秸秆气化焦油蒸馏产物GC-MS与TG-DTA测定分析
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摘要
为了利用秸秆气化焦油,测定了秸秆气化焦油112～150℃蒸馏产物上层液的pH、凝点、闪点、恩氏黏度、密度、高位发热量,利用气相色谱-质谱联用仪和综合热分析仪进行秸秆气化焦油112～150℃蒸馏产物上层液GC-MS分析试验和TG-DTA试验,得到试样的化学组成、热重曲线、差热曲线,并从化合物、元素方面与柴油进行对比分析。从挥发分的析出和燃烧特性,升温速率的影响,动力学3方面进行了热分析。结果表明:试样芳香烃质量分数接近柴油,试样成分中不含硫、氮,燃烧污染小;试样易挥发,挥发分质量分数高,挥发分吸热后不断析出,析出较为集中,灰分低、易于燃尽,具备液体燃料喷雾燃烧的特性,具有作为车用燃料的可能性与价值。
In order to study the utilization of straw gasification tar,the pH value,condensation point,flash point,Engler viscosity,density and gross calorific value of the upper straw gasification tar distillation ranging from 112 ℃ to 150 ℃were determined.GC-MS analytic experiment and TG-DTA test of which were conducted by using gas chromatography-mass spectrometry and integrated thermal analyzer.The chemical compositions,the thermogravimetric(TG)curves and the differential thermal analysis(DTA)curves of sample were obtained.Comparative analyses of compounds,elements and diesel were conducted.Thermal analyses were carried out from three aspects of precipitation of volatiles and combustion characteristics,influence of heating rate,and kinetics.The results showed that aromatic hydrocarbon mass fraction in the sample was close to diesel oil.The combustion pollution of the sample with no sulfur,nitrogen,and the pollution was small.The sample was volatile and had a high mass fraction of volatiles.The volatiles were continuously precipitated after heat absorption and the precipitation was concentrated.The sample with low ash content was easy to burn out.It had the characteristics of liquid fuel spray combustion and had the possibility and value of being used as fuel for vehicles.
In order to study the utilization of straw gasification tar,the pH value,condensation point,flash point,Engler viscosity,density and gross calorific value of the upper straw gasification tar distillation ranging from 112 ℃ to 150 ℃were determined.GC-MS analytic experiment and TG-DTA test of which were conducted by using gas chromatography-mass spectrometry and integrated thermal analyzer.The chemical compositions,the thermogravimetric(TG)curves and the differential thermal analysis(DTA)curves of sample were obtained.Comparative analyses of compounds,elements and diesel were conducted.Thermal analyses were carried out from three aspects of precipitation of volatiles and combustion characteristics,influence of heating rate,and kinetics.The results showed that aromatic hydrocarbon mass fraction in the sample was close to diesel oil.The combustion pollution of the sample with no sulfur,nitrogen,and the pollution was small.The sample was volatile and had a high mass fraction of volatiles.The volatiles were continuously precipitated after heat absorption and the precipitation was concentrated.The sample with low ash content was easy to burn out.It had the characteristics of liquid fuel spray combustion and had the possibility and value of being used as fuel for vehicles.
引文
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[26] 于海龙,姜秀民.升温速率对油页岩燃烧特性与动力学参数的影响[J].燃烧科学与技术,2003,9(1):54-57.YU H L,JIANG X M.Influence of temperature rising rate on combustion property and kinetic parameter of oil shale[J].Journal of Combustion Science and Technology,2003,9(1):54-57.
[27] 蔡智鸣,张俊勇,杨科峰,等.色谱-质谱测定市售0号柴油成分[J].同济大学学报(自然科学版),2002,30(1):124-126.CAI Z M,ZHANG J Y,YANG K F,et al.Determination of composition of 0# diesel being sold at market oil by gas chromatography-mass spectrometry[J].Journal of Tongji University(Natural Science),2002,30(1):124-126.
[28] 韦淡平.我国柴油的润滑性——一个潜在的重要问题[J].石油炼制与化工,2001,32(1):37-40.WEI D P.The lubricity of domestic diesel fuel:A hidden danger[J].Petroleum Processing and Petrochemicals,2001,32(1):37-40.
[2] 马隆龙,吴创之,孙立.生物质气化技术及其应用[M].北京:化学工业出版社,2003.MA L L,WU C Z,SUN L.Biomass gasification technology and its application[M].Beijing:Chemical Industry Press,2003.
[3] 张全国.生物质焦油燃烧动力学及其燃料特性实验研究[D].大连:大连理工大学,2006.ZHANG Q G.Experimental study on combustion kinetics and fuel characteristics of biomass tar[D].Dalian:Dalian University of Technology,2006.
[4] 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.LI L H,WHEN G D,YANG Q W,et al.Advance in the treatment methods of biomass tar[J].Chemical Industry and Engineering Progress,2017,36(7):2407-2416.
[5] 张彦,范振山,贾孟立.秸秆气化焦油蒸馏产物的GC-MS分析[J].湖北农业科学,2015,54(8):1979-1980.ZHANG Y,FAN Z S,JIA M L.Analysis of the components in straw gasification tar distillation by GC-MS[J].Hubei Agricultural Science,2015,54(8):1979-1980.
[6] 范振山,张彦.秸秆气化焦油蒸馏产物热重分析试验研究[J].农机化研究,2014,36(3):220-223.FAN Z S,ZHANG Y.Study of thermal analytic experiment of straw gasification tar distillation[J].Journal of Agricultural Mechanization Research,2014,36(3):220-223.
[7] 杨秀山,赵军,骆海鹏,等.微生物降解生物质气化洗焦废水和焦油的研究[J].中国环境科学,2001,21(2):109-111.YANG X S,ZHAO J,LUO H P,et al.Study on microbial degradation of tar-wash wastewater and tar in biomass gasification by microorganisms[J].China Environmental Science,2001,21(2):109-111.
[8] 何选明,陈芸,戴丹,等.生物质焦油改性提质制取燃料油的研究进展[J].能源化工,2016,37(3):24-27.HE X M,CHEN Y,DAI D et al.Research progress of modifying and upgrading biomass tar to produce fuel oil[J].Energy Chemical Industry,2016,37(3):24-27.
[9] 张寰.秸秆类生物质焦油热解动力学及碳纤维制备实验研究[D].郑州:河南农业大学,2014.ZHANG H.Study on thermal properties of biomass tar using straw and manufacture technology of carbon fiber[D].Zhengzhou:Henan Agricultural University,2014.
[10] 赵创,蒋恩臣.催化裂解生物质焦油提质试验研究[J].化肥设计,2016,54(5):15-19.ZHAO C,JIANG N C.Experimental study on biomass tar upgrading through catalytic cracking[J].Chemical Fertilizer Design,2016,54(5):15-19.
[11] 王素兰.生物质气化副产物焦油热重分析[J].河南科技大学学报(自然科学版),2008,29(5):101-104.WANG S L.Study on kinetic characteristics of biomass tar[J].Journal of Henan University of Science and Technology(Natural Science),2008,29(5):101-104.
[12] 陈冠益,刘聪,颜蓓蓓,等.生物质焦油热解动力学分析[J].太阳能学报,2016,37(3):529-534.CHEN G Y,LIU C,YAN B B,et al.Kinetic analysis of corn-cob tar pyrolysis[J].Acta Energiae Solaris Sinica,2016,37(3):529-534.
[13] 孙鹏鹏.基于生物质焦油还原的铬渣解毒机理与动力学规律研究[D].青岛:青岛理工大学,2015.SUN P P.Study on detoxification and kinetics laws of chromite ore processing residue based on biomass tar[D].Qingdao:Qingdao Technological University,2015.
[14] 曾艳.生物质及其气化焦油的热解及动力学特性与机理[D].重庆:重庆大学,2008.ZENG Y.Study on pyrolysis mechanism characteristic and pyrolysis kinetics of biomass and gasified tar[D].Chongqing:Chongqing University,2008.
[15] 江程程.生物质焦油的热裂解特性研究[D].武汉:华中科技大学,2011.JIANG C C.Research on thermal cracking characteristic of biomass tar[D].Wuhan:Huazhong University of Science and Technology,2011.
[16] 杨玉琼,卢仕远,杜松,等.生物质焦油成分分析及综合利用研究[J].广州化工,2014,42(10):134-136.YANG Y Q,LU S Y,DU S,et al.Research of biomass tar analysis and utilization[J].Guangzhou Chemical Industry,2014,42(10):134-136.
[17] 张素萍,颜涌捷,李庭琛,等.生物质裂解焦油的燃烧特性及动力学模型[J].华东理工大学学报(自然科学版),2002,28(1):104-106.ZHANG,S P,YAN Y J,LI T C,et al.Combustion characteristics and kinetic analysis of bio-oil from flash pyrolysis of biomass[J].Journal of East China University of Science and Technology(Natural Science Edition),2002,28(1):104-106.
[18] 丛浦珠.质谱学在天然有机化学中的应用[M].北京:科学出版社,1987.CONG P Z.Application of mass spectrometry in natural organic chemistry[M].Beijing:Science Press,1987.
[19] 科特.有机质谱法导论[M].北京:科学出版社,1982.KURT L A.Introduction to organic mass spectrometry[M].Beijing:Science Press,1982.
[20] 汪正范,杨树民,吴侔天,等.色谱联用技术[M].北京:化学工业出版社,2001.WANG Z F,YANG S M,WU M T,et al.Chromatography combined technology[M].Beijing:Chemical Industry Press,2001.
[21] 李继红,雷廷宙,宋华民,等.GC/MS法分析生物质焦油的化学组成[J].河南科学,2005,23(1):41-43.LI J H,LEI T Z,SONG H M,et al.Analysis of chemical component of biomass-based tar by GC/MS[J].Henan Sciences,2005,23(1):41-43.
[22] 沈兴.差热、热重分析与非等温固相反应动力学[M].北京:冶金工业出版社,1995.SHEN X.Differential thermal and thermogravimetric analysis and kinetics of non-isothermal solid state reaction[M].Beijing:Metallurgical Industry Press,1995.
[23] 李继红.生物质焦油及其馏分的热动力学研究[D].郑州:河南农业大学,2005.LI J H.Study on thermal kinetics characteristics of biomass tar and its distillations[D].Zhengzhou:Henan Agricultural University,2005.
[24] 王树荣,廖艳芬,骆仲泱,等.生物质热裂解制油的动力学及技术研究[J].燃烧科学与技术,2002,8(2):176-180.WANG S R,LIAO Y F,LUO Z Y,et al.Kinetic research on pyrolysis of biomass for bio-oil production[J].Journal of Combustion Science and Technology,2002,8(2):176-180.
[25] 顾利锋,陈晓平,赵长遂,等.城市污泥和煤混燃特性的热重分析法研究[J].热能动力工程,2003,18(6):561-563.GU L F,CHEN X P,ZHAO C S,et al.A study of the characteristics of mixed burning of municipal sewage sludge and coal by a thermogravimetric method[J].Journal of Engineering for Thermal Energy and Power,2003,18(6):561-563.
[26] 于海龙,姜秀民.升温速率对油页岩燃烧特性与动力学参数的影响[J].燃烧科学与技术,2003,9(1):54-57.YU H L,JIANG X M.Influence of temperature rising rate on combustion property and kinetic parameter of oil shale[J].Journal of Combustion Science and Technology,2003,9(1):54-57.
[27] 蔡智鸣,张俊勇,杨科峰,等.色谱-质谱测定市售0号柴油成分[J].同济大学学报(自然科学版),2002,30(1):124-126.CAI Z M,ZHANG J Y,YANG K F,et al.Determination of composition of 0# diesel being sold at market oil by gas chromatography-mass spectrometry[J].Journal of Tongji University(Natural Science),2002,30(1):124-126.
[28] 韦淡平.我国柴油的润滑性——一个潜在的重要问题[J].石油炼制与化工,2001,32(1):37-40.WEI D P.The lubricity of domestic diesel fuel:A hidden danger[J].Petroleum Processing and Petrochemicals,2001,32(1):37-40.
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