吡啶抽提前后柳林3~#煤的FTIR结构特征分析
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摘要
为了解处于第二次煤化跃变过程中的柳林3~#煤的大分子结构特征,采用溶剂吡啶对柳林3~#原煤进行索氏抽提,借助FTIR分析测试手段并通过分段分峰拟合对柳林3~#原煤、抽提后残煤及抽提物的结构组成及其变化进行了研究。结果表明:抽提过程中,在吡啶溶剂的作用下,部分抽提物从煤大分子结构中脱离出来,这些抽提物包括短链脂肪结构和芳香醚、酚、酯等含氧官能团结构。抽提前后煤大分子骨架保持相对稳定,与原煤和抽提后残煤相比,抽提物的苯环四取代明显增加,二取代明显减少,说明残煤的脂肪链长、支链少,抽提物的脂肪链短、支链多。抽提后残煤、抽提物与原煤显示出不同的芳香度,其由大到小依次为抽提后残煤的芳香度、原煤的芳香度、抽提物的芳香度;柳林3~#原煤、抽提后残煤及抽提物中主要羟基类型是自缔合羟基,说明煤中羟基类型以缔合结构为主。
In order to understand the macromolecular structure characteristics of Liulin3~# coal during the second coalification jump process,Liulin 3~# raw coal was extracted by pyridine.By means of FTIR,the raw coal,residues and extracts were studied with curve-fitting analysis to obtain the strcture and its change information.The results show that under the action of pyridine solvent,some extracts are separated from the macromolecular structures.These extracts include short chain aliphatic structure,aromatic ether,phenol and other oxygen-containing functional groups.The skeleton of coal macromolecule remains relatively stable before and after extraction.Compared with the raw coal and the residual coal,the benzene ring tetrasubstitution of the extract increases obviously,while the disubstitution decreases obviously.The results show that the residuals have a longer aliphatic chain and fewer branched chains,and the extracts have short fat chains and many branched chains.Different aromaticity is shown in residues,extracts and raw coal,and the aromaticity order is residues,raw coal,extracts from large to small.The main hydroxyl groups in Liulin 3~# coal,residues and extracts are self-associating hydroxyl groups,which indicates that the main hydroxyl groups in coal are associative structures.
In order to understand the macromolecular structure characteristics of Liulin3~# coal during the second coalification jump process,Liulin 3~# raw coal was extracted by pyridine.By means of FTIR,the raw coal,residues and extracts were studied with curve-fitting analysis to obtain the strcture and its change information.The results show that under the action of pyridine solvent,some extracts are separated from the macromolecular structures.These extracts include short chain aliphatic structure,aromatic ether,phenol and other oxygen-containing functional groups.The skeleton of coal macromolecule remains relatively stable before and after extraction.Compared with the raw coal and the residual coal,the benzene ring tetrasubstitution of the extract increases obviously,while the disubstitution decreases obviously.The results show that the residuals have a longer aliphatic chain and fewer branched chains,and the extracts have short fat chains and many branched chains.Different aromaticity is shown in residues,extracts and raw coal,and the aromaticity order is residues,raw coal,extracts from large to small.The main hydroxyl groups in Liulin 3~# coal,residues and extracts are self-associating hydroxyl groups,which indicates that the main hydroxyl groups in coal are associative structures.
引文
[1]虞继舜.煤化学[M].北京:冶金工业出版社,2000.YU Jishun.Coal Chemistry[M].Beijing:Metallurgical Industry Press,2000.
[2]陈润,王治洋,秦勇,等.黔西滇东镜煤CS2抽余物的甲烷吸附特征及地球化学机理[J].中国矿业大学学报,2015,44(4):726-730.CHEN Run,WANG Zhiyang,QIN Yong,et al.Adsorption Characteristics of CS2-extracted Vitrains from Western Guizhou and Eastern Yunnan and Its Geochemical Mechanism[J].Journal of China University of Mining and Technology,2015,44(4):726-730.
[3]GREEN T,KOVAC J,BRENNER D,et al.Coal Structure[M].New York:Academic Press,1982.
[4]IINO M.Network Structure of Coals and Association Behavior of Coal-derived Materials[J].Fuel Processing Technology,2000,62(2/3):89-101.
[5]TIAN Bin,QIAO Yingyun,TIAN Yuanyu,et al.FTIR Study on Structural Changes of Different-rank Coals Caused by Single/Multiple Extraction with Cyclohexanone and NMP/CS2 Mixed Solvent[J].Fuel Processing Technology,2016,154:210-218.
[6]张硕,张小东,杨延辉,等.溶剂萃取下构造煤的XRD结构演化特征[J].光谱学与光谱分析,2017(10):3220-3224.ZHANG Shuo,ZHANG Xiaodong,YANG Yanhui,et al.XRD Structure Evolution Characteristics of Tectonic Coal Under Solvent Extraction[J].Spectroscopy and Spectral Analysis,2017(10):3220-3224.
[7]刘颖,张蓬洲,吴奇虎.抚顺烟煤及其抽出物的FTIR光谱结构表征[J].燃料化学学报,1992(1):96-101.LIU Ying,ZHANG Pengzhou,WU Qihu.FTIR Spectroscopic Analysis of Fushun Bituminous Coal and Coal Extracts[J].Journal of Fuel Chemistry and Technology,1992(1):96-101.
[8]CHEN Yanyan,MASTALERZ M,SCHIMMELMANN A.Characterization of Chemical Functional Groups in Macerals Across Different Coal Ranks via Micro-FTIR Spectroscopy[J].International Journal of Coal Geology,2012,104(1):22-33.
[9]江春,孙昊,张迪,等.FTIR法对准格尔煤两级分次萃取物的分析[J].煤炭学报,2007,32(1):85-89.JIANG Chun,SUN Hao,ZHANG Di,et al.FTIR Analysis of Fractional Extracts from Zhunge’er Bituminous Coal[J].Journal of China Coal Society,2007,32(1):85-89.
[10]郭崇涛.煤化学[M].北京:化学工业出版社,1992.GUO Chongtao.Coal Chemistry[M].Beijing:Chemical Industry Press,1992.
[11]IBARRA J,MUOZ E,MOLINER R.FTIR Study of the Evolution of Coal Structure During the Coalification Process[J].Organic Geochemistry,1996,24(6/7):725-735.
[12]ZHAO Yan,LIU Li,QIU Penghua,et al.Impacts of Chemical Fractionation on Zhundong Coal’s Chemical Structure and Pyrolysis Reactivity[J].Fuel Processing Technology,2017,155:144-152.
[13]赵杏媛,张有瑜.黏土矿物与黏土矿物分析[M].北京:海洋出版社,1990.ZHAO Xingyuan,ZHANG Youyu.Clay Minerals and Analysis of Clay Minerals[M].Beijing:China Ocean Press,1990.
[14]PAINTER P C,SOBKOWIAK M,YOUTCHEFF J.FTIR Study of Hydrogen Bonding in Coal[J].Fuel,1987,66(7):973-978.
[15]冯杰,李文英,谢克昌.傅立叶红外光谱法对煤结构的研究[J].中国矿业大学学报,2002,31(5):362-366.FENG Jie,LI Wenying,XIE Kechang.Research on Coal Structure Using FTIR[J].Journal of China University of Mining and Technology,2002,31(5):362-366.
[16]WANG Shaoqing,TANG Yuegang,SCHOBERT H H,et al.FTIR and 13C-NMR Investigation of Coal Component of Late Permian Coals from Southern China[J].Energy and Fuels,2011,25(12):5672-5677.
[17]李霞,曾凡桂,王威,等.低中煤级煤结构演化的FTIR表征[J].煤炭学报,2015,40(12):2900-2908.LI Xia,ZENG Fangui,WANG Wei,et al.FTIR Characterization of Structural Evolution in Low-middle Rank Coals[J].Journal of China Coal Society,2015,40(12):2900-2908.
[2]陈润,王治洋,秦勇,等.黔西滇东镜煤CS2抽余物的甲烷吸附特征及地球化学机理[J].中国矿业大学学报,2015,44(4):726-730.CHEN Run,WANG Zhiyang,QIN Yong,et al.Adsorption Characteristics of CS2-extracted Vitrains from Western Guizhou and Eastern Yunnan and Its Geochemical Mechanism[J].Journal of China University of Mining and Technology,2015,44(4):726-730.
[3]GREEN T,KOVAC J,BRENNER D,et al.Coal Structure[M].New York:Academic Press,1982.
[4]IINO M.Network Structure of Coals and Association Behavior of Coal-derived Materials[J].Fuel Processing Technology,2000,62(2/3):89-101.
[5]TIAN Bin,QIAO Yingyun,TIAN Yuanyu,et al.FTIR Study on Structural Changes of Different-rank Coals Caused by Single/Multiple Extraction with Cyclohexanone and NMP/CS2 Mixed Solvent[J].Fuel Processing Technology,2016,154:210-218.
[6]张硕,张小东,杨延辉,等.溶剂萃取下构造煤的XRD结构演化特征[J].光谱学与光谱分析,2017(10):3220-3224.ZHANG Shuo,ZHANG Xiaodong,YANG Yanhui,et al.XRD Structure Evolution Characteristics of Tectonic Coal Under Solvent Extraction[J].Spectroscopy and Spectral Analysis,2017(10):3220-3224.
[7]刘颖,张蓬洲,吴奇虎.抚顺烟煤及其抽出物的FTIR光谱结构表征[J].燃料化学学报,1992(1):96-101.LIU Ying,ZHANG Pengzhou,WU Qihu.FTIR Spectroscopic Analysis of Fushun Bituminous Coal and Coal Extracts[J].Journal of Fuel Chemistry and Technology,1992(1):96-101.
[8]CHEN Yanyan,MASTALERZ M,SCHIMMELMANN A.Characterization of Chemical Functional Groups in Macerals Across Different Coal Ranks via Micro-FTIR Spectroscopy[J].International Journal of Coal Geology,2012,104(1):22-33.
[9]江春,孙昊,张迪,等.FTIR法对准格尔煤两级分次萃取物的分析[J].煤炭学报,2007,32(1):85-89.JIANG Chun,SUN Hao,ZHANG Di,et al.FTIR Analysis of Fractional Extracts from Zhunge’er Bituminous Coal[J].Journal of China Coal Society,2007,32(1):85-89.
[10]郭崇涛.煤化学[M].北京:化学工业出版社,1992.GUO Chongtao.Coal Chemistry[M].Beijing:Chemical Industry Press,1992.
[11]IBARRA J,MUOZ E,MOLINER R.FTIR Study of the Evolution of Coal Structure During the Coalification Process[J].Organic Geochemistry,1996,24(6/7):725-735.
[12]ZHAO Yan,LIU Li,QIU Penghua,et al.Impacts of Chemical Fractionation on Zhundong Coal’s Chemical Structure and Pyrolysis Reactivity[J].Fuel Processing Technology,2017,155:144-152.
[13]赵杏媛,张有瑜.黏土矿物与黏土矿物分析[M].北京:海洋出版社,1990.ZHAO Xingyuan,ZHANG Youyu.Clay Minerals and Analysis of Clay Minerals[M].Beijing:China Ocean Press,1990.
[14]PAINTER P C,SOBKOWIAK M,YOUTCHEFF J.FTIR Study of Hydrogen Bonding in Coal[J].Fuel,1987,66(7):973-978.
[15]冯杰,李文英,谢克昌.傅立叶红外光谱法对煤结构的研究[J].中国矿业大学学报,2002,31(5):362-366.FENG Jie,LI Wenying,XIE Kechang.Research on Coal Structure Using FTIR[J].Journal of China University of Mining and Technology,2002,31(5):362-366.
[16]WANG Shaoqing,TANG Yuegang,SCHOBERT H H,et al.FTIR and 13C-NMR Investigation of Coal Component of Late Permian Coals from Southern China[J].Energy and Fuels,2011,25(12):5672-5677.
[17]李霞,曾凡桂,王威,等.低中煤级煤结构演化的FTIR表征[J].煤炭学报,2015,40(12):2900-2908.LI Xia,ZENG Fangui,WANG Wei,et al.FTIR Characterization of Structural Evolution in Low-middle Rank Coals[J].Journal of China Coal Society,2015,40(12):2900-2908.