生物质废物催化热解特性及多因素优化实验
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摘要
生物质废物催化热解所得生物油中富含多环芳烃(PAHs)污染物,但其分布特征及相应影响因素尚缺乏深入探讨。以Co_3O_4为催化剂,采用管式炉反应器在不同温度下热解水曲柳木屑制备生物油,并分析其化学组分和16种PAHs污染物分布特征。结果表明,生物油中以酚类化合物为主,而PAHs污染物的种类与含量均随反应温度的升高而增加,PAHs总含量从389.60μg·g~(-1)(400℃)攀升至105 435.12μg·g~(-1)(700℃)。同时,将CO_2引入热解气氛,利用Box-Benhnken曲面响应法对催化热解过程的多个工艺因素进行优化。结果显示,在热解温度为511℃、停留时间为12.7 min、热解气氛的CO_2/N_2比例为88/12时,生物油产率达到最大值,约45%。研究结果对生物质废物的高效、低污染资源化利用具有参考价值。
Bio-oil obtained from biomass pyrolysis contains polycyclic aromatic hydrocarbons(PAHs)pollutants,which are teratogenic,carcinogenic,and mutagenic to humans.As a result,it causes a concern about the potential risk for environmental and human health during its subsequent processing.In this study,Co_3O_4 was used as a catalyst to perform saw dust pyrolysis for bio-oil production in a tube furnace reactor.The chemical composition of the bio-oil and the distribution of 16 kinds of PAHs were analyzed.The results showed that the bio-oil mainly consisted of phenolic compounds;the species and content of PAHs in bio-oil increased with the rise of pyrolysis temperature,and the amount of the total PAHs sharply increased from 389.60μg·g~(-1) at 400℃to 105 435.12μg·g~(-1)at 700℃.At the same time,CO_2 was induced into the pyrolysis atmosphere,an optimization of multiple pyrolysis factors for the bio-oil yield was performed by using Box-Benhnken response surface method,and it was found that the highest yield of bio-oil was achieved with a value of about 45% at the pyrolysis temperature of 511℃,the residence time of 12.7 min and the CO_2/N_2 ratio of 88/12 in the reaction atmosphere.This study will provide a reference for the high effective and low pollution resource recycling of biomass waste.
Bio-oil obtained from biomass pyrolysis contains polycyclic aromatic hydrocarbons(PAHs)pollutants,which are teratogenic,carcinogenic,and mutagenic to humans.As a result,it causes a concern about the potential risk for environmental and human health during its subsequent processing.In this study,Co_3O_4 was used as a catalyst to perform saw dust pyrolysis for bio-oil production in a tube furnace reactor.The chemical composition of the bio-oil and the distribution of 16 kinds of PAHs were analyzed.The results showed that the bio-oil mainly consisted of phenolic compounds;the species and content of PAHs in bio-oil increased with the rise of pyrolysis temperature,and the amount of the total PAHs sharply increased from 389.60μg·g~(-1) at 400℃to 105 435.12μg·g~(-1)at 700℃.At the same time,CO_2 was induced into the pyrolysis atmosphere,an optimization of multiple pyrolysis factors for the bio-oil yield was performed by using Box-Benhnken response surface method,and it was found that the highest yield of bio-oil was achieved with a value of about 45% at the pyrolysis temperature of 511℃,the residence time of 12.7 min and the CO_2/N_2 ratio of 88/12 in the reaction atmosphere.This study will provide a reference for the high effective and low pollution resource recycling of biomass waste.
引文
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[22]BLANCO P H,WU C F,ONWUDILI J A,et al.Characterization of tar from the pyrolysis/gasification of refuse derived fuel:Influence of process parameters and catalysis[J].Energy&Fuels,2012,26(4):2107-2115.
[23]王芸,邵珊珊,张会岩,等.生物质模化物催化热解制取烯烃和芳香烃[J].化工学报,2015,66(8):3022-3028.
[24]DAI Q J,JIANG X G,JIANG Y F.Formation of PAHs during the pyrolysis of dry sewage sludge[J].Fuel,2014,130:92-99.
[25]SHARMA R K,HAJALIGOL M R.Effect of pyrolysis conditions on the formation of polycyclic aromatic hydrocarbons(PAHs)from polyphenolic compounds[J].Journal of Analytical and Applied Pyrolysis,2003,66(1):123-144.
[26]NISBET I C,LAGOY P K.Toxic equivalency factors(TEFs)for polycyclic aromatic hydrocarbons(PAHs)[J].Regulatory Toxicology and Pharmacology,1992,16(3):290-300.
[27]陈温福,张伟明,孟军.农用生物炭研究进展与前景[J].中国农业科学,2013,46(16):3325-3333.
[28]丁文川,曾晓岚,王永芳,等.生物炭载体的表面特征和挂膜性能研究[J].中国环境科学,2011,31(9):1451-1455.
[29]CHEN W H,LIN B J.Characteristics of products from the pyrolysis of oil palm fiber and its pellets in nitrogen and carbon dioxide atmospheres[J].Energy,2016,94:569-578.
[30]MANTE O D,AGBLEVOR F A,OYAMA S T,et al.The influence of recycling non-condensable gases in the fractional catalytic pyrolysis of biomass[J].Bioresource Technology,2012,111:482-490.
[2]林顺洪,李伟,柏继松,等.TG-FTIR研究生物质成型燃料热解与燃烧特性[J].环境工程学报,2017,11(11):312-317.
[3]王攀,于宏兵,薛旭方,等.废弃植物中药渣的热解特性及动力学研究[J].环境工程学报,2010,4(9):2115-2119.
[4]秦丽元,孙焱,蒋恩臣,等.NiO/HZSM-5催化改性生物油模拟物研究[J].农业机械学报,2014,45(8):206-217.
[5]秦丽元,贾月雯,魏晓莉,等.生物油重质油醇类添加剂提质研究[J].农业机械学报,2017,48(11):324-329.
[6]LIU C J,WANG H M,KARIM A M.Catalytic fast pyrolysis of lignocellulosic biomass[J].Chemical Society Reviews,2014,43(22):7594-7623.
[7]DICKERSON T,SORIA J.Catalytic fast pyrolysis:A review[J].Energies,2013,6(1):514-538.
[8]STOCKER M.Biofuels and biomass-to-liquid fuels in the biorefinery:Catalytic conversion of lignocellulosic biomass using porous materials[J].Angewandte Chemie:International Edition,2008,47(48):9200-9211.
[9]ASADIERAGHI M,DAUD W M A W,ABBAS H F.Heterogeneous catalysts for advanced bio-fuel production through catalytic biomass pyrolysis vapor upgrading:A review[J].RSC Advances,2015,5(28):22234-22255.
[10]闵凡飞,张明旭,陈清如,等.新鲜生物质催化热解特性的研究[J].林产化学与工业,2008,28(3):28-34.
[11]ILIOPOULOU E F,STEFANIDIS S,KALOGIANNIS K,et al.Pilot-scale validation of Co-ZSM-5 catalyst performance in the catalytic upgrading of biomass pyrolysis vapours[J].Green Chemistry,2014,16(2):662-674.
[12]MA Z Q,CUSTODIS V,BOKHOVEN J A.Selective deoxygenation of lignin during catalytic fast pyrolysis[J].Catalysis Science&Technology,2014,4(3):766-772.
[13]LIU X,ZHANG G,JONES K C,et al.Compositional fractionation of polycyclic aromatic hydrocarbons(PAHs)in mosses(Hypnum plumaeformae WILS)from the northern slope of Nanling Mountains,South China[J].Atmospheric Environment,2005,39(30):5490-5499.
[14]ZHANG Y X,TAO S.Global atmospheric emission inventory of polycyclic aromatic hydrocarbons(PAHs)for 2004[J].Atmospheric Environment,2009,43(4):812-819.
[15]KWON E E,EUI C J,MARCO J C,et al.Effect of carbon dioxide on the thermal degradation of lignocellulosic biomass[J].Environmental Science&Technology,2013,47(18):10541-10547.
[16]MANTE O D,AGBLEVOR F A,OYAMA S T.The influence of recycling non-condensable gases in the fractional catalytic pyrolysis of biomass[J].Bioresource Technology,2012,111:482-490.
[17]ZHANG H Y,XIAO R,WANG D H,et al.Biomass fast pyrolysis in a fluidized bed reactor under N2,CO2,CO,CH4and H2atmospheres[J].Bioresource Technology,2011,102(5):4258-4264.
[18]JINDAROM C,MEEYOO V,RIRKSOMBOON T.Thermochemical decomposition of sewage sludge CO2and N2atmosphere[J].Chemosphere,2007,67(8):1477-1484.
[19]陆强,朱锡锋,李文志,等.生物质快速热解产物在线催化提质研究[J].科学通报,2009,54(9):1139-1146.
[20]郑云武,杨晓琴,王霏,等.生物质催化裂解制备芳烃化合物的研究进展[J].林产化学与工业,2015,35(5):149-158.
[21]王玉珏,苏露,李翔宇,等.生物质组分在催化快速热解中的相互影响[J].清华大学学报(自然科学版),2013,53(4):531-536.
[22]BLANCO P H,WU C F,ONWUDILI J A,et al.Characterization of tar from the pyrolysis/gasification of refuse derived fuel:Influence of process parameters and catalysis[J].Energy&Fuels,2012,26(4):2107-2115.
[23]王芸,邵珊珊,张会岩,等.生物质模化物催化热解制取烯烃和芳香烃[J].化工学报,2015,66(8):3022-3028.
[24]DAI Q J,JIANG X G,JIANG Y F.Formation of PAHs during the pyrolysis of dry sewage sludge[J].Fuel,2014,130:92-99.
[25]SHARMA R K,HAJALIGOL M R.Effect of pyrolysis conditions on the formation of polycyclic aromatic hydrocarbons(PAHs)from polyphenolic compounds[J].Journal of Analytical and Applied Pyrolysis,2003,66(1):123-144.
[26]NISBET I C,LAGOY P K.Toxic equivalency factors(TEFs)for polycyclic aromatic hydrocarbons(PAHs)[J].Regulatory Toxicology and Pharmacology,1992,16(3):290-300.
[27]陈温福,张伟明,孟军.农用生物炭研究进展与前景[J].中国农业科学,2013,46(16):3325-3333.
[28]丁文川,曾晓岚,王永芳,等.生物炭载体的表面特征和挂膜性能研究[J].中国环境科学,2011,31(9):1451-1455.
[29]CHEN W H,LIN B J.Characteristics of products from the pyrolysis of oil palm fiber and its pellets in nitrogen and carbon dioxide atmospheres[J].Energy,2016,94:569-578.
[30]MANTE O D,AGBLEVOR F A,OYAMA S T,et al.The influence of recycling non-condensable gases in the fractional catalytic pyrolysis of biomass[J].Bioresource Technology,2012,111:482-490.