生物质低温脱氧中产物特性变化及其反应动力学研究
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摘要
对棉秆和玉米秆在200～390℃范围内的低温脱氧过程进行研究。分析其产物特性并对脱氧过程进行动力学分析,为进一步探索生物质低温脱氧的反应机理提供理论依据。结果发现与原样相比,390℃低温脱氧棉秆O/C和H/C分别降低78.5%和60.9%,390℃低温脱氧玉米秆O/C和玉米秆的热值分别提高36.4%和31.9%;棉秆与玉米秆在290～390℃时的失重比其在200～290℃时分别提高28.22%和52.28%;棉秆和玉米秆的热解可运用分级反应模型求其动力学参数,低温脱氧过程中棉秆和玉米秆的活化能分别为120.91、109.27 kJ/mol;生物质三组分可运用一级反应模型求其动力学参数,低温脱氧过程中半纤维素、纤维素、木质素的反应活化能分别为77.19、238.99、28.42 kJ/mol。
The low temperature deoxidation processes of cotton stalk and corn stalk ranged from 200 ℃ to 390 ℃ were studied. The product characteristics and the kinetics of the deoxidation processes were analyzed to provide a theoretical basis for further exploration of the reaction mechanism of low temperature deoxidation of biomass. The results showed that compared with the raw biomass,after 390 ℃ low temperature deoxidation reaction,the O/C and H/C of cotton stalk dropped 78.5% and 60.9%,the O/C and H/C of corn stalk dropped 71.8% and 59.7%,the effect on deoxidation is obvious,and the calorific value of cotton stalk and corn stalk increased 36.4% and 31.9%. The weightlessness of cotton stalk and corn stalk during 290-390 ℃ were increased by 28.22% and 52.28% over the weightlessness during 200 and290 ℃. The pyrolysis process of both cotton stalk and corn stalk can be described by hierarchical reaction model,the activation energy of cotton stalk and corn stalk during low temperature deoxidation are 120.91,109.27 kJ/mol. The pyrolysis process of biomass three components can be described by first order model,the activation energy of hemicellulose,cellulose,lignin during low temperature deoxidationare 77.19,238.99,28.42 kJ/mol.
The low temperature deoxidation processes of cotton stalk and corn stalk ranged from 200 ℃ to 390 ℃ were studied. The product characteristics and the kinetics of the deoxidation processes were analyzed to provide a theoretical basis for further exploration of the reaction mechanism of low temperature deoxidation of biomass. The results showed that compared with the raw biomass,after 390 ℃ low temperature deoxidation reaction,the O/C and H/C of cotton stalk dropped 78.5% and 60.9%,the O/C and H/C of corn stalk dropped 71.8% and 59.7%,the effect on deoxidation is obvious,and the calorific value of cotton stalk and corn stalk increased 36.4% and 31.9%. The weightlessness of cotton stalk and corn stalk during 290-390 ℃ were increased by 28.22% and 52.28% over the weightlessness during 200 and290 ℃. The pyrolysis process of both cotton stalk and corn stalk can be described by hierarchical reaction model,the activation energy of cotton stalk and corn stalk during low temperature deoxidation are 120.91,109.27 kJ/mol. The pyrolysis process of biomass three components can be described by first order model,the activation energy of hemicellulose,cellulose,lignin during low temperature deoxidationare 77.19,238.99,28.42 kJ/mol.
引文
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[2]Dickerson T,Soria J.Catalytic fast pyrolysis:A review[J].Energies,2013,6(1):514-538.
[3]Vitolo S,Bresci B,Seggiani M,et al.Catalytic upgrading of pyrolytic oils over HZSM-5 zeolite:behaviour of the catalyst when used in repeated upgrading-regenerating cycles[J].Fuel,2001,80(1):17-26.
[4]Gayubo A G,Aguayo A T,Atutxa A,et al.Deactivation of a HZSM-5 zeolite catalyst in the transformation of the aqueous fraction of biomass pyrolysis oil into hydrocarbons[J].Energy&Fuels,2004,18(6):1640-1647.
[5]Lu Qiang,Zhang Zhifeng,Dong Changqing,et al.Catalytic upgrading of biomass fast pyrolysis vapors with nano metaloxides:An analytical Py-GC/MS study[J].Energies,2010,3(11):1805-1820.
[6]Meng J,Park J,Tilotta D,et al.The effect of torrefaction on the chemistry of fast-pyrolysis bio-oil[J].Bioresource Technology,2012,111(5):439-446.
[7]杨晴,梅艳阳,郝宏蒙,等.烘焙对生物质热解产物特性的影响[J].农业工程学报,2013,29(20):214-219.[7]Yang Qing,Mei Yanyang,Hao Hongmeng,et al.Effect of torrefaction on characteristics of pyrolytic products of biomass[J].Transactions of the Chinese Society of Agricultural Engineering:Transactions of the CSAE,2013,29(20):214-219.
[8]张杨,梅艳阳,杨晴,等.烘焙与HZSM-5催化剂联用改善柏木热解产物品质[J].农业工程学报,2015,31(23):208-213.[8]Zhang Yang,Mei Yanyang,Yang Qing,et al.Torrefaction and HZSM-5 catalyst combination improving pyrolytic products of cedarwood[J].Transactions of the Chinese Society of Agricultural Engineering:Transactions of the CSAE,2015,31(23):208-213.
[9]Liaw S S,Wang Z,Ndegwa P,et al.Effect of pretreatment temperature on the yield and properties of bio-oils obtained from the auger pyrolysis of douglas fir wood[J].Journal of Analytical and Applied Pyrolysis,2012,93(1):52-62.
[10]Medic D,Darr M,Shah A,et al.Effects of torrefaction process parameters on biomass feedstock upgrading[J].Fuel,2012,91(1):147-154.
[11]朱波,王贤华,杨海平,等.农业秸秆烘焙热分析[J].中国电机工程学报,2011,31(20):121-126.[11]Zhu Bo,Wang Xianhua,Yang Haiping,et al.Thermal analysis of agricultural straw torrefaction[J].Proceedings of the CSEE,2011,31(20):121-126.
[12]陈应泉,王贤华,李开志,等.温度对棉杆热解多联产过程中产物特性的影响[J].中国电机工程学报,2012,32(17):117-124,53.[12]Chen Yingquan,Wang Xianhua,Li Kaizhi,et al.Effectof temperature on product property during biomass ploy-generation based on cotton stalk pyrolysis[J].Proceedings of the CSEE,2012,32(17):117-124,53.
[13]索娅,张建民,屈星星,等.能源作物与传统生物质热重实验的对比研究[J].转化利用,2007,13(2):55-59.[13]Suo Ya,Zhang Jianmin,Qu Xingxing,et al.The study of TG experiment for energy crops and traditional biomass[J].Journal of Conversion,2007,13(2):55-59.
[14]Yang Haiping,Yan Rong,Chen Hanping,et al.Characteristics of hemicellulose,cellulose and lignin pyrolysis[J].Fuel,2007,86(12):1781-1788.
[15]Van der Stelt M J C,Gerhauser H,Kiel J H A,et al.Biomass upgrading by torrefaction for the production of biofuels:A review[J].Biomass and Bioenergy,2011,35(9):3748-3762.
[16]辛善志,米铁,杨海平,等.纤维素低温炭化特性[J].化工学报,2015,66(11):4603-4610.[16]Xin Shabzhi,Mi Tie,Yang Haiping,et al.Features of low temperature carbonization of cellulose[J].CIESCJournal,2015,66(11):4603-4610.
[17]周志杰,范晓雷,张薇,等.非等温热重分析研究煤焦气化动力学[J].煤炭学报,2006,31(2):219-222.[17]Zhou Zhijie,Fan Xiaolei,Zhang Wei,et al.Char gasification kinetics using non-isothermal TGA[J].Journal of China Coal Socirty,2006,31(2):219-222..
[18]Cumming J W.Reactivity assessment of coals via a weighted mean activation energy[J].Fuel,1984,63(10):1436-1440.
[19]Rao T R,Sharma A.Pyrolysis rates of biomass materials[J].Energy,1998,23(11):973-978.
[20]Orfao J,Antunes F,Figueiredo J.Pyrolysis kinetics of lignocellulosic materials-three independent reaction model[J].Fuel,1999,78(3):349-358.
[21]Antal M J,Varhegyi G.Cellulose pyrolysis kinetics:The current state of knowledge[J].Industrial&Engineering Chemistry Research,1995,34(3):703-717.
[22]Liu Qian,Zhong Zhaoping,Wang Shurong,et al.Interactions of biomass components during pyrolysis:ATG-FTIR study[J].Journal of Analytical&Applied Pyrolysis,2011,90(2):213-218.
[23]Blasi C D,Branca C,Errico G D.Degradation characteristics of straw and washed straw[J].Thermochimica Acta,2000,364:133-142.