AJ.Foster et al./Applied Catalysis A:General 423-424(2012)154-161 161 CFP was not possible,but it can be approximated from the com- official views or policies,either expressed or implied,of the Defense position of the other reaction products.The identified reaction Advanced Research Projects Agency or the Department of Defense products,including coke,had an atomic composition of approxi- mately 4.5 mol C/mol O and 1.1 mol C/mol H,compared to the furan Appendix A.Supplementary data feed with 4.0mol C/mol O and 1.0 mol C/mol H.From this infor- mation,it can be calculated that approximately 0.1 mol H2O is Supplementary data associated with this article can be found,in produced per mole of furan reacted. the online version,at doi:10.1016/j.apcata.2012.02.030. Treatment of samples with tartaric acid to remove external surface acid sites does not seem to improve the CFP of furan to References hydrocarbons.Some minor differences in the aromatic yield and distribution were observed between dealuminated samples and 以S%n9A.9e9e52x1838880s898. the untreated parent materials.Furan conversion over MicZSM-5* [3]A.V.Bridgwater.Chemical Engineering lournal 91(2003)87-102. formed more coke than on MicZSM-5.However,this observation [4]F.Talebnia.D.Karakshev.I.Angelidaki.Bioresource Technology 101 (2010) 4744-4753. may be the result of the higher furan conversion on MicZSM-5.As [5]R.Hilten,R.Speir,J.Kastner,K.C.Das.Journal of Analyticaland Applied Pyrolysis more of the furan is reacted,the potential for secondary reactions 88(2010)30-38. to form coke also increases.Overall,the results from furan conver- [6]M.R.Jan,F.Jabeen,J.Shah,F.Mabood,Journal ofThermal Analysis and Calorime- ty101(2010)303-308. sion suggest that the role of external surface acid sites during the [7]H.T.Lin,M.S.Haung.J.W.Luo.L.H.Lin,C.M.Lee,K.L Ou,Fuel Processing Tech- CFP of biomass is not critical enough to impact the distribution of nology91(2010)1355-1363. observed aromatic products. [8]A.Demirbas,Energy Conversion and Management 50(2009)2782-2801. [9]T.R.Carlson,Y.T.Cheng.J Jae,G.W.Huber,Energy Environmental Science 4 (2011)145-161. 4.Conclusions [10]T.R.Carlson,I.Jae,G.W.Huber,ChemCatChem 1(2009)107-110. 11]TRCarlson.]Jae.Y.C.Lin.G.A.Tompsett.G.W.Huber.Journal of Catalysis 270 2010110-124. We have investigated the catalytic fast pyrolysis of glucose, [12]T.R.Carlson,G.A Tompsett,W.C.Conner,G.W.Huber.Topics in Catalysis 52 maple wood,and furan over different types of ZSM-5 catalyst.The (2009)241-252. aromatic yield from glucose CFP goes through a maximum as a [13]T.R.Carlson,T.P.Vispute,G.W.Huber,ChemSusChem 1(2008)397-400. 141 function of framework silica-to-alumina ratio with an optimum Y.T.Cheng.G.W.Huber.ACS Catalysis 1(2011)611-628. [15]J.Jae.G.A.Tompsett,A.J.Foster,K.D.Hammond,S.M.Auerbach.R.F.Lobo.G.W. at SAR=30.This composition also minimizes the amount of coke Huber.Journal of Catalysis 279(2011)257-268. formed during reaction.This suggests that tuning the acid concen- [16]J.Jae,G.A.Tompsett,Y.C.Lin,T.R.Carlson.J.Shen.T.Zhang.B.Yang.C.E.Wyman. W.C.Conner.G.W.Huber.Energy Environmental Science 3(2010)358-365. tration within the zeolite framework is necessary to obtain high [17]N.M.Al-Otaibi.G.Hutchings,Catalysis Letters 134(2010)191-195. aromatic yields. [18]A.Bhan.N.Delgass,Catalysis Reviews 50(2008)19-151. Creating hierarchical mesopores within the zeolite catalyst had 19] M.Bjorgen.S.Svelle.F.Joense .J.Nerlov S.Kolboe,F.Bonino,L.Palumbo.S. little effect on the aromatic yield from the semi-batch CFP of glu- Bordiga,U.Olsbye,Journal of Catalysis 249(2007)195-207. [20]N.Y.Chen.T.F.Degnan,LR.Koenig.Chemtech 16(1986)506-511. cose and maple wood.Pyrolysis over mesoporous ZSM-5 catalysts [21]M.I.Haniff,L.H.Dao,Applied Catalysis 39(1988)33-47. yielded slightly more coke than the purely microporous samples. 22]J.D.Adjaye,N.N.Bakhshi,Fuel Processing Technology 45(1995)161-183. This suggests that the mesopores may act as spaces for coke to form 1231 J.D.Adjaye,N.N.Bakhshi,Fuel Processing Technology 45(1995)185-202. 24]AG.Gayubo,A.T.Aguayo.A.Atutxa,B.Valle,J.Bilbao.Journal of Chemical and accumulate.The purely microporous ZSM-5 catalyst favors Technology and Biotechnology 80(2005)1244-1251. the production of smaller monoaromatics(benzene,toluene,and [25]A.V.Bridgwater,M.L Cottam,Energy Fuels 6(1992)113-120. xylene)while hierarchically mesoporous samples shifts the prod- 26]R.K.Sharma.N.N.Bakhshi,Canadian Journal of Chemical Engineering 71(1993) 383-391. uct distribution towards heavier alkylated monoaromatics.Similar [27]T.P.Vispute,H.Y.Zhang.A.Sanna.R.Xiao.G.W.Huber.Science 330(2010) observations were made in the CFP offuran in the fixed-bed reactor 1222-1227. studies.Mesoporous catalysts tended to produce more coke and [28]S.Vitolo.M.Seggiani,P.Frediani.G.Ambrosini.L Politi.Fuel 78 (1999) 1147-1159. were more selective for the production of larger monoaromatic [29]A.Corma,G.W.Huber.L Sauvanaud,P.O'Connor,Journal of Catalysis 247(2007) products than purely microporous ZSM-5.The reaction rate of furan 307-327. over mesoporous ZSM-5 was also found to be slightly slower on [30]T.F.Degnan,Journal of Catalysis 216(2003)32-46. mesoporous ZSM-5. 31]C.M.Lew,R.Cai,Y.Yan,Accounts of Chemical Research 43(2009)210-219. [32]S.van Donk,A.H.Janssen.J.H.Bitter,K.P.de Jong.Catalysis Reviews 45(2003) The selective removal of external acid sites from the ZSM-5 cat- 297-319 alysts decreased the selectivity to the desired aromatic products [33]S.Zheng.H.R.Heydenrych,A.Jentys.JA.Lercher.Journal of Physical Chemistry and had little effect on the rate of furan conversion during CFP. B106(2002)9552-9558. [34]M.Choi,H.S.Cho,R.Srivastava,V.Chithravel,D.H.Choi,R.Ryoo,Nature Mate- The aromatic yield and selectivity from surface dealuminated sam- ias52006718-723. ples were largely the same as the untreated parent material.This [35]L.Rodriguez-Gonzalez,F.Hermes,M.Bertmer,E.Rodriguez-Castellon,A. suggests that the presence of these external surface sites has only Jimenez-Lopez,U.Simon,Applied Catalysis A:General 328(2007)174-182. 361 minor effects on the overall CFP chemistry. A.Ausavasukhi.T.Sooknoi,D.E.Resasco.Journal of Catalysis268(2009)68-78. [37]P.A.Horne.P.T.Williams,Renewable Energy 7(1996)131-144. The results from this paper show that the concentration of acid [38]A.M.Azeez,D.Meier.J.Odermatt,T.Willner,Energy Fuels 24(2010) sites on the ZSM-5 catalyst and mesopores within the ZSM-5 can be 2078-2085. [39]D.Mores,J.Kornatowski,U.Olsbye,B.M.Weckhuysen,Chemistry:A European adjusted to tune the conversion of biomass-derived molecules over Journal17(2011)2874-2884. ZSM-5 catalysts.The presence of external surface acid sites plays [40]T.A.Peters.J.van der Tuin,C.Houssin.M.A.G.Vorstman,N.E.Benes,Z.A.E.P. only a small role,and may not be an important factor in designing Vroon.A.Holmen,Catalysis Today 104(2005)288-295. catalysts for biomass CFP. [41]J.Zhao.W.Guo.G.Liu,X.Zhang.L Wang.Fuel Processing Technology 91(2010) 1090-1097. [42]V.N.Shetti.J.Kim,R.Srivastava,M.Choi,R.Ryoo.Journal of Catalysis 254(2008) 296-303 Acknowledgements [43]K.H.Park.HJ.Park.J.Kim.R.Ryoo. 1K.Jeor J.Park.Y.-K.Park,Journal of Nanoscience and Nanotechnology 10(2010)355-359. This work was supported through funding from the Defense [44]HJ.Park.H.S.Heo.J.-K.Jeon,J.Kim,R.Ryoo.K.-E.Jeong.Y.-K.Park,Applied Advanced Research Projects Agency (Surf-cat:Catalysts for Pro- Catalysis B:Environmental 95(2010)365-373. duction of JP-8 range molecules from Lignocellulosic Biomass).The [45]C.Fernandez.I.Stan,J.-P.Gilson.K.Thomas,A.Vicente.A.Bonilla.J.Perez- Ramirez,Chemistry:A European Journal 16(2010)6224-6233. views,opinions,and/or findings contained in this article are those [46]T.Q.Hoang.X.Zhu,L.L Lobban,D.E.Resasco,RG.Mallinson,Catalysis Commu- of the author and should not be interpreted as representing the nications11(2010)977-981.A.J. Foster et al. / Applied Catalysis A: General 423–424 (2012) 154–161 161 CFP was not possible, but it can be approximated from the com￾position of the other reaction products. The identified reaction products, including coke, had an atomic composition of approxi￾mately 4.5 mol C/mol O and 1.1 mol C/mol H, compared to the furan feed with 4.0 mol C/mol O and 1.0 mol C/mol H. From this infor￾mation, it can be calculated that approximately 0.1 mol H2O is produced per mole of furan reacted. Treatment of samples with tartaric acid to remove external surface acid sites does not seem to improve the CFP of furan to hydrocarbons. Some minor differences in the aromatic yield and distribution were observed between dealuminated samples and the untreated parent materials. Furan conversion over MicZSM-5* formed more coke than on MicZSM-5. However, this observation may be the result of the higher furan conversion on MicZSM-5. As more of the furan is reacted, the potential for secondary reactions to form coke also increases. Overall, the results from furan conver￾sion suggest that the role of external surface acid sites during the CFP of biomass is not critical enough to impact the distribution of observed aromatic products. 4. Conclusions We have investigated the catalytic fast pyrolysis of glucose, maple wood, and furan over different types of ZSM-5 catalyst. The aromatic yield from glucose CFP goes through a maximum as a function of framework silica-to-alumina ratio with an optimum at SAR = 30. This composition also minimizes the amount of coke formed during reaction. This suggests that tuning the acid concen￾tration within the zeolite framework is necessary to obtain high aromatic yields. Creating hierarchical mesopores within the zeolite catalyst had little effect on the aromatic yield from the semi-batch CFP of glu￾cose and maple wood. Pyrolysis over mesoporous ZSM-5 catalysts yielded slightly more coke than the purely microporous samples. This suggests thatthe mesopores may act as spaces for coke to form and accumulate. The purely microporous ZSM-5 catalyst favors the production of smaller monoaromatics (benzene, toluene, and xylene) while hierarchically mesoporous samples shifts the prod￾uct distribution towards heavier alkylated monoaromatics. Similar observations were made in the CFP of furan in the fixed-bed reactor studies. Mesoporous catalysts tended to produce more coke and were more selective for the production of larger monoaromatic products than purely microporous ZSM-5. The reaction rate offuran over mesoporous ZSM-5 was also found to be slightly slower on mesoporous ZSM-5. The selective removal of external acid sites from the ZSM-5 cat￾alysts decreased the selectivity to the desired aromatic products and had little effect on the rate of furan conversion during CFP. The aromatic yield and selectivity from surface dealuminated sam￾ples were largely the same as the untreated parent material. This suggests that the presence of these external surface sites has only minor effects on the overall CFP chemistry. The results from this paper show that the concentration of acid sites on the ZSM-5 catalyst and mesopores within the ZSM-5 can be adjusted to tune the conversion of biomass-derived molecules over ZSM-5 catalysts. The presence of external surface acid sites plays only a small role, and may not be an important factor in designing catalysts for biomass CFP. Acknowledgements This work was supported through funding from the Defense Advanced Research Projects Agency (Surf-cat: Catalysts for Pro￾duction of JP-8 range molecules from Lignocellulosic Biomass). The views, opinions, and/or findings contained in this article are those of the author and should not be interpreted as representing the official views or policies, either expressed or implied, ofthe Defense Advanced Research Projects Agency or the Department of Defense. Appendix A. 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