHEINVENTION

[0014]Theinventionisdirectedtomixedmetaloxide（MMO）catalystsbasedonZrO2.Themixedmetaloxidecomprisesatleasttwometals,atleastoneofwhichiszirconium（Zr）andhavingatleastoneothermetalselectedfromtransitionmetalsotherthanZr.Themixedmetaloxidesoftheinventionaremadebyco-precipitationoftheatleasttwometals.Themixedmetaloxidesaccordingtotheinventionareusefulfortheproductionofisopropylalcohol（IPA）,aswellasotherolefinsintherangeofC2toC5carbonlength.

[0015]Inpreferredembodiments,theDHcatalystsaccordingtotheinventionarestablefortheconversionofpropylenetoIPAathighertemperaturesthantheacidicresinsandstrongacidsolidcatalysts.

[0016]Inanotherpreferredembodiments,thecatalystsoftheinventionfunctionasDHcatalystsfortheconversionofpropylenetoIPAoverawideroperationalrange.

[0017]Instillanotherembodiment,theDHcatalystsoftheinventionhavegoodhydrolyticstability.

[0018]Inyetstillanotherembodiment,theDHcatalystsoftheinventionareregenerable.

[0019]Moreover,inotherembodiments,theDHcatalystoftheinventioncanberunatlowwatertopropyleneratios（Qratio）withouttheco-productionoflargeamountsofIPEfortheconversionofpropylenetoIPA.

[0020]ItisanobjectoftheinventiontoprovideMMOsthatareactiveforthedirecthydrationofpropylenetoproduceisopropylalcohol（IPA）withoutco-productionoflargeamountsofisopropylether（IPE）.

[0021]Itisanobjectoftheinventiontoprovidehigh-temperaturestableZr[theta]2-based

MMOsoperatingoverawidevariationofoperatingconditions,havinggoodhydrolyticstability,thatproduceIPAatlowwaterpropyleneratiosandwhichareregenerable.

[0022]Theseandotherobjects,features,andadvantageswillbecomeapparentasreferenceismadetothefollowingdetaileddescription,preferredembodiments,examples,andappendedclaims.

DETAILEDDESCRIPTIONOFTHEINVENTION

[0023]Accordingtotheinvention,mixedmetaloxide（MMO）catalystsbasedonZrO2aremadebyaprocesscomprisingco-precipitationofthemetalspeciesfromsolution,followedbycalcination.TheMMOsoftheinventionareusefulfortheproductionofisopropylalcohol（IPA）.

[0024]Themixedmetaloxideoftheinventioncomprisesatleasttwometals,atleastoneofwhichiszirconium（Zr）andhavingatleastoneothermetalselectedfromtransitionmetalsotherthanZr.

[0025]Themixedmetaloxideoftheinventioniszirconium-based（or"Zr[theta]2-based"）,whereintheterm"zirconium-based"meansthatzirconiummetal,regardlessofoxidationstate,ispresentintheamountofatleastgreaterthan50wt%,basedontheweightofthemetalspresentinthemixedmetaloxidecatalyst.Itispreferredthatzirconiumbepresentintheamountofgreaterthan50.0wt%to99.5wt%,or60.0wt%,to99.0wt%,or70.0wt%to98.5wt%,or80wt%to98.0wt%,balancetheatleastoneothermetal.Usefulrangesincludefromanyoftheminimumamountspecifiedabovetoanyofthemaximumamountspecifiedabove,e.g.,rangessuchas>50wt%to98.0wt%and80wt%to99.0wt%arealsocontemplated.

[0026]TheatleastoneothermetalinthemixedmetaloxideoftheinventionisselectedfromGroups3-11ofthePeriodicTable,i.e.,thetransitionmetals,whichincludestheLanthanidesandActinides.MorethanonemetalotherthanzirconiummaybepresentintheMMO,providedthattheoneormoremetalsotherthanzirconiumareco-precipitatedalongwithzirconium.

[0027]Inanembodiment,thetransitionmetalotherthanZrisselectedfromatleastoneofGroups3-9（again,thetransitionmetalsincludingLanthanidesandActinides.Inanotherembodiment,thetransitionmetalotherthanZrisselectedfromatleastoneofCe,Mn,W,Cu,Mo,Fe,andCr.InstillanotherembodimentthemetalisselectedfromatleastoneofthetransitionmetalsinGroups3-9.InyetanotherembodimenttheyareselectedfromCe,W,Mo,andmixturesthereof.Inyetanotherembodimentthemetalsusedareselectedfromtungsten,molybdenum,copper,manganese,ironandmixturesthereof.

[0028]Themixedmetaloxidesoftheinventionaremadebyco-precipitationoftheatleasttwometalsfromsolution.Themetalsaltsusedtoco-precipitatewiththeZrOcanincludeone,twoormoremetals.Theatleasttwometalsaredissolvedinasuitablesolvent,suchaswater,andcausedtobesimultaneouslyprecipitated,suchasbyadditionofasuitablebase.Asolublesaltofthemetalispreferablyused,forexample:

halides,sulfates,nitrates,andpolymetallatessuchaszirconylchloride,ammoniummetaltungstate,ceriumsulfateandthelike.Morethanonedifferentsaltcontainingthesamemetalmaybeused.Thenon-metalcounterion（e.g.,halide,sulfate,nitrate,andthelike）maybethesameordifferentfortheatleasttwometalsandmaybeindependentlyselected.

[0029]Theterm"solublesalt"wouldbeunderstoodbyoneofordinaryskillinthearttobearelativetermanddependsonthesolventused.Theexactamountofsaltthatneedstobedissolvedisnotparticularlyimportantexceptwithrespecttothetimeandeffortittakestoobtainausefulamountofthemixedmetal,butthisisnomorethan"routine"experimentationbyoneofordinaryskillinposse