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ConversionofxyloseintofurfuralinaMOF-basedmixedmatrixmembranereactorHuaJina,b,XinleiLiuc,YujieBana,b,YuanPenga,b,WenmeiJiaoa,b,PoWanga,b,AngGuoa,b,YanshuoLia,⇑,WeishenYanga,⇑aStateKeyLaboratoryofCatalysis,DalianInstituteofChemicalPhysics,ChineseAcademyofSciences,Dalian116023,ChinabUniversityofChineseAcademyofSciences,Beijing100049,ChinacDepartmentofChemicalEngineering,ImperialCollegeLondon,LondonSW72AZ,UnitedKingdomhighlightsAnovelZn2(bim)4-PMPSmembraneforfurfuralrecoverywasprepared.Themembranedemonstratedhighvaporpermeationperformance.In-situremovaloffurfuralbythemembraneincreasedthefurfuralyieldgreatly.StronginteractionoflayeredZn2(bim)4andPMPSmatrixwasfound.graphicalabstractarticleinfoArticlehistory:Availableonline14November2015Keywords:FurfuralXyloseMixedmatrixmembraneVaporpermeationMembranereactorabstractFurfuralisregardedasanimportantplatformchemicalwithawiderangeofapplications.Becauseofthelowconcentrationoffurfuralinthehydrolysate,energy-savingandenvironmentallyfriendlyseparationmethodisurgentlydemanded.Inthiswork,ahomogeneousmixedmatrixmembrane(MMM)consistingofZn2(bim)4asinorganicfillerandPMPS(polymethylphenylsiloxane)aspolymermatrixwassuccessfullyfabricatedbyemployingasolution-blendingmethod.Thevaporpermeationexperimentsdemonstratedthatthepervaporationseparationindex(PSI)increasedwithincreasingtemperature,indicatingthehighperformanceoftheas-synthesizedZn2(bim)4-PMPSmembraneforseparatingfurfuralathightempera-ture.Hereafter,thedehydrationreactionofxyloseintofurfuralinamembranereactorcoupledwithZn2(bim)4-PMPSmembranewascarriedout.Incontrasttotheconventionalreactor,thefurfuralyieldinmembranereactorkeptincreasingduetothein-siturecoveryoffurfuralbyvaporpermeation.Thehighestfurfuralyieldachievedtillnowwas41.1%at140Cinaqueoussolution.OwingtotheintrinsicseparationpropertiesofZn2(bim)4crystalsandtheeffectiveenhancementofmembranestabilitybyinteractionofZn2(bim)4withPMPSmatrix,theZn2(bim)4-PMPSmembranecoupledreactorexhibitedbetterperformancethanpurePMPSmembranecoupledreactor.2015ElsevierB.V.Allrightsreserved.1.IntroductionBiomass-basedplatformchemicalshaveattractedintenseinter-estinrecentyearsasasustainableandenvironment-friendlyalternativetofossil-basedchemicals[1–4].Furfural(2-furancarbox-aldehyde),akeyplatformchemical,canbeusedin2015ElsevierB.V.Allrightsreserved.⇑Correspondingauthors.E-mailaddresses:leeys@dicp.ac.cn(Y.Li),yangws@dicp.ac.cn(W.Yang).URL:(W.Yang).ChemicalEngineeringJournal305(2016)12–18ContentslistsavailableatScienceDirectChemicalEngineeringJournaljournalhomepage:[5,6].Fur-furalistypicallyproducedbythedehydrationofxylosecontainedinlignocelluloseoveranacidiccatalyst[7,8].Alongwiththedehydrationreaction,severalotherreactions,suchastheisomer-izationordecompositionreactionofthepentoses,alsotakeplace.Meanwhile,theformedfurfuralcanundergocondensation,resini-ficationordecomposition[9].Asaresult,theselectivitytowardfurfuraldecreasedwithreactiontime,leadingtoadeclineoffurfuralyield.Tothisend,in-situremovaloffurfuraltoavoidtheundesiredsidereactionsisofgreatimportance.Manymethods(e.g.,liquid–liquidextraction[10],supercriticalCO2extraction[11]andadsorption[12])havebeenadoptedforfurfuralsepara-tion.However,theapplicationoftheseseparationmethodsislimitedbecauseofmanydrawbackssuchascomplicatedprocessandenergy-intensive.Forexample,extractionsolventsemployedinabiphasicsystemforin-situremovaloffurfuralaregenerallytoxicandexpensive.Therefore,itisanurgentdemandtodevelopamoreeconomicalandenvironmentallyfriendlymethodforfurfuralrecovery.Membraneseparationhasbecomeaveryattractiveseparationtechnologyowingtoitsenergy-savingandefficiency.Pervapora-tion(PV)andvaporpermeation(VP)areconsideredtobeeffectivefortheremovaloftracevolatileorganiccompoundsfromwater[13].Forseparatingfurfuralfromaqueoussolution,bothpurepoly-mermembranesandmixedmatrixmembraneshavebeenreportedwithgoodpervaporationperformance[14–17].EarlierstudiedPUUmembranedisplaysextremelowflux(below60gm2h1)whichretardstheindustrialapplication.Silicone(PDMS)membranereportedlatelyshowsmuchhigherfluxwithacceptableseparationfactor.WiththerapidlygrowingattentiononMOFseparationmembranes[18–23],ourgroupfabricatedaZIF-8-siliconerubbermixedmatrixmembranewithremarkablypervaporationperfor-mance(separationfactor53.3andtotalflux900gm2h1).Alltheseresultsdisplaypromisingpotentialforin-situfurfuralrecov-eryinbiorefineryindustry.Nevertheless,efficientproductionoffurfuralcontinuouslybymeansofamembranereactorwhichinte-gratesthedehydrationreactionofxylosewithPVorVPprocessstillhasn’tbeeninvestigated.Inthecurrentwork,aZn2(bim)4-PMPSmixedmatrixmem-braneforin-situfurfuralrecoverywasintegratedwithxylosedehydrationtoachieveefficientproductionoffurfural.Incontrasttotheconventionalreactor,thefurfuralyieldinmembranereactorcoupledwithVPprocesskeptincreasingwithtime.Moreover,intermsofthefurfuralyield,theZn2(bim)4-PMPSmembranecoupledreactordem