玉米秸秆棒状燃料热解过程和产物特征研究
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摘要
以玉米秸秆棒状燃料为原料,在固定床反应器上探究热解温度对玉米秸秆棒状燃料热解过程和热解产品性质的影响。研究发现,随着热解温度的升高,热解气体产量增加,固体炭产量逐渐减少,生物油产量先增后减在450℃时达到最大值35.61%。对固体炭进行工业分析,发现其灰分含量较高;FT-IR分析表明:玉米秸秆棒状燃料的热解反应主要发生在650℃之前;SEM图显示断截面表现为蜂窝状的孔结构。生物油的GC-MS分析表明:在250~750℃下生物油的组成主要是呋喃、酮、醛和酚类等含氧化合物,其中酚类和呋喃类化合物是含量最多的物质;而在850~950℃下以多环芳烃类化合物为主。热解气的主要组成是CO_2、CO、CH_4和H_2,同时有少量的C_2H_n化合物,在250~450℃范围内,气体的主要组成是CO和CO_2,随着温度升高,CO、H_2、CH_4和C_2Hn逐渐增加,热解气的热值逐渐增加,在650℃下气体产品的热值已达到13.05 MJ/m~3,当温度大于650℃后,热值增加速率变慢。
The pyrolysis of corn stalk briquette in a fixed bed was investigated. The influences of pyrolysis temperature on the pyrolysis process and the properties of products( solid charcoal,bio-oil and gaseous product) were studied,too. The research found that with the increase of the pyrolysis temperature,the yield of solid charcoal decreased,and the production of gaseous product increased. The bio-oil yield firstly increased and then decreased with the maximum of 35. 61 % at 450 ℃. The proximate,FT-IR and SEM analyses of solid charcoal showed that the charcoal had high ash content,the pyrolysis reaction of corn stalk briquette occuried mainly before 650 ℃ and the pore structure was honeycomb on the broken section. The GC-MS analyses of biooil showed that at low temperature( 250-750 ℃),the organic compounds identified from pyrolysis bio-oil mainly included many oxygenated compounds such as aldehydes,ketones,furans and phenols; the phenolic compounds and furans were most abundant compounds. Nevertheless,the major compounds in the pyrolysis bio-oil obtained at higher temperatures( 850-950 ℃) were polycyclic aromatic hydrocarbons( PAHS). The main compositions of gaseous product were CO_2,CO,H_2,CH_4 and a spot of C_2H_n. In the temperature of 250-450 ℃,the high proportion in gaseous were CO and CO_2. With the increase of temperature,the productions of CO,H_2,CH_4 and C_2H_n increased,then the calorific value of gaseous product increased. At 650 ℃,the calorific value of the pyrolysis gas had reached 13. 05 MJ / m~3 and the rate of increasing slowed down when temperature exceed 650℃.
The pyrolysis of corn stalk briquette in a fixed bed was investigated. The influences of pyrolysis temperature on the pyrolysis process and the properties of products( solid charcoal,bio-oil and gaseous product) were studied,too. The research found that with the increase of the pyrolysis temperature,the yield of solid charcoal decreased,and the production of gaseous product increased. The bio-oil yield firstly increased and then decreased with the maximum of 35. 61 % at 450 ℃. The proximate,FT-IR and SEM analyses of solid charcoal showed that the charcoal had high ash content,the pyrolysis reaction of corn stalk briquette occuried mainly before 650 ℃ and the pore structure was honeycomb on the broken section. The GC-MS analyses of biooil showed that at low temperature( 250-750 ℃),the organic compounds identified from pyrolysis bio-oil mainly included many oxygenated compounds such as aldehydes,ketones,furans and phenols; the phenolic compounds and furans were most abundant compounds. Nevertheless,the major compounds in the pyrolysis bio-oil obtained at higher temperatures( 850-950 ℃) were polycyclic aromatic hydrocarbons( PAHS). The main compositions of gaseous product were CO_2,CO,H_2,CH_4 and a spot of C_2H_n. In the temperature of 250-450 ℃,the high proportion in gaseous were CO and CO_2. With the increase of temperature,the productions of CO,H_2,CH_4 and C_2H_n increased,then the calorific value of gaseous product increased. At 650 ℃,the calorific value of the pyrolysis gas had reached 13. 05 MJ / m~3 and the rate of increasing slowed down when temperature exceed 650℃.
引文
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[2]高鸿宾.实用有机化学词典[M].北京:高等教育出版社,1997.
[3]VAMVUKA D.Bio-oil,solid and gaseous biofuels from biomass pyrolysis processes:An overview[J].International Journal of Energy Research,2011,35(10):835-862.
[4]王冠,赵立欣,孟海波,等.我国生物质热解特性及工艺研究进展[J].节能技术,2014,32(2):120-124.
[5]胡威,胡建杭,王华,等.生物质炭化原料选择及需热量分析[J].煤炭转化,2012,35(3):80-83.
[6]ENSZ S,ANGLN D.Pyrolysis of safflower(Charthamus tinctorius L.)seed press cake.Part 1:The effects of pyrolysis parameters on the product yields[J].Bioresource Technology,2008,99(13):5492-5497.
[7]YANG Hua,HUANG Li,LIU Shi-cai,et al.Pyrolysis process and characteristics of products from sawdust briquettes[J].Bio Resources,2016,11(1):2438-2456.
[8]RAVEENDRAN K,GANESH A,KHILAR K C.Influence of mineral matter on biomass pyrolysis characteristics[J].Fuel,1995,74(12):1812-1822.
[9]王贤华,陈汉平,王静,等.无机矿物质盐对生物质热解特性的影响[J].燃料化学学报,2008,36(6):679-683.
[10]AYSU T,KK M M.Biomass pyrolysis in a fixed-bed reactor:Effects of pyrolysis parameters on product yields and characterization of products[J].Energy,2014,64:1002-1025.
[11]SHAABAN A,SE S M,MITAN N M M,et al.Characterization of biochar derived from rubber wood sawdust through slow pyrolysis on surface porosities and functional groups[J].Procedia Engineering,2013,68:365-371.
[12]刘圣勇,杨国峰,苏超杰,等.玉米秸秆成型燃料的微观结构观察与分析[J].热科学与技术,2009,8(3):277-282.
[13]WANG Xiao-hua,CHEN Hai-ping,DING Xue-jun,et al.Properties of gas and char from microwave pyrolysis of pine sawdust[J].Bio Resources,2009,4(3):946-959.
[14]VAN DE VELDEN M,BAEYENS J,BREMS A,et al.Fundamentals,kinetics and endothermicity of the biomass pyrolysis reaction[J].Renewable Energy,2010,35(1):232-242.
[15]COLLARD F X,BLIN J.A review on pyrolysis of biomass constituents:Mechanisms and composition of the products obtained from the conversion of cellulose,hemicelluloses and lignin[J].Renewable and Sustainable Energy Reviews,2014,38:594-608.
[16]SHEN D K,GU S.The mechanism for thermal decomposition of cellulose and its main products[J].Bioresource Technology,2009,100(24):6496-6504.
[17]SHEN K D,GU S,LUO K H,et al.The pyrolytic degradation of wood-derived lignin from pulping process[J].Bioresource Technology,2010,101(15):6136-6146.
[18]HOSOYA T,KAWAMOTO H,SAKA S.Role of methoxyl group in char formation from lignin-related compounds[J].Journal of Analytical and Applied Pyrolysis,2009,84(1):79-83.
[19]YU Hai-miao,ZHANG Ze,LI Ze-shen,et al.Characteristics of tar formation during cellulose,hemicellulose and lignin gasification[J].Fuel,2014,118:250-256.
[20]孙云娟,将剑春.生物质热解气化产物中焦油的催化裂解研究[J].林产化学与工业,2007,27(5):15-20.
[21]YANG Hai-ping,YAN Rong,CHEN Han-ping,et al.Characteristics of hemicellulose,cellulose and lignin pyrolysis[J].Fuel,2007,86(12):1781-1788.
[22]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.