基于副产物揭示条浒苔热解机理
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摘要
以生物质条浒苔为原料,石英管管式炉为反应器,在190、320、550℃热解温度下制备半焦,以X射线光电子能谱法(XPS)为主要分析手段,利用XPS检测不同热解温度下半焦表面结构变化,同时结合热解气和半焦电镜扫描的分析结果揭示条浒苔的热解机理。研究结果表明:条浒苔在低温段(<190℃)热解过程中主要以脱水和部分小分子侧链的解聚为主;在中温段(190～320℃)热解过程中,蛋白质、硫酸多糖及一些脂类物质开始不断解聚和重组;在高温段(320～550℃)热解过程中,蛋白质与水溶性多糖基本热解完毕,少量纤维素碳化生成CO、CH_4气体并析出。
In this study,the char was prepared in a horizon tube furnace reactor by heating seaweed samples at 190 ℃,320 ℃,and 550 ℃. The surface structures of char at different pyrolysis temperatures were analyzed by XPS and the differences were given. The pyrolysis gas was analyzed by a gas chromatography,and the semicoke was tested by a scanning electron microscope. The experiment results reveal the pyrolysis mechanism of Enteromorpha clathrata. It was indicated that the Enteromorpha clathrata in low temperature stage(<190 ℃)pyrolysis processed mainly by dehydration and part of the small molecular side chain depolymerization. During pyrolysis in middle temperature stage(190-320 ℃),protein,sulfated polysaccharide and some lipids started to depolymerize and recombine constantly. And in high temperature stage(320-550 ℃),decomposition of protein and water-soluble polysaccharide have finished basically and a little cellulose carbonized,generating CO,CH_4 and separating them out.
In this study,the char was prepared in a horizon tube furnace reactor by heating seaweed samples at 190 ℃,320 ℃,and 550 ℃. The surface structures of char at different pyrolysis temperatures were analyzed by XPS and the differences were given. The pyrolysis gas was analyzed by a gas chromatography,and the semicoke was tested by a scanning electron microscope. The experiment results reveal the pyrolysis mechanism of Enteromorpha clathrata. It was indicated that the Enteromorpha clathrata in low temperature stage(<190 ℃)pyrolysis processed mainly by dehydration and part of the small molecular side chain depolymerization. During pyrolysis in middle temperature stage(190-320 ℃),protein,sulfated polysaccharide and some lipids started to depolymerize and recombine constantly. And in high temperature stage(320-550 ℃),decomposition of protein and water-soluble polysaccharide have finished basically and a little cellulose carbonized,generating CO,CH_4 and separating them out.
引文
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[18]Li Xiufeng,Xu Han,Wu Qingyu.Large-scale biodiesel production from microalga Chlorella protothecoides through heterotrophic cultivation in bioreactors[J].Biotechnology and Bioengineering,2007,98(4):764-771.
[19]向军,胡松,孙路石,等.煤燃烧过程中碳、氧官能团演化行为[J].化工学报,2006,57(9):2180-2184.[19]Xiang Jun,Hu Song,Sun Lushi,et al.Evolution of carbon and oxygen functional groups during coal combustion[J].Journal of Chemical Industry and Engineering,2006,57(9):2180-2184.
[20]Zhang Min,Resende F L P,Moutsoglou A,et al.Pyrolysis of lignin extracted from prairie cordgrass,aspen,and Kraft lignin by Py-GC/MS and TGA/FTIR[J].Journal of Analytical and Applied Pyrolysis,2012,98:65-71.
[21]陈应泉,朱波,王贤华,等.生物质热解过程中焦炭物化结构演变特性[J].太阳能学报,2012,33(8):1267-1272.[21]Chen Yingquan,Zhu Bo,Wang Xianhua,et al.Evolution of char’s physical and chemical structure during biomass pyrolysis[J].Acta Energiae Solaris Sinica,2012,33(8):1267-1272.
[22]Sun Lina,Tuo Jincai,Zhang Mingfeng,et al.Formation and development of the pore structure in Chang 7member oil-shale from Ordos Basin during organic matter evolution induced by hydrous pyrolysis[J].Fuel,2015,158:549-557.
[2]Bae Yoon Ju,Ryu Changkook,Jeon Jong-Ki,et al.The characteristics of bio-oil produced from the pyrolysis of three marine macroalgae[J].Bioresource Technology,2011,102(3):3512-3520.
[3]Du Zhenyi,Hu Bing,Ma Xiaochen,et al.Catalytic pyrolysis of microalgae and their three major components:Carbohydrates,proteins,and lipids[J].Bioresource Technology,2013,130:777-782.
[4]Anastasakis K,Ross A B,Jones J M.Pyrolysis behaviour of the main carbohydrates of brown macroalgae[J].Fuel,2011,90(2):598-607.
[5]刘艳华,车得福,徐通模.利用X射线光电子能谱确定煤及其残焦中硫的形态[J].西安交通大学学报,2004,38(1):101-104.[5]Liu Yanhua,Che Defu,Xu Tongmo.X-ray photoelectron spectroscopy determination of the forms of sulfur in coal and its chars[J].Journal of Xi’an Jiaotong University,2004,38(1):101-104.
[6]王鹏,张坚,陈振国,等.基于XPS的纤维素热解焦表面结构分析[J].燃烧科学与技术,2015,21(4):378-381.[6]Wang Peng,Zhang Jian,Chen Zhenguo,et al.Surface structure of pyrolytic char of cellulose based on XPSanalysis[J].Journal of Combustion Science and Technology,2015,21(4):378-381.
[7]李培生,胡益,胡念苏,等.污泥和煤混烧过程中含氧官能团的变化规律[J].中国电机工程学报,2009,29(8):40-44.[7]Li Peisheng,Hu Yi,Hu Niansu,et al.Evolution of oxygen functionality during co-combustion of sewage sludge and coal[J].Proceedings of the CSEE,2009,29(8):40-44.
[8]Wang S,Wang Q,Hu Y M,et al.Study on the synergistic co-pyrolysis behaviors of mixed rice husk and two types of seaweed by a combined TG-FTIR technique[J].Journal of Analytical and Applied Pyrolysis,2015,114:109-118.
[9]Kelemen S R,Afeworki M,Gorbaty M L,et al.Characterization of organically bound oxygen forms in lignites,peats,and pyrolyzed peats by X-ray photoelectron spectroscopy(XPS)and solid-state 13CNMR methods[J].Energy&Fuels,2002,16(6):1450-1462.
[10]Kozlowski M.XPS study of reductively and nonreductively modified coals[J].Fuel,2004,83(3):259-265.
[11]Grzybek T,Pietrzak R,Wachowska H.X-ray photoelectron spectroscopy study of oxidized coals with different sulphur content[J].Fuel Processing Technology,2002,77:1-7.
[12]Harrison E Z,Oakes S R,Hysell M,et al.Organic chemicals in sewage sludges[J].Science of the Total Environment,2006,367(2-3):481-497.
[13]王爽,胡亚敏,王谦,等.基于不同组分的海藻热分解机理研究[J].太阳能学报,2016,15(12):201-205.[13]Wang Shuang,Hu Yamin,Wang Qian,et al.Pyrolysis mechanism based in different components of seawed[J].Acta Energiae Solaris Sinica,2016,15(12):201-205.
[14]Oliveiral R C,Hammer P,Guibal E,et al.Characterization of metal-biomass interactions in the lanthanum(III)Biosorption on Sargassum sp.using SEM/EDX,FTIR,and XPS:Preliminary studies[J].Chemical Engineering Journal,2014,239:381-391.
[15]Fullana A,Conesa J A,Font R,et al.Pyrolysis of sewage sludge:Nitrogenated compounds and pretreatment effects[J].Journal of Analytical and Applied Pyrolysis,2003,68:561-575.
[16]赵世永,吴沛沛,李鑫,等.神府煤中低温热解前后表面官能团和孔隙变化规律的研究[J].煤炭工程,2006,47(12):114-117.[16]Zhao Shiyong,Wu Peipei,Li Xin,et al.Study on variation law of surface functional groups and pore of Shenfu coal after low-middle temperature pyrolysis[J].Coal Engineering,2006,47(12):114-117.
[17]Wang Shuang,Jiang Xiumin,Wang Ning,et al.Research on pyrolysis characteristics of seaweed[J].Energy&Fuels,2007,21(6):3723-3729.
[18]Li Xiufeng,Xu Han,Wu Qingyu.Large-scale biodiesel production from microalga Chlorella protothecoides through heterotrophic cultivation in bioreactors[J].Biotechnology and Bioengineering,2007,98(4):764-771.
[19]向军,胡松,孙路石,等.煤燃烧过程中碳、氧官能团演化行为[J].化工学报,2006,57(9):2180-2184.[19]Xiang Jun,Hu Song,Sun Lushi,et al.Evolution of carbon and oxygen functional groups during coal combustion[J].Journal of Chemical Industry and Engineering,2006,57(9):2180-2184.
[20]Zhang Min,Resende F L P,Moutsoglou A,et al.Pyrolysis of lignin extracted from prairie cordgrass,aspen,and Kraft lignin by Py-GC/MS and TGA/FTIR[J].Journal of Analytical and Applied Pyrolysis,2012,98:65-71.
[21]陈应泉,朱波,王贤华,等.生物质热解过程中焦炭物化结构演变特性[J].太阳能学报,2012,33(8):1267-1272.[21]Chen Yingquan,Zhu Bo,Wang Xianhua,et al.Evolution of char’s physical and chemical structure during biomass pyrolysis[J].Acta Energiae Solaris Sinica,2012,33(8):1267-1272.
[22]Sun Lina,Tuo Jincai,Zhang Mingfeng,et al.Formation and development of the pore structure in Chang 7member oil-shale from Ordos Basin during organic matter evolution induced by hydrous pyrolysis[J].Fuel,2015,158:549-557.