沁水盆地北部中高煤阶煤结构的FTIR特征研究
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摘要
为了研究中高煤阶煤中官能团的变化特征,以采自沁水盆地北部不同变质程度的10个煤样为研究对象,采用傅里叶变换红外光谱仪对样品进行了红外光谱(FTIR)分析。通过对FTIR曲线分峰拟合,可以获得煤中脂肪结构、含氧官能团和芳香结构的相对含量。研究结果表明:中高煤阶煤中,脂肪结构含量较低;芳香结构中,只有一个邻近氢原子的芳香环含量最高,芳香结构被替代的程度高;含氧官能团中,醚氧逐渐成为含量较高的含氧官能团,表明以醚氧形式存在的氧原子稳定性强。通过对煤样的最大镜质体反射率R_(max)进行测试,探讨样品红外结构参数与R_(max)的相关性,发现随R_(max)(1.1%～2.7%)的增大,芳香度增大,芳香结构的缩聚程度增加,反应生烃潜力的‘A’因子降低,表明在此阶段煤化作用的结果是芳香烃类物质增多。
In order to study the variation features of the functional group in the middle and high rank coal,10 coal samples with different metamorphic grades were collected from the north part of Qinshui Basin as the study objects. A Fourier transform infrared spectrometer was applied to the infrared spectrum analysis on the coal samples. With the peak sharing fitting of the FTIR curves,the relative contents of the aliphatic structures,oxygen functional groups and aromatic structure could be obtained. The study results showed that in the middle and high rank coal,the content of the aliphatic structures would be low. The aromatic rings with only one adjacent hydrogen atom was the main aromatic structure,and showed that the aromatic structures had a high substitution.In the oxygen functional group,the ether oxygen would steadily became the oxygen functional group with a high content and indicted a high stability of the oxygen atom existed with the ether oxygen mode. With a test conducted on the maximum reflectance R_(max)of the vitrinite in the coal samples,the infrared structure parameter and the R_(max)relevance of the coal samples were discussed. The test showed that with the R_(max)( 1.1% ～2.7%) increased,the aromaticity would be increased,the condensation degree of the aromatic structure would be increased and the‘A'factor of the reactive hydrocarbon potential would be decreased. Thus the results of the coalification at this stage would have more increased aromatic hydrocarbons.
In order to study the variation features of the functional group in the middle and high rank coal,10 coal samples with different metamorphic grades were collected from the north part of Qinshui Basin as the study objects. A Fourier transform infrared spectrometer was applied to the infrared spectrum analysis on the coal samples. With the peak sharing fitting of the FTIR curves,the relative contents of the aliphatic structures,oxygen functional groups and aromatic structure could be obtained. The study results showed that in the middle and high rank coal,the content of the aliphatic structures would be low. The aromatic rings with only one adjacent hydrogen atom was the main aromatic structure,and showed that the aromatic structures had a high substitution.In the oxygen functional group,the ether oxygen would steadily became the oxygen functional group with a high content and indicted a high stability of the oxygen atom existed with the ether oxygen mode. With a test conducted on the maximum reflectance R_(max)of the vitrinite in the coal samples,the infrared structure parameter and the R_(max)relevance of the coal samples were discussed. The test showed that with the R_(max)( 1.1% ～2.7%) increased,the aromaticity would be increased,the condensation degree of the aromatic structure would be increased and the‘A'factor of the reactive hydrocarbon potential would be decreased. Thus the results of the coalification at this stage would have more increased aromatic hydrocarbons.
引文
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[18] IGLESIAS M,JIMENEZ A,LAGGOUN Défarge F,et al. FTIR study of pure vitrains and associated coals[J]. Energy&Fuels,1995,9,458-466.
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[20] GUO Y,BUSTIN R M.Micro-FTIR spectroscopy of liptinite macerals in coal[J]. International Journal of Coal Geology,1998,36(3):259-275.
[21] SUN Xuguang.The investigation of chemical structure of coal macerals via transmitted-light FT-IR microspectroscopy[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy.2005,62(1/3),557-564.
[2] LI W,ZHU Y.Structural characteristics of coal vitrinite during pyrolysis[J].Energy&Fuels,2014,28(6):3645-3654.
[3] IBARRA J,MUNOZ E,MOLINER R.FTIR study of the evolution of coal structure during the coalification process[J]. Organic Geochemistry,1996,24(6-7):725-735.
[4] CHEN Y,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.
[5]朱学栋,朱子彬,韩崇家,等.煤中含氧官能团的红外光谱定量分析[J].燃料化学学报,1999,27(4):335-339.ZHU Xuedong,ZHU Zibin,HAN Chongjia,et al. Quantitative determination of oxygen-containing functional groups in coal by FTIR spectroscopy[J].Journal of Fuel Chemistry and Technology,1999,27(4):335-339.
[6] SOBKOWIAK M,PAINTER P,GIVEN P,et al.Determination of aromatic and aliphatic CH groups in coal by FT-IR 1,Studies of coal extracts[J].Fuel,1992,71(10):1105-1125.
[7] REISSER E,SOBKOWIAK M,SQUIRES E,et al.Determination of aromatic and aliphatic CH groups in coal by FT-IR 2,Studies of coals and vitrinite concentration[J]. Fuel,1984,63(9):1253-1261.
[8]郑庆荣,曾凡桂,张世同.中变质煤结构演化的FT-IR分析[J].煤炭学报,2011,36(3):481-486.ZHENG Qingrong,ZENG Fangui,ZHANG Shitong.FT-IR study on structure evolution of middle maturate coals[J]. Journal of China Coal Society,2011,36(3):481-486.
[9]李霞,曾凡桂,王威,等.低中煤阶煤结构演化的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.
[10]张永平,杨艳磊,邵国良,等.沁水盆地煤层结构及煤岩储层特征研究[J].煤炭科学技术,2017,45(4):131-136.ZHANG Yongping,YANG Yanlei,SHAO Guoliang,et al.Study of coal seam structure and reservoirs properties of in Qinshui Basin[J].Coal Science and Technology,2017,45(4):131-136.
[11]李喆,康永尚,姜杉钰,等.沁水盆地高煤阶煤吸附时间主要影响因素分析[J].煤炭科学技术,2017,45(2):115-121.LI Zhe,KANG Yongshang,JIANG Shanyu,et al. Analysis on major factors affected to adsorption time of high rank coal in Qinshui Basin[J]. Coal Science and Technology,2017,45(2):115-121.
[12] SOLOMON P,CARRNGELO R.FTIR analysis of coal:techniques and determination of hydroxyl concentrations[J]. Fuel,1982,61(7):663-669.
[13] PAINTER P,SOBKOWIAK M,YOUTCHEFF J.FT-IR study of hydrogen bonding in coal[J].Fuel,1987,66(7):973-978.
[14] MACHNIKOWSKA H,KRZTON A,MACHNIKOWSKI J. The characterization of coal macerals by diffuse reflectance infrared spectroscopy[J].Fuel,2002,81(2):245-252.
[15] CHARLAND J,MACPHEE J,GIROUX L,et al.Application of TG-FTIR to the determination of oxygen content of coal[J]. Fuel Processing Technology,2003,81(3):211-221.
[16] GENG W,NAKAJIMA T,Takanashi H,et al.Analysis of carboxyl group in coal and coal aromaticity by Fourier transform infrared(FT-IR)spectrometry[J].Fuel,2009,88(4):139-144.
[17] PAINTER P,OPAPRAKASIT P,SCARONI A.Ionomers and the structure of coal[J].Energy&Fuels,2000,14(5):1115-1118.
[18] IGLESIAS M,JIMENEZ A,LAGGOUN Défarge F,et al. FTIR study of pure vitrains and associated coals[J]. Energy&Fuels,1995,9,458-466.
[19]余海洋,孙旭光,焦宗福.华南晚二叠世“树皮体”显微傅里叶红外光谱(Micro-FTIR)特征及意义[J].北京大学学报:自然科学版,2004,40(6):879-885.YU Haiyang,SUN Xuguang,JIAO Zongfu.Characteristics and implications of micro-FTIR spectroscopy of barkinite from Upper Permian Coals,South China[J]. Acta Scientiarum Naturalium Universitatis Pekinensis,2004,40(6):879-885.
[20] GUO Y,BUSTIN R M.Micro-FTIR spectroscopy of liptinite macerals in coal[J]. International Journal of Coal Geology,1998,36(3):259-275.
[21] SUN Xuguang.The investigation of chemical structure of coal macerals via transmitted-light FT-IR microspectroscopy[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy.2005,62(1/3),557-564.