424ꢀ
HirokazuꢀKobayashiꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ38ꢀ(2017)ꢀ420–425ꢀ
smallerꢀ amountꢀ ofꢀ mesoporesꢀ andꢀ SO
mesopore.ꢀAsꢀaꢀcontrolꢀinꢀaꢀliterature,ꢀH‐ZSM‐5ꢀpredominantlyꢀ
4
2–/ZrO
2
ꢀ possessesꢀ noꢀ
Scienceꢀ(JSPS).ꢀOpenꢀFacilityꢀofꢀInstituteꢀforꢀCatalysisꢀwasꢀuti‐
lizedꢀforꢀTEMꢀmeasurement.ꢀ
hasꢀ Brønstedꢀ acidꢀ sitesꢀ withꢀ similarꢀ strengthꢀ (Hdesꢀ =ꢀ 135ꢀ kJꢀ
–1
2–/MZS,ꢀbutꢀtheꢀzeoliteꢀrequiresꢀhigherꢀ
mol ꢀ[31])ꢀtoꢀthatꢀofꢀSO
4
Referencesꢀ
temperatureꢀtoꢀconvertꢀglycerolꢀ(588ꢀK)ꢀ[8].ꢀThus,ꢀweꢀassumeꢀ
thatꢀgoodꢀdiffusionꢀofꢀglycerolꢀinꢀlargeꢀporesꢀbenefitsꢀtheꢀcata‐
lyticꢀperformance.ꢀ
[1]ꢀ A.ꢀCorma,ꢀS.ꢀIborra,ꢀA.ꢀVelty,ꢀChem.ꢀRev.,ꢀ2007,ꢀ107,ꢀ24112502.ꢀ
[
2]ꢀ H.ꢀKobayahsi,ꢀA.ꢀFukuoka,ꢀGreenꢀChem.,ꢀ2013,ꢀ15,ꢀ17401763.ꢀ
[3]ꢀ A.ꢀ F.ꢀ Lee,ꢀ J.ꢀ A.ꢀ Bennett,ꢀ J.ꢀ C.ꢀ Manayil,ꢀ K.ꢀ Wilson,ꢀ Chem.ꢀ Soc.ꢀ Rev.,ꢀ
014,ꢀ43,ꢀ78877916.ꢀ
Durabilityꢀofꢀ SO 2
–/MZSꢀwasꢀstudiedꢀinꢀlongꢀtimeꢀreactionꢀ
4
2
(Fig.ꢀ 6).ꢀ Sinceꢀ theꢀ vaporizationꢀ ofꢀ glycerolꢀ takesꢀ timeꢀ inꢀ thisꢀ
[4]ꢀ Z.ꢀHelwani,ꢀM.ꢀR.ꢀOthman,ꢀN.ꢀAziz,ꢀJ.ꢀKim,ꢀW.ꢀJ.ꢀN.ꢀFernando,ꢀAppl.ꢀ
Catal.ꢀA,ꢀ2009,ꢀ363,ꢀ110.ꢀ
reaction,ꢀ theꢀ firstꢀ analysisꢀ (2ꢀ h)ꢀ providesꢀ apparentlyꢀ higherꢀ
conversionꢀandꢀlowerꢀyieldꢀofꢀacroleinꢀthanꢀrealꢀvalues.ꢀAfterꢀ
theꢀinductionꢀperiod,ꢀconversionꢀofꢀglycerolꢀasꢀwellꢀasꢀyieldꢀofꢀ
acroleinꢀcontinuouslyꢀdecreasedꢀoverꢀ6ꢀh,ꢀandꢀcolorꢀofꢀtheꢀcat‐
alystꢀ changedꢀ fromꢀoffꢀwhiteꢀtoꢀblack.ꢀ Therefore,ꢀ theꢀ catalystꢀ
wasꢀonceꢀcalcinedꢀatꢀ673ꢀKꢀforꢀ2ꢀhꢀinꢀair,ꢀalthoughꢀcokeꢀwasꢀnotꢀ
completelyꢀremoved.ꢀCatalyticꢀactivityꢀwasꢀslightlyꢀrecovered,ꢀ
butꢀtheꢀyieldꢀofꢀacroleinꢀwasꢀagainꢀdecreasedꢀwithꢀincreasingꢀ
theꢀtimeꢀonꢀstream.ꢀTheꢀusedꢀcatalystꢀhadꢀlowerꢀsurfaceꢀareaꢀ
[5]ꢀ T.ꢀM.ꢀHsin,ꢀS.ꢀChen,ꢀE.ꢀGuo,ꢀC.ꢀH.ꢀTsai,ꢀM.ꢀPruski,ꢀV.ꢀS.ꢀY.ꢀLin,ꢀTop.ꢀ
Catal.,ꢀ2010,ꢀ53,ꢀ746754.ꢀ
[
[
6]ꢀ http://www.smartcatalyst.net/res/Biofuels%20smartcatalysts.ꢀpdfꢀ
7]ꢀ B.ꢀ Katryniok,ꢀ S.ꢀ Paul,ꢀ F.ꢀ Dumeignil,ꢀ ACSꢀ Catal.,ꢀ 2013,ꢀ 3,ꢀ
18191834.ꢀ
[8]ꢀ B.ꢀKatryniok,ꢀS.ꢀPaul,ꢀV.ꢀBellière‐Baca,ꢀP.ꢀRey,ꢀF.ꢀDumeignil,ꢀGreenꢀ
Chem.,ꢀ2010,ꢀ12,ꢀ20792098.ꢀ
[9]ꢀ A.ꢀCorma,ꢀG.ꢀW.ꢀHuber,ꢀL.ꢀSauvanaud,ꢀP.ꢀO’Connor,ꢀJ.ꢀCatal.,ꢀ2008,ꢀ
2
–1
3
–1
257,ꢀ163171.ꢀ
(
(
140ꢀ m ꢀ g )ꢀ andꢀ poreꢀ volumeꢀ (0.30ꢀ cm ꢀ g )ꢀ thanꢀ freshꢀ oneꢀ
[
[
[
[
10]ꢀ Q.ꢀB.ꢀLiu,ꢀZ.ꢀZhang,ꢀY.ꢀDu,ꢀJ.ꢀLi,ꢀX.ꢀG.ꢀYang,ꢀCatal.ꢀLett.,ꢀ2009,ꢀ127,ꢀ
19428.ꢀ
11]ꢀ A.ꢀAlhanash,ꢀE.ꢀF.ꢀKozhevnikova,ꢀI.ꢀV.ꢀKozhevnikov,ꢀAppl.ꢀCatal.ꢀA,ꢀ
010,ꢀ378,ꢀ1118.ꢀ
12]ꢀ J.ꢀ Deleplanque,ꢀ J.ꢀ L.ꢀ Dubios,ꢀ J.ꢀ F.ꢀ Devaux,ꢀ W.ꢀ Ueda,ꢀ Catal.ꢀ Today,ꢀ
010,ꢀ157,ꢀ351358.ꢀ
2
–1
3
–1
260ꢀm ꢀg ,ꢀ0.40ꢀcm ꢀg )ꢀdueꢀtoꢀpresenceꢀofꢀcoke,ꢀwhileꢀleach‐
4
ingꢀofꢀsulfurꢀdidꢀnotꢀoccurꢀinꢀtheꢀreactionꢀasꢀtheꢀtrapꢀaqueousꢀ
solutionꢀwasꢀnearlyꢀneutralꢀ(pHꢀ=ꢀ4–5,ꢀcorrespondingꢀtoꢀonlyꢀ
2
1
%ꢀ lossꢀ ofꢀ Sꢀ asꢀ H
2
SO ).ꢀ Thusꢀ theꢀ deactivationꢀ isꢀ ascribedꢀ toꢀ
4
coveringꢀ ofꢀ acidꢀ sitesꢀ byꢀ coke,ꢀ andꢀ weꢀ expectꢀ thatꢀ completeꢀ
removalꢀofꢀcokeꢀrecoversꢀtheꢀcatalyticꢀactivity.ꢀ
2
13]ꢀ L.ꢀYang,ꢀJ.ꢀB.ꢀJoo,ꢀY.ꢀJ.ꢀKim,ꢀS.ꢀOh,ꢀN.ꢀD.ꢀKim,ꢀJ.ꢀYi,ꢀKoreanꢀJ.ꢀChem.ꢀ
Eng.,ꢀ2008,ꢀ25,ꢀ10141017.ꢀ
4.ꢀ ꢀ Conclusionsꢀ
[14]ꢀ L.ꢀYang,ꢀJ.ꢀB.ꢀJoo,ꢀN.ꢀD.ꢀKim,ꢀK.ꢀS.ꢀJung,ꢀJ.ꢀYi,ꢀKoreanꢀJ.ꢀChem.ꢀEng.,ꢀ
010,ꢀ27,ꢀ16951699.ꢀ
2
2–/MZSꢀcatalystꢀselectivelyꢀpossessesꢀBrønstedꢀacidꢀsitesꢀ
andꢀconvertsꢀglycerolꢀtoꢀacroleinꢀinꢀ81%ꢀyieldꢀ(STYꢀ=ꢀ9.0ꢀmmolꢀ
[15]ꢀ F.ꢀ Cavani,ꢀ S.ꢀ Guidetti,ꢀ L.ꢀ Marinelli,ꢀ M.ꢀ Piccinini,ꢀ E.ꢀ Ghedini,ꢀ M.ꢀ
SO
4
Signoretto,ꢀAppl.ꢀCatal.ꢀB,ꢀ2010,ꢀ100,ꢀ197204.ꢀ
[16]ꢀ F.ꢀCavani,ꢀS.ꢀGuidetti,ꢀC.ꢀTrevisanut,ꢀE.ꢀGhedini,ꢀM.ꢀSignoretto,ꢀAppl.ꢀ
–1
–1
g ꢀh )ꢀandꢀ82%ꢀselectivityꢀatꢀaꢀlowꢀtemperatureꢀofꢀ523ꢀK.ꢀWeꢀ
proposeꢀ thatꢀ milderꢀ acidityꢀ thanꢀ sulfatedꢀ zirconiaꢀ andꢀ goodꢀ
diffusionꢀofꢀglycerolꢀbenefitsꢀtheꢀcatalyticꢀactivityꢀandꢀselectivi‐
ty.ꢀTheꢀcatalystꢀisꢀdeactivatedꢀbyꢀcokingꢀwithoutꢀlossꢀofꢀsulfur,ꢀ
andꢀthereforeꢀcompleteꢀremovalꢀofꢀcokeꢀmayꢀrecoverꢀtheꢀcata‐
lyticꢀactivity.ꢀ
Catal.ꢀA,ꢀ2011,ꢀ409410,ꢀ267278.ꢀ
[
[
17]ꢀ G.ꢀRaju,ꢀP.ꢀS.ꢀReddy,ꢀB.ꢀM.ꢀReddy,ꢀOpenꢀCatal.ꢀJ.,ꢀ2011,ꢀ4,ꢀ8387.ꢀ
18]ꢀ C.ꢀ García‐Sancho,ꢀ R.ꢀ Moreno‐Tost,ꢀ J.ꢀ Mérida‐Robles,ꢀ J.ꢀ
Santamaría‐González,ꢀA.ꢀJiménez‐López,ꢀP.ꢀMaireles‐Torres,ꢀAppl.ꢀ
Catal.ꢀA,ꢀ2012,ꢀ433434,ꢀ179187.ꢀ
[19]ꢀ N.ꢀPethanꢀRajan,ꢀG.ꢀS.ꢀRao,ꢀV.ꢀPavankumar,ꢀK.ꢀV.ꢀR.ꢀChary,ꢀCatal.ꢀSci.ꢀ
Technol.,ꢀ2014,ꢀ4,ꢀ8192.ꢀ
Acknowledgmentꢀ
[20]ꢀ X.ꢀZ.ꢀFeng,ꢀY.ꢀYao,ꢀQ.ꢀSu,ꢀL.ꢀZhao,ꢀW.ꢀJiang,ꢀW.ꢀJ.ꢀJi,ꢀC.ꢀT.ꢀAu,ꢀAppl.ꢀ
Catal.ꢀB,ꢀ2015,ꢀ164,ꢀ3139.ꢀ
[
21]ꢀ L.ꢀC.ꢀLiu,ꢀB.ꢀWang,ꢀY.ꢀH.ꢀDu,ꢀA.ꢀBorgna,ꢀAppl.ꢀCatal.ꢀA,ꢀ2015,ꢀ489,ꢀ
241.ꢀ
22]ꢀ S.ꢀ H.ꢀ Chai,ꢀ H.ꢀ P.ꢀ Wang,ꢀ Y.ꢀ Liang.ꢀ B.ꢀ Q.ꢀ Xu,ꢀ Greenꢀ Chem.,ꢀ 2007,ꢀ 9,ꢀ
ThisꢀworkꢀwasꢀsupportedꢀbyꢀGrant‐in‐AidꢀforꢀResearchꢀAc‐
tivityꢀStart‐upꢀ(KAKENHI,ꢀ21860004)ꢀandꢀforꢀYoungꢀScientistsꢀ
3
[
(KAKENHI,ꢀ26709060)ꢀfromꢀJapanꢀSocietyꢀforꢀtheꢀPromotionꢀofꢀ
GraphicalꢀAbstractꢀ
Chin.ꢀJ.ꢀCatal.,ꢀ2017,ꢀ38:ꢀ420–425ꢀ ꢀ ꢀ doi:ꢀ10.1016/S1872‐2067(16)62564‐0
Conversionꢀofꢀglycerolꢀtoꢀacroleinꢀbyꢀmesoporousꢀsulfatedꢀ
zirconia‐silicaꢀcatalystꢀ
ꢀ
HirokazuꢀKobayashi,ꢀShogoꢀIto,ꢀKenjiꢀHara,ꢀAtsushiꢀFukuoka*ꢀ ꢀ
HokkaidoꢀUniversity,ꢀJapan;ꢀTokyoꢀUniversityꢀofꢀTechnology,ꢀJapanꢀ
Mesoporousꢀsulfatedꢀzirconia‐silicaꢀcatalystꢀbearingꢀonlyꢀBrønstedꢀ
acidꢀsitesꢀselectivelyꢀconvertsꢀglycerolꢀtoꢀacroleinꢀinꢀgasꢀphaseꢀatꢀ
523ꢀ K.ꢀ Mildꢀ acidꢀ strength,ꢀ absenceꢀ ofꢀ Lewisꢀ acidꢀ sitesꢀ andꢀ largeꢀ
poreꢀbenefitꢀtheꢀreaction.ꢀ