桉木屑在离子液体[C_4H_8SO_3 Hmim]HSO_4催化下液化行为研究
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摘要
以乙二醇为溶剂,在1-磺酸丁基-3-甲基咪唑硫酸氢盐([C_4H_8SO_3 Hmim]HSO_4)酸性离子液体催化下,进行桉木屑的液化反应。考察了反应温度、反应时间、催化剂用量对液化率以及产物分布的影响,并对液化产物进行了表征。结果表明:在最优液化条件10 g桉木屑,60 g乙二醇,[C_4H_8SO_3 Hmim]HSO_4用量为10 mmol,液化温度为160℃,液化时间150 min下,桉木屑的液化率最高可达96.41%。在离子液体催化下,桉木屑中的半纤维素和木质素快速液化;液化残渣的主要成分为未降解的结晶区纤维素(结晶度75%左右),液化产物水不溶性级分主要为木质素的降解产物,液化产物水溶性级分主要由纤维素的降解产物乙酰丙酸以及乙酰丙酸甲酯组成。
Eucalyptus sawdust was liquefied in ethylene glycol under atmospheric pressure using 1-( 4-sulfobutyl)-3-methylimidazolium hydrosulfate( [C_4H_8SO_3 Hmim]HSO_4) as catalyst. The effects of the reaction time,temperature and dosage of catalyst on the liquefaction yield and the distribution of liquefaction products were studied. The results showed that the optimal conditions of liquefaction were: 10 g eucalyptus sawdust,60 g ethylene glycol,10 mmol [C_4H_8SO_3 Hmim]HSO_4,160 ℃ and150 min. The liquefaction yield was up to 96. 41% under the optimal conditions. The Fourier transform-infrared( FT-IR)spectra,thermal gravimetric and the X-ray diffraction analysis of the residual showed that the major component in the residue was cellulose with high crystallinity. The FT-IR analysis of water-insoluble products showed that water-insoluble products mainly included degradation products from lignin. The GC-MS analysis showed the water-soluble products mainly included levulinic acid and methyl levulinate which was originated from cellulose.
Eucalyptus sawdust was liquefied in ethylene glycol under atmospheric pressure using 1-( 4-sulfobutyl)-3-methylimidazolium hydrosulfate( [C_4H_8SO_3 Hmim]HSO_4) as catalyst. The effects of the reaction time,temperature and dosage of catalyst on the liquefaction yield and the distribution of liquefaction products were studied. The results showed that the optimal conditions of liquefaction were: 10 g eucalyptus sawdust,60 g ethylene glycol,10 mmol [C_4H_8SO_3 Hmim]HSO_4,160 ℃ and150 min. The liquefaction yield was up to 96. 41% under the optimal conditions. The Fourier transform-infrared( FT-IR)spectra,thermal gravimetric and the X-ray diffraction analysis of the residual showed that the major component in the residue was cellulose with high crystallinity. The FT-IR analysis of water-insoluble products showed that water-insoluble products mainly included degradation products from lignin. The GC-MS analysis showed the water-soluble products mainly included levulinic acid and methyl levulinate which was originated from cellulose.
引文
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[3]LEE S H,YOSHIOKA M,SHIRAISHI N.Liquefaction of corn bran(CB)in the presence of alcohols and preparation of polyurethane foam from its liquefied polyol[J].Journal of Applied Polymer Science,2000,78(2):319-325.
[4]PAN H,SHUPE T F,HSE C Y.Characterization of liquefied wood residues from different liquefaction conditions[J].Journal of Applied Polymer Science,2007,105(6):3740-3746.
[5]LIU J J,CHEN F G,QIU M H.Liquefaction of bagasse and preparation of rigid polyurethane foam from liquefaction products[J].Journal of Biobased Materials and Bioenergy,2009,3(4):401-407.
[6]LU Z X,ZHENG H Y,FAN L W,et al.Liquefaction of sawdust in 1-octanol using acidic ionic liquids as catalyst[J].Bioresource Technology,2013,142:579-584.
[7]ZHANG H R,PANG H,SHI J,et al.Investigation of liquefied wood residues based on cellulose,hemicellulose,and lignin[J].Journal of Applied Polymer Science,2012,123(2):850-856.
[8]郭贵全,王红娟,谌凡更.蔗渣在四氢化萘中的液化反应[J].林产化学与工业,2004,24(3):52-56.GUO G Q,WANG H J,CHEN F G.Liquefaction of bagasse in tetralin[J].Chemistry and Industry of Forest Products,2004,24(3):52-56.
[9]DEMIRBAS A.Liquefaction of biomass using glycerol[J].Energy Sources:Part A,2008,30(12):1120-1126.
[10]SCHWANNINGER M,RODRIGUES J C,PEREIRA H,et al.Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose[J].Vibrational Spectroscopy,2004,36(1):23-40.
[11]郭立颖,史铁钧,李忠,等.两种咪唑类离子液体对杉木粉的溶解性能[J].化工学报,2008,59(5):1299-1304.GUO L Y,SHI T J,LI Z,et al.Solubilities of two kinds of imidazolium ionic liquids for fir powder[J].Journal of Chemical Industry and Engineering,2008,59(5):1299-1304.
[12]张克宏,杜俊娟.杉木粉液化与液化产物树脂化的研究[J].林产化学与工业,2009,29(5):59-63.ZHANG K H,DU J J.Study on liquefaction of Chinese fir wood powder and resinification of the liquefied products[J].Chemistry and Industry of Forest Products,2009,29(5):59-63.
[13]张婷,周玉杰,张建安,等.木质纤维原料各组分温和液化行为[J].清华大学学报:自然科学版,2006,46(12):2011-2014.ZHANG T,ZHOU Y J,ZHANG J A,et al.Mild liquefaction behavior of lignocellulosic material components[J].Journal of Tsinghua University:Science and Technology,2006,46(12):2011-2014.
[14]OUAJAI S,SHANKS R A.Composition,structure and thermal degradation of hemp cellulose after chemical treatments[J].Polymer Degradation and Stability,2005,89(2):327-335.
[15]YANG H P,YAN R,CHIN T,et al.Thermogravimetric analysis-Fourier transform infrared analysis of palm oil waste pyrolysis[J].Energy&Fuels,2004,18(6):1814-1821.
[16]RFO J J M,ANTUNES F J A,FIGUEIREDO J L.Pyrolysis kinetics of lignocellulosic materials:Three independent reactions model[J].Fuel,1999,78(3):349-358.
[17]张海荣,庞浩,石锦志,等.生物质化学组分及其液化残渣的热重行为[J].化工进展,2011,30(10):2194-2199.ZHANG H R,PANG H,SHI J Z,et al.TG study on major biomass components and its liquefied residues from pyrolysis[J].Chemical Industry and Engineering Progress,2011,30(10):2194-2199.
[18]ZHANG T,ZHOU Y J,LIU D H,et al.Qualitative analysis of products formed during the acid catalyzed liquefaction of bagasse in ethylene glycol[J].Bioresource Technology,2007,98(7):1454-1459.