ꢀ
DanꢀDangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ720–726ꢀ
725ꢀ
+
–
cationꢀofꢀtheꢀcatalyst.ꢀCH
3
ꢀfromꢀmethanolꢀandꢀtheꢀPh–O ꢀfromꢀ
phenolꢀgaveꢀanisole.ꢀ ꢀ
phenolꢀthenꢀcombinedꢀtoꢀgiveꢀanisole,ꢀandꢀwaterꢀwasꢀalsoꢀgen‐
+
–
eratedꢀ byꢀ theꢀ combinationꢀ ofꢀ H ꢀ andꢀ OH.ꢀ So,ꢀ theꢀ catalyticꢀ
mechanismꢀcanꢀbeꢀattributedꢀtoꢀaꢀ‘K‐acid’ꢀbifunctionalꢀprocess.ꢀ
Accordingꢀ toꢀ thisꢀ mechanism,ꢀ anꢀ excessꢀ ofꢀ Kꢀ canꢀ occupyꢀ theꢀ
Lewisꢀacidꢀsites,ꢀandꢀthusꢀdecreaseꢀtheꢀactivationꢀofꢀmethanol,ꢀ
whileꢀaꢀlowꢀKꢀloadingꢀwouldꢀgiveꢀdecreasedꢀactivationꢀofꢀphe‐
nol.ꢀ Thisꢀ explainsꢀ theꢀ phenomenonꢀ thatꢀ theꢀ catalystꢀ withꢀ theꢀ
bestꢀperformanceꢀhasꢀaꢀmediumꢀloading.ꢀ ꢀ
Referencesꢀ
[1] G.ꢀ N.ꢀ Kirichenko,ꢀ V.ꢀ I.ꢀ Glazunova,ꢀ A.ꢀ V.ꢀ Balaev,ꢀ U.ꢀ M.ꢀ Dzhemilev,ꢀ
Petrol.ꢀChem.,ꢀ2008,ꢀ48,ꢀ389–392.ꢀ
[
[
[
2] X.ꢀJ.ꢀSong,ꢀC.ꢀS.ꢀWang,ꢀFineꢀChem.,ꢀ2000,ꢀ17,ꢀ42–44.ꢀ
3] Z.ꢀH.ꢀFu,ꢀY.ꢀOno,ꢀCatal.ꢀLett.,ꢀ1993,ꢀ21,ꢀ43–47.ꢀ
4] S.ꢀOuk,ꢀS.ꢀThiebaud,ꢀE.ꢀBorredon,ꢀP.ꢀLeꢀGars,ꢀGreenꢀChem.,ꢀ2002,ꢀ4,ꢀ
431–435.ꢀ
[5] G.ꢀD.ꢀWu,ꢀX.ꢀL.ꢀWang,ꢀB.ꢀChen,ꢀJ.ꢀP.ꢀLi,ꢀN.ꢀZhao,ꢀW.ꢀWei,ꢀY.ꢀH.ꢀSun,ꢀ
Appl.ꢀCatal.ꢀA,ꢀ2007,ꢀ329,ꢀ106–111.ꢀ
4.ꢀ ꢀ Conclusionsꢀ
[
6] Y.ꢀOno,ꢀCatal.ꢀToday,ꢀ1997,ꢀ35,ꢀ15–25.ꢀ
7] M.ꢀRenavd,ꢀP.ꢀD.ꢀChantal,ꢀS.ꢀKaliaguine,ꢀCan.ꢀJ.ꢀChem.ꢀEng.,ꢀ1986,ꢀ64,ꢀ
787–791.ꢀ
Synthesisꢀofꢀanisoleꢀbyꢀvaporꢀphaseꢀmethylationꢀofꢀphenolꢀ
[
withꢀ methanolꢀ overꢀ activatedꢀ aluminaꢀ supportedꢀ catalystsꢀ
wereꢀinvestigatedꢀinꢀaꢀfixedꢀbedꢀreactor.ꢀTheꢀKH PO /AAꢀcata‐
2
4
[8] S.ꢀR.ꢀKirumakki,ꢀN.ꢀNagaraju,ꢀK.ꢀV.ꢀR.ꢀChary,ꢀS.ꢀNarayanan,ꢀJ.ꢀCatal.,ꢀ
2004,ꢀ221,ꢀ549–559.ꢀ
lystꢀwithꢀtheꢀcalcinationꢀtemperatureꢀofꢀ700ꢀ°Cꢀforꢀ8ꢀhꢀgaveꢀtheꢀ
bestꢀ performance.ꢀ Theꢀ optimalꢀ Kꢀ contentꢀ wasꢀ 7.53ꢀ wt%.ꢀ Theꢀ
levelꢀofꢀanisoleꢀyieldꢀhasꢀaꢀmaximumꢀvalueꢀatꢀ400–450ꢀ°Cꢀinꢀtheꢀ
rangeꢀ fromꢀ 300ꢀ toꢀ 500ꢀ °C,ꢀ decreasedꢀ slightlyꢀ withꢀ increasingꢀ
WHSV,ꢀandꢀincreasedꢀwithꢀincreasingꢀmoleꢀfractionꢀofꢀmetha‐
nol.ꢀ Onꢀ comparingꢀ theꢀ O‐methylationꢀ andꢀ C‐methylationꢀ ofꢀ
phenol,ꢀ aꢀ lowꢀ reactionꢀ temperature,ꢀ highꢀ WHSV,ꢀ andꢀ lowꢀ
[9] S.ꢀC.ꢀLee,ꢀS.ꢀW.ꢀLee,ꢀK.ꢀS.ꢀKim,ꢀT.ꢀJ.ꢀLee,ꢀD.ꢀH.ꢀKim,ꢀJ.ꢀC.ꢀKim,ꢀCatal.ꢀ
Today,ꢀ1998,ꢀ44,ꢀ253–258.ꢀ
[
[
[
[
10] M.ꢀE.ꢀSad,ꢀC.ꢀL.ꢀPadró,ꢀC.ꢀR.ꢀApesteguía,ꢀJ.ꢀMol.ꢀCatal.ꢀA,ꢀ2010,ꢀ327,ꢀ
63–72.ꢀ
11] K.ꢀG.ꢀBhattacharyya,ꢀ A.ꢀK.ꢀ Talukdar,ꢀP.ꢀDas,ꢀ S.ꢀ Sivasanker,ꢀ J.ꢀMol.ꢀ
Catal.ꢀA,ꢀ2003,ꢀ197,ꢀ255–262.ꢀ
12] M.ꢀE.ꢀSad,ꢀC,ꢀL,ꢀPadró,ꢀC.ꢀR.ꢀApesteguía,ꢀAppl.ꢀCatal.ꢀA,ꢀ2008,ꢀ342,ꢀ
methanolꢀ fractionꢀ overꢀ aꢀ KH
2
PO /AAꢀ catalystꢀ withꢀ higherꢀ Kꢀ
4
40–48.ꢀ
contentꢀ favoredꢀ theꢀ increaseꢀ ofꢀ anisoleꢀ selectivityꢀ byꢀ
O‐methylationꢀofꢀphenol.ꢀTheꢀlevelꢀofꢀanisoleꢀyieldꢀwasꢀmaxim‐
izedꢀ underꢀ theꢀ optimizedꢀ reactionꢀ conditionsꢀ ofꢀ aroundꢀ
13] K.ꢀSreekumar,ꢀS.ꢀSugunan,ꢀJ.ꢀMol.ꢀCatal.ꢀA,ꢀ2002,ꢀ185,ꢀ259–268.ꢀ
[14] Q.ꢀY.ꢀYu,ꢀX.ꢀY.ꢀChou,ꢀC.ꢀH.ꢀXu,ꢀZ.ꢀL.ꢀXu,ꢀSpecialityꢀPetrochem.,ꢀ2009,ꢀ
26,ꢀ12–14.ꢀ
–1
[15] L.ꢀXu,ꢀS.ꢀJ.ꢀWu,ꢀW.ꢀX.ꢀZhang,ꢀM.ꢀJ.ꢀJia,ꢀG.ꢀLiu,ꢀActaꢀPhys.ꢀChim.ꢀSin.,ꢀ
4
00–450ꢀ°C,ꢀlowꢀWHSVꢀbelowꢀ0.18ꢀh ,ꢀandꢀhighꢀmolarꢀratioꢀofꢀ
2
009,ꢀ25,ꢀ242–246.ꢀ
16] G.ꢀSaralaꢀDevi,ꢀD.ꢀGiridhar,ꢀB.ꢀM.ꢀReddy,ꢀJ.ꢀMol.ꢀCatal.ꢀA,ꢀ2002,ꢀ181,ꢀ
73–178.ꢀ
methanolꢀtoꢀphenolꢀofꢀ5.ꢀTheꢀcatalystꢀpreparationꢀandꢀanisoleꢀ
synthesisꢀprocessꢀareꢀveryꢀsimpleꢀwithꢀlowꢀcostꢀandꢀaꢀrelativelyꢀ
goodꢀresult,ꢀandꢀthusꢀisꢀadvantageousꢀforꢀpracticalꢀapplication.ꢀ
Theꢀcatalyticꢀmechanismꢀwasꢀdeducedꢀtoꢀbeꢀthatꢀtheꢀadsorptionꢀ
[
1
Pageꢀnumbersꢀreferꢀtoꢀtheꢀcontentsꢀinꢀtheꢀprintꢀversion,ꢀwhichꢀincludeꢀ
2 4
ofꢀ phenolꢀ onꢀ theꢀ Kꢀ siteꢀ ofꢀ KH PO /AAꢀ andꢀ theꢀ adsorptionꢀ ofꢀ
bothꢀtheꢀEnglishꢀversionꢀandꢀextendedꢀChineseꢀabstractꢀofꢀtheꢀpaper.ꢀTheꢀ
onlineꢀversionꢀonlyꢀhasꢀtheꢀEnglishꢀversion.ꢀTheꢀpagesꢀwithꢀtheꢀextendedꢀ
Chineseꢀabstractꢀareꢀonlyꢀavailableꢀinꢀtheꢀprintꢀversion.ꢀ
methanolꢀonꢀtheꢀLewisꢀacidꢀsiteꢀasꢀtheꢀfirstꢀreactionꢀsteps.ꢀTheꢀ
+
–
followingꢀcombinationꢀofꢀtheꢀCH ꢀofꢀmethanolꢀandꢀtheꢀPh–O ꢀofꢀ
3
GraphicalꢀAbstractꢀ
Chin.ꢀJ.ꢀCatal.,ꢀ2016,ꢀ37:ꢀ720–726ꢀ ꢀ ꢀ doi:ꢀ10.1016/S1872‐2067(15)61074‐9
Synthesisꢀofꢀanisoleꢀbyꢀvaporꢀphaseꢀmethylationꢀofꢀphenolꢀwithꢀmethanolꢀoverꢀcatalystsꢀsupportedꢀonꢀactivatedꢀaluminaꢀ
ꢀ
DanꢀDang,ꢀZeꢀWang*,ꢀWeigangꢀLin,ꢀWenliꢀSongꢀ
InstituteꢀofꢀProcessꢀEngineering,ꢀChineseꢀAcademyꢀofꢀSciencesꢀ
H
CH
3
H C
3
O
O
+
H O
2
+
O
H
H
3
H C
H
O
O
K
Al
UnderꢀcatalysisꢀofꢀKH
2
PO
4
/Al
2
O ,ꢀphenolꢀandꢀmethanolꢀwasꢀactivatedꢀbyꢀKꢀandꢀAlꢀsitesꢀrespectively.ꢀAnisoleꢀyieldꢀdecreasedꢀwithꢀincreas‐
3
ingꢀspaceꢀvelocity,ꢀincreasedꢀwithꢀincreasingꢀmethanolꢀfraction,ꢀandꢀappearedꢀaꢀmaximumꢀvalueꢀwithꢀincreasingꢀtemperature.ꢀ