生物质炭对聚丙烯热解焦油降解作用分析
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摘要
以玉米秸秆为原料,分别负载Fe_2O_3,Na_2CO_3,CaO得到生物质炭基催化剂,利用炭基催化剂对聚丙烯(PP)进行催化热解反应,采用FTIR和GC-MS方法对热解产物中的焦油进行分析,研究了液体产物产率和焦油成分的变化规律。实验结果表明,炭基催化剂可明显降低PP的液相产物产率,催化剂催化作用效果由大到小顺序为:炭-Na_2CO_3>炭-CaO>炭-Fe_2O_3>生物质炭。炭基催化剂均能促进焦油中醚类、酮类、取代苯、醇酚和芳香醚等裂解、重整,生成热解气和焦炭;可以促进取代苯脱甲基和芳香构化,促进醛类加成氧化成醇类和酸类。PP热解液相产物主要成分有苯、茚、萘、菲、烷烃、烯烃、环烯烃、芳香烃及其衍生物。采用炭-Na_2CO_3进行热解时,液体产物中十四烷相对含量很大,芳香类和含氧有机物种类增加,但含量降低,萘、苯酚及其衍生物的含量增加,菲的含量减小。
Corn stalk as raw material was loaded with Fe_2O_3,Na_2CO_3 and CaO,respectively,to obtain biomass carbon-based catalysts.The tar of polypropylene(PP),which was pyrolyzed by carbonbased catalysts,was analyzed by FTIR and GC-MS.The change rules of the tar yield and the tar composition under different reaction conditions were explored.The results showed that the liquid phase product yield of PP could be significantly reduced by the carbon-based catalysts and the order of the catalytic effects of the catalysts was:carbon-Na_2CO_3>carbon-CaO>carbon-Fe_2O_3>biomass carbon.The carbon-based catalysts could promote the cracking and reforming of ether,ketone,substituted benzene,alcohol phenol and aromatic ether in tar to generate pyrolysis gas and coke.They could promote the demethylation and aromatization of substituted benzene and the oxidation of aldehydes into alcohols and acids.The main components of PP pyrolysis liquid phase products were benzene,indene,naphthalene,phenanthrene,alkane,olefin,cyclic olefin,aromatic hydrocarbon and their derivatives.When carbon-Na_2CO_3 was used for pyrolysis,the relative content of tetradecane in liquid products was very high.The number of aromatic and oxygen-containing organic compounds increased.However,the content of naphthalene,phenol and their derivatives increased,while the content of phenanthrene decreased.
Corn stalk as raw material was loaded with Fe_2O_3,Na_2CO_3 and CaO,respectively,to obtain biomass carbon-based catalysts.The tar of polypropylene(PP),which was pyrolyzed by carbonbased catalysts,was analyzed by FTIR and GC-MS.The change rules of the tar yield and the tar composition under different reaction conditions were explored.The results showed that the liquid phase product yield of PP could be significantly reduced by the carbon-based catalysts and the order of the catalytic effects of the catalysts was:carbon-Na_2CO_3>carbon-CaO>carbon-Fe_2O_3>biomass carbon.The carbon-based catalysts could promote the cracking and reforming of ether,ketone,substituted benzene,alcohol phenol and aromatic ether in tar to generate pyrolysis gas and coke.They could promote the demethylation and aromatization of substituted benzene and the oxidation of aldehydes into alcohols and acids.The main components of PP pyrolysis liquid phase products were benzene,indene,naphthalene,phenanthrene,alkane,olefin,cyclic olefin,aromatic hydrocarbon and their derivatives.When carbon-Na_2CO_3 was used for pyrolysis,the relative content of tetradecane in liquid products was very high.The number of aromatic and oxygen-containing organic compounds increased.However,the content of naphthalene,phenol and their derivatives increased,while the content of phenanthrene decreased.
引文
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[2]蒋忠新,江国防,蒋颖.缺氧热解气化法城市垃圾处理新工艺[J].科技创新导报,2017(16):93-94.
[3]Asadieraghi M,Wan Daud W M A.Characterization of lignocellulosic biomass thermal degradation and physiochemical structure:Effects of demineralization by diverse acid solutions[J].Energy Convers Manage,2014,82:71-82.
[4]Williams P T,Slaney E.Analysis of products from the pyrolysis and liquefaction of single plastics and waste plastic mixtures[J].Resources Conservation Recycl,2007,51(4):754-769.
[5]孙运兰,朱宝忠,祝易松.生物质与废塑料共热解的研究进展[J].江西能源,2009(1):11-15.
[6]刘波,李世青,廖洪强,等.煤与城市生活垃圾共热解焦油成分分析[J].燃料与化工,2011,42(6):1-4.
[7]李晓娜,宋洋,贾明云,等.生物质炭对有机污染物的吸附及机理研究进展[J].土壤学报,2017(6):3-15.
[8]李乐豪,闻光东,杨启炜,等.生物质焦油处理方法研究进展[J].化工进展,2017,36(7):2407-2416.
[9]Nestler F,Burhenne L,Amtenbrink M J,et al.Catalytic decomposition of biomass tars:The impact of wood char surface characteristics on the catalytic performance for naphthalene removal[J].Fuel Process Technol,2016,145:31-41.
[10]Burhenne L,Aicher T.Benzene removal over a fixed bed of wood char:The effect of pyrolysis temperature and activation with CO2 on the char reactivity[J].Fuel Process Technol,2014,127:140-148.
[11]于波.废弃塑料的回收利用探究[J].内蒙古石油化工,2015(12):2-4.
[12]李向辉.废塑料热解机理及低温热解研究[J].再生资源与循环经济,2011,4(6):37-41.
[13]张尚毅,刘国涛,唐利兰,等.温度对城市有机垃圾热解焦油成分的影响[J].中国环境科学,2016,36(3):827-832.
[14]武治勇,刘世功.煤焦油中酚类化合物的提取[J].化工管理,2018(2):102.
[15]Shen Yafei.Chars as carbonaceous adsorbents/catalysts for tar elimination during biomass pyrolysis or gasification[J].Renew Sustain Energy Rev,2015,43:281-295.
[16]邓代举.聚丙烯催化热解及与几种典型生物质共热解研究[D].成都:四川大学,2006.
[17]周五青.生物质炭负载镍催化裂解甲苯的研究[D].北京:北京化工大学,2016.
[18]Yang Shuangxia,Zhang Xiaodong,Chen Lei,et al.Characteristics and catalytic properties of bi-functional Fe/CaOcatalyst for syngas production from pyrolysis of biomass[J].JBiobased Mater Bioenergy,2016,10(6):415-422.
[19]李姝姝.生物质焦油催化裂解的实验研究[D].包头:内蒙古科技大学,2016.
[20]Sekine Y,Fujimoto K.Catalytic degradation of PP with an Fe/activated carbon catalyst[J].J Mater Cycles Waste Manage,2003,5(2):107-112.
[21]潘春鹏,陈翀,黄群星,等.添加CaO对生物质热解焦油生成的影响研究[J].热力发电,2012,41(8):18-23.
[22]贾晋炜.生活垃圾和农业秸秆共热解及液体产物分离研究[D].北京:中国矿业大学(北京),2013.
[23]翁诗甫.傅里叶变换红外光谱分析[M].北京:化学工业出版社,2010:490-507.
[24]李庆钊,林柏泉,赵长遂,等.基于傅里叶红外光谱的高温煤焦表面化学结构特性分析[J].中国电机工程学报,2011,31(32):46-52.
[25]Zhang Xiaodong,Sun Laizhi,Chen Lei,et al.Comparison of catalytic upgrading of biomass fast pyrolysis vapors over CaO and Fe(Ⅲ)/CaO catalysts[J].J Anal Appl Pyrolysis,2014,108:35-40.
[26]Uemichi Y,Kashiwaya Y,Ayame A,et al.Formation of aromatic hydrocarbons in degradation of polyethylene over an activated carbon catalyst[J].Chem Lett,1984(1):41-44.