HZSM-5催化条件下反应温度对热解油品质影响规律
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摘要
在酸性分子筛HZSM-5催化条件下,以玉米秸秆粉为原料,考察了反应温度对热解油品质的影响。在自制流化床热裂解装置上,选取了5种反应温度(450℃、500℃、550℃、600℃及650℃),进行催化热裂解实验,探究热解油含水率、pH和化学组分的变化规律。结果表明:在HZSM-5催化剂作用下,热解油含水率与pH随反应温度线性增加,酸性随着含水率的升高而减弱(pH增大);热解油中酸类、酚类、酯类及醇类相对含量比酮类、醛类及糖类受反应温度影响更加明显;在HZSM-5催化剂与物料质量比1∶10,反应温度为500℃时,热解油品质较好,腐蚀性低、稳定性高,酚类物质种类丰富、相对含量高。研究结果为HZSM-5催化条件下反应温度调控、改善热解油品质提供了一定的科学依据,有利于热解油后续高值化、环保化利用。
The effect of reaction temperatures on the quality of pyrolysis oil was investigated over acidic HZSM-5 zeolite, using corn stalk powder as raw material. In the self-made fluidized bed pyrolysis device, five reaction temperatures(450℃, 500℃, 550℃, 600℃ and 650℃) were tested in the catalytic pyrolysis experiments to study the moisture content, pH and chemical composition of pyrolysis oil. The results showed that, under the action of HZSM-5 catalyst, the moisture content and pH of pyrolysis oil increased linearly with the reaction temperature, and the acidity decreased with the increase of water content(pH increased); the content of phenols, esters and alcohols was more sensitive than that of ketones, aldehydes and sugars by the reaction temperature; under the conditions of HZSM-5 catalyst and material mass ratio of 1∶10, the reaction temperature was 500℃, oil quality was in a good state, corrosive low, high stability, rich phenolic species and high relative content. The results provided a scientific evident that the reaction temperature controlled and improved the quality of pyrolysis oil over HZSM-5 catalyst, which will be beneficial to the subsequent high-value and environmental protection utilization of pyrolysis oil.
The effect of reaction temperatures on the quality of pyrolysis oil was investigated over acidic HZSM-5 zeolite, using corn stalk powder as raw material. In the self-made fluidized bed pyrolysis device, five reaction temperatures(450℃, 500℃, 550℃, 600℃ and 650℃) were tested in the catalytic pyrolysis experiments to study the moisture content, pH and chemical composition of pyrolysis oil. The results showed that, under the action of HZSM-5 catalyst, the moisture content and pH of pyrolysis oil increased linearly with the reaction temperature, and the acidity decreased with the increase of water content(pH increased); the content of phenols, esters and alcohols was more sensitive than that of ketones, aldehydes and sugars by the reaction temperature; under the conditions of HZSM-5 catalyst and material mass ratio of 1∶10, the reaction temperature was 500℃, oil quality was in a good state, corrosive low, high stability, rich phenolic species and high relative content. The results provided a scientific evident that the reaction temperature controlled and improved the quality of pyrolysis oil over HZSM-5 catalyst, which will be beneficial to the subsequent high-value and environmental protection utilization of pyrolysis oil.
引文
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[23]GüLLüD,DEMIRBA?A.Biomass to methanol via pyrolysis process[J].Energy Conversion&Management,2001,42(11):1349-1356.
[24]白甜甜.农林生物质热解油组分分离及热解木质素表征研究[D].北京:北京林业大学,2015.BAI Tiantian.Research on fractionation of pyrolysis-oil from agricultural and forestry biomass and characterization of pyrolytic lignin[D].Beijing:Beijing Forestry University,2015.
[25]俞宁,蔡忆昔,李小华,等.HZSM-5分子筛催化热裂解油菜秸秆制取精制生物油[J].农业工程学报,2014,30(15):264-271.YU Ning,CAI Yixi,LI Xiaohua,et al.Catalytic pyrolysis of rape straw for upgraded bio-oil production using HZSM-5 zeolite[J].Transactions of the Chinese Society of Agricultural Engineering,2014,30(15):264-271.
[26]骆仲泱,王树荣,王琦,等.生物质液化原理及技术应用[M].北京:化学工业出版社,2013.LUO Zhongyang,WANG Shurong,WANG Qi,et al.Biomass liquefaction principle and application[M].Beijing:Chemical Industry Press,2013.
[27]王文亮.木质生物质热裂解定向调控酚类化合物研究[D].北京:北京林业大学,2016.WANG Wenliang.Study on the oriented regulation of phenols derived from fast pyrolysis of woody biomass[D].Beijing:Beijing Forestry University,2016.
[28]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.
[29]吴晓娜,赵炜,闫彩辉,等.酚类化合物在生物质利用中的研究进展[J].化工中间体,2012,9(01):10-14.WU Xiaona,ZHAO Hui,YAN Caihui,et al.Research progress of phenolic compounds in biomass utilization[J].Chemical Intermediates,2012,9(01):10-14.
[30]JIANG G,NOWAKOWSKI D J,BRIDGWATER A V.Effect of the temperature on the composition of lignin pyrolysis products[J].Energy Fuels,2010,24(8):4470-4475.
[31]尹海云,李小华,张蓉仙,等.HZSM-5在线提质生物油及催化剂失活机理分析[J].燃料化学学报,2014,42(9):1077-1086.YI Haiyun,LI Xiaohua,ZHANG Rongxian,et al.Online catalytic cracking of bio-oil over HZSM-5 zeolite and analysis of catalyst deactivation[J].Journal of Fuel Chemistry and Technology,2014,42(9):1077-1086.
[2]LAESECKE J,ELLIS N,KIRCHEN P.Production,analysis and combustion characterization of biomass fast pyrolysis oil:biodiesel blends for use in diesel engines[J].Fuel,2017,199:346-357.
[3]LU Qiang,ZHANG Ying.Catalytic upgrading of biomass fast pyrolysis vapors with titania and zirconia/titania based catalysts[J].Fuel,2010,89(8):2096-2103.
[4]高新源,徐庆,李占勇,等.生物质快速热解装置研究进展[J].化工进展,2016,35(10):3032-3041.GAO Xinyuan,XU Qing,LI Zhanyong,et al.Progress in the study of biomass fast pyrolysis equipment[J].Chemical Industry and Engineering Progress,2016,35(10):3032-3041
[5]ELLIOTT D C,HART T R,NEUENSCHWANDER G G,et al.Catalytic hydroprocessing of biomass fast pyrolysis bio-oil to produce hydrocarbon products[J].Environmental Progress&Sustainable Energy,2009,28(3):441-449.
[6]徐艺,陈宇,华德润,等.固定床反应器中生物质/废塑料共热解制备燃料油[J].化工进展,2013,32(3):563-569.XU Yi,CHEN Yu,HUA Derun,et al.Co-pyrolysis of biomass and waste plastic for biofuel in fixed-bed reactor[J].Chemical Industry and Engineering Progress,2013,32(3):563-569.
[7]KABIR G,HAMEED B H.Recent progress on catalytic pyrolysis of lignocellulosic biomass to high-grade bio-oil and bio-chemicals[J].Renewable and Sustainable Energy Reviews,2017,70:945-967.
[8]AHO A,KUMAR N,ERANEN K,et.al.Catalytic pyrolysis of woody biomass in a fluidized bed reactor:inf1uence of the zeolite structure[J].Fuel,2008,87:2493-2501.
[9]JACKSON M A,COMPTON D L,BOATENG A A.Screening heterogeneous catalysts for the Pyrolysis of lignin[J].J.Anal.Appl.Pyrolysis,2009,85:226-230.
[10]LU C B,YAO J Z,LIN W G,et al.Study on biomass catalytic pyrolysis for production of bio-gasoline by on-line FTIR[J].Chinese Chemical Letters,2007,18:445-448.
[11]李攀,王贤华,邵敬爱,等.不同Si/Al的氢型分子筛催化热解对生物油特性的影响[J].农业工程学报,2014,20:252-258.Li Pan,Wang Xianhua,Shao Jing’ai,et al.Effect of HZSM-5 catalyst with different Si/Al ratios on characterization of pyrolysis bio-oil[J].Transactions of the Chinese Society of Agricultural Engineering,2014,30(20):252-258.
[12]PAN P,HU C W,YANG W Y,et.al.The direct pyrolysis and catalytic pyrolysis of Nannochloropsis sp.residue for renewable bio-oils[J].Bioresource Technology,2010,101:4593-4599.
[13]ZHANG Q,CHANG J,WANG T,et al.Review of biomass pyrolysis oil properties and upgrading research[J].Energy Conversion and Management,2007,48(1):87-92.
[14]刘荣厚,牛卫生,张大雷.生物质热化学转换技术[M].北京:化学工业出版社,2005.LIU Ronghou,NIU Weisheng,ZHANG Dalei.Thermochemical conversion technology of biomass[M].Beijing:Chemical Industry Press,2005.
[15]董良秀,李小华,张瑾,等.HZSM-5和MCM-41分子筛催化剂比例对油菜秸秆热解的影响[J].农业工程学报,2017,33(16):241-247.DONG Liangxiu,LI Xiaohua,ZHANG Jin,et al.Effects of HZSM-5and MCM-41 mixing ratios on rape straw catalytic pyrolysis[J].Transactions of the Chinese Society of Agricultural Engineering,2017,33(16):241-247.
[16]朱锡锋,陆强.生物质热解原理与技术[M].北京:科学出版社,2014.ZHU Xifeng,LU Qiang.Principle and technology of biomass pyrolysis[M].Beijing:Science Press,2014.
[17]刘小娟,于凤文,罗瑶,等.生物质催化热解研究进展[J].能源工程,2010(1):15-18.LIU Xiaojuan,YU Fengwen,LUO Yao,et al.Development on catalytic pyrolysis of biomass[J].Energy Engineering,2010(1):15-18.
[18]KAI S,KUOPPALA E,FAGERN?S L,et al.Characterization of biomass-based flash pyrolysis oils[J].Biomass&Bioenergy,1998,14(2):103-113.
[19]费雯婷,刘荣厚,周维奇,等.添加乙酸乙酯对生物油稳定性的影响[J].燃料化学学报,2013,41(06):667-672.FEI Wenting,LIU Ronghou,ZHOU Weiqi,et al.Effect of ethyl acetate addition on the stability of bio-oil[J].Journal of Fuel Chemistry and Technology,2013,41(06):667-672.
[20]鲁长波,杨昌炎,林伟刚,等.生物质催化热解的TG-FTIR研究[J].太阳能学报,2007,28(6):638-643.LU Changbo,YANG Changyan,LIN Weigang,et al.TG-FTIR research of biomass catalytic pyrolysis[J].Acta Energiae Solaris Sinica,2007,28(6):638-643.
[21]刘荣厚,王华.生物质快速热裂解反应温度对生物油产率及特性的影响[J].农业工程学报,2006,22(6):138-143.LIU Ronghou,WANG Hua.Effects of temperature of biomass fast pyrolysis on yield and properties of bio-oil[J].Transactions of the Chinese Society of Agricultural Engineering,2006,22(6):138-143.
[22]叶江明,潘其文,张会岩,等.内循环串行流化床生物质催化热解试验研究[J].动力工程学报,2011,31(3):220-226.YE Jiangming,PAN Qiwen,ZHANG Huiyan,et al.Experimental investigation on biomass catalytic pyrolysis in an internal interconnected fluidized bed[J].Chinese Journal of Power Engineering,2011,31(3):220-226.
[23]GüLLüD,DEMIRBA?A.Biomass to methanol via pyrolysis process[J].Energy Conversion&Management,2001,42(11):1349-1356.
[24]白甜甜.农林生物质热解油组分分离及热解木质素表征研究[D].北京:北京林业大学,2015.BAI Tiantian.Research on fractionation of pyrolysis-oil from agricultural and forestry biomass and characterization of pyrolytic lignin[D].Beijing:Beijing Forestry University,2015.
[25]俞宁,蔡忆昔,李小华,等.HZSM-5分子筛催化热裂解油菜秸秆制取精制生物油[J].农业工程学报,2014,30(15):264-271.YU Ning,CAI Yixi,LI Xiaohua,et al.Catalytic pyrolysis of rape straw for upgraded bio-oil production using HZSM-5 zeolite[J].Transactions of the Chinese Society of Agricultural Engineering,2014,30(15):264-271.
[26]骆仲泱,王树荣,王琦,等.生物质液化原理及技术应用[M].北京:化学工业出版社,2013.LUO Zhongyang,WANG Shurong,WANG Qi,et al.Biomass liquefaction principle and application[M].Beijing:Chemical Industry Press,2013.
[27]王文亮.木质生物质热裂解定向调控酚类化合物研究[D].北京:北京林业大学,2016.WANG Wenliang.Study on the oriented regulation of phenols derived from fast pyrolysis of woody biomass[D].Beijing:Beijing Forestry University,2016.
[28]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.
[29]吴晓娜,赵炜,闫彩辉,等.酚类化合物在生物质利用中的研究进展[J].化工中间体,2012,9(01):10-14.WU Xiaona,ZHAO Hui,YAN Caihui,et al.Research progress of phenolic compounds in biomass utilization[J].Chemical Intermediates,2012,9(01):10-14.
[30]JIANG G,NOWAKOWSKI D J,BRIDGWATER A V.Effect of the temperature on the composition of lignin pyrolysis products[J].Energy Fuels,2010,24(8):4470-4475.
[31]尹海云,李小华,张蓉仙,等.HZSM-5在线提质生物油及催化剂失活机理分析[J].燃料化学学报,2014,42(9):1077-1086.YI Haiyun,LI Xiaohua,ZHANG Rongxian,et al.Online catalytic cracking of bio-oil over HZSM-5 zeolite and analysis of catalyst deactivation[J].Journal of Fuel Chemistry and Technology,2014,42(9):1077-1086.