不同变质变形煤微晶结构的XRD试验研究
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摘要
煤的变质、变形作用不仅对煤的宏观特征具有重要影响,而且也影响着煤的微晶结构,煤微晶结构是影响煤储层物性的内在因素之一。为深入研究不同变质变形煤的微晶结构演化特征,本文采用X射线衍射(XRD)试验方法,综合前人的试验结果,对全煤级不同变质变形煤的微晶结构参数进行研究。结果表明:随着煤级的升高,面网间距d002逐渐减小、堆砌度Lc以及芳香层数Nc逐渐增大,呈现一定的阶段性,其数值最终趋于稳定;延展度La与最大反射率Ro,max呈线性关系,随着煤级的升高而逐渐增大。在变质作用的基础上,构造变形作用拉长了煤微晶参数的变化区间,使微晶结构得以提前演化;构造变形作用对堆砌度Lc、延展度La以及芳香层数Nc的增大有积极的影响;弱构造变形作用对d002最终稳定值影响较小,强构造变形煤d002的最终稳定值较原生煤的小;原生结构煤、弱构造变形煤以及强构造变形煤微晶参数随煤级变化时具有不同的特征,构造变形煤的微晶参数较原生结构煤变化空间更大。
Metamorphism and deformation of coal not only have an important impact on its macroscopic characteristics,but also affect its microcrystalline structure. The microcrystalline structure of coal is one of the intrinsic factors that affect the physical properties of coal reservoir. In order to study the evolution characteristics of microcrystalline structure of different metamorphic and deformed coal,X-ray diffraction( XRD) was used for studying the microcrystalline structure parameters of different metamorphic and deformed coals in the whole coal ranks. The results showed that,with the increase of coal rank,interplanar distance d002 decreased gradually,stacking height Lcand aromatic layer mumber Ncincreased gradually,which showed a certain stage,and the values of above parameters tended to be stable eventually. The relationship between Laand Ro,maxwas linear,and the value increased with the increase of coal rank. Tectonic deformation of coal lengthened the variation range of microcrystalline parameters of coal,and made coal microcrystalline structure evolved ahead of time in the basis of metamorphism. The tectonic deformation of coal had a positive effect on the increase of Lc,Laand Nc. The weak tectonic deformation had little effect on the final stability value of d002,and the final stability value of d002 for strong tectonic coal was smaller than that of raw coal. The microcrystalline parameters of raw coal,the weak and strong tectonic coal had different characteristics with the changed of coal rank. The microcrystalline parameters for the tectonic deformed coal change more widely than that of raw coal.
Metamorphism and deformation of coal not only have an important impact on its macroscopic characteristics,but also affect its microcrystalline structure. The microcrystalline structure of coal is one of the intrinsic factors that affect the physical properties of coal reservoir. In order to study the evolution characteristics of microcrystalline structure of different metamorphic and deformed coal,X-ray diffraction( XRD) was used for studying the microcrystalline structure parameters of different metamorphic and deformed coals in the whole coal ranks. The results showed that,with the increase of coal rank,interplanar distance d002 decreased gradually,stacking height Lcand aromatic layer mumber Ncincreased gradually,which showed a certain stage,and the values of above parameters tended to be stable eventually. The relationship between Laand Ro,maxwas linear,and the value increased with the increase of coal rank. Tectonic deformation of coal lengthened the variation range of microcrystalline parameters of coal,and made coal microcrystalline structure evolved ahead of time in the basis of metamorphism. The tectonic deformation of coal had a positive effect on the increase of Lc,Laand Nc. The weak tectonic deformation had little effect on the final stability value of d002,and the final stability value of d002 for strong tectonic coal was smaller than that of raw coal. The microcrystalline parameters of raw coal,the weak and strong tectonic coal had different characteristics with the changed of coal rank. The microcrystalline parameters for the tectonic deformed coal change more widely than that of raw coal.
引文
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[2] MARZEC ANNA. Towards an understanding of the coal structure:A review[J]. Fuel Processing Technology,2002,77(25):25-32.
[3] PEPPAS N A,LUCHT L M. Macromolecular structure of coals:I. The organic phase of bituminous coals as a macromolecular network[J]. Chemical Engineering Communications,1984,30(3-5):291-310.
[4] TAKAGI H,MARUYAMA K,YOSHIZAWA N,et al.XRD analysis of carbon stacking structure in coal during heat treatment[J]. Fuel,2004,83(17):2427-2433.
[5] SAIKIA BINOY K,BORUAH R K,GOGOI P K. FT-IR and XRD analysis of coal from Makum coalfield of Assam[J]. Journal of Earth System Science,2007,116(6):575-579.
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[9]罗陨飞,李文华.中低变质程度煤显微组分大分子结构的XRD研究[J].煤炭学报,2004,29(3):338-341.LUO Y F,LI W H. XRD study of macromolecular structure of medium-low metamorphic coal[J]. Journal of China Coal Society,2004,29(3):338-341.
[10]宋党育,张小东.应用XRD对煤微晶结构的研究[C]//中国煤炭学会第三届瓦斯地质专业委员会第九次全国学术年会,2009.SONG D Y,ZHANG X D. The study of coal microcrystalline structure by XRD[J]. The China coal society,2009.
[11]苏现波,司青,王乾.煤变质演化过程中的XRD响应[J].河南理工大学学报(自然科学版),2016,35(4):487-492.SU X B,SI Q,WANG Q. XRD response in the process of coal metamorphism[J]. Journal of Henan Polytechnic University(Natural Science),2016,35(4):487-492.
[12]王崇敬,曹代勇,陈健明,等.聚集型高演化天然固体沥青成因——以湘西脉状碳沥青为例[J].科技导报,2014,32(24):40-45.WANG C J,CAO D Y,CHEN J M,et al. The formation of highly evolved high evolution natural solid bitumen:Taking Xiangxi pulse carbon asphalt as an example[J]. Science&Technology Review,2014,32(24):40-45.
[13]李霞,曾凡桂,王威,等.低中煤级煤结构演化的XRD表征[J].燃料化学学报,2016,44(7):777-783.LI X,CENG F G,WANG W,et al. XRD characterization of the evolution of low and middle coal grade coal structure[J]. Journal of Fuel Chemistry and Technology,2016,44(7):777-783.
[14]姜波,秦勇.高温高压实验变形煤XRD结构演化[J].煤炭学报,1998,23(2):188-193.JIANG B,QIN Y. XRD structure evolution of deformed coal at high temperature and high pressure[J]. Journal of China Coal Society,1998,23(2):188-193.
[15]姜波,秦勇.高煤级构造煤的XRD结构及其构造地质意义[J].中国矿业大学学报,1998(2):115-118.JIANG B,QIN Y. XRD structure of high coal grade coal and its tectonic significance[J]. Journal of China University of Mining&Technology,1998(2):115-118.
[16]白何领,潘结南,赵艳青,等.不同变质程度脆性变形煤的XRD研究[J].煤矿安全,2013,44(11):12-14.BAI H L,PAN J N,ZHAO Y Q,et al. XRD study of brittle deformed coal with different metamorphism[J].Safety in Coal Mines,2013,44(11):12-14.
[17]琚宜文,林红,李小诗,等.煤岩构造变形与动力变质作用[J].地学前缘,2009(1):158-166JU Y W,LIN H,LI X S,et al. Structural deformation and dynamic metamorphism of coal petrography[J].Earth Science Frontiers,2009(1):158-166.
[18]琚宜文,姜波,侯泉林,等.构造煤13C NMR谱及其结构成分的应力效应[J].中国科学,2005,35(9):847-861.JU Y W,JIANG B,HOU Q L,et al. The stress effect of13C NMR spectra and its structural components[J].SCIENCE CHINA PRESS,2005,35(9):847-861.
[19]李小明,曹代勇,张守仁,等.不同变质类型煤的XRD结构演化特征[J].煤田地质与勘探,2003,31(3):5-7.LI X M,CAO D Y,ZHANG S R,et al. Evolution characteristics of XRD structure of different metamorphic types of coal[J]. Coal Geology&Exploration,2003,31(3):5-7.
[20]屈争辉,姜波,汪吉林,等.不同煤级煤大分子结构对应力-应变环境的响应分析[J].中国矿业大学学报,2015,44(4):656-663.QU Z H,JIANG B,WANG J L,et al. The analysis of different large molecular structure of coal in the stressstrain environment[J]. Journal of China University of Mining&Technology,2015,44(4):656-663.
[21] SONIBARE OLUWADAYO O,HAEGER TOBIAS,FOLEY STEPHEN F. Structural characterization of Nigerian coals by X-ray diffraction,Raman and FTIR spectroscopy[J]. Energy,2010,35(12):5347-5353.
[22] BUSTIN R M,ROSS J V,ROUZAUD J N. Mechanisms of graphite formation from kerogen:experimental evidence[J]. International Journal of Coal Geology,1995,28(1):1-36.
[23]曲星武,王金城.煤的X射线分析[J].煤田地质与勘探,1980(2):36-43.QU X W,WANG J C. X ray analysis of coal[J]. Coal Geology&Exploration,1980(2):36-43.
[24] PAN J N,HOU Q L,JU Y W,et al. Coalbed methane sorption related to coal deformation structures at different temperatures and pressures[J]. Fuel,2012,102(6):760-765.
[25] PAN J N,WANG S,JU Y W,et al. Quantitative study of the macromolecular structures of tectonically deformed coal using high-resolution transmission electron microscopy[J]. Journal of Natural Gas Science&Engineering,2015,27:1852-1862.
[26] PAN J N,LI M,BAI H L,et al. Effects of metamorphism and deformation on the coal macromolecular structure by laser Raman spectroscopy[J]. Energy&Fuels,2017,31(2):1136-1146.
[27]王丽,张蓬洲.煤的XRD的结构分析[J].煤炭转化,1997(1):50-53.WANG L,ZHANG P Z. Structural analysis of coal XRD[J]. Coal Conversion,1997(1):50-53.
[28]田承圣,曾凡桂.镜煤与丝炭结构的X射线衍射初步分析[J].太原理工大学学报,2001,32(2):102-105.TIAN C S,CENG F G. The structure analysis of X ray diffraction of vitrain and fusain[J]. Journal of Taiyuan University of Technology,2001,32(2):102-105.
[29]张小东,张鹏.不同煤级煤分级萃取后的XRD结构特征及其演化机理[J].煤炭学报,2014,39(5):941-946.ZHANG X D,ZHANG P. XRD structure characteristics and evolution mechanism of different coal rank after fractionated extraction[J]. Journal of China Coal Society,2014,39(5):941-946.
[30] DE FONTON S,OBERLIN A,INAGAKi M. Characterization by electron microscopy of carbon phases(intermediate turbostratic phase and graphite)in hard carbons when heat-treated under pressure[J]. Journal of Materials Science,1980,15(4):909-917.
[31]姜波,秦勇,宋党育,等.高煤级构造煤的XRD结构及其构造地质意义[J].中国矿业大学学报,1998(2):115-118.JIANG B,QIN Y,SONG D Y,et al. XRD structure of high rank structural coal and its tectonic significance[J]. Journal of China University of Mining&Technology,1998(2):115-118.
[32] LI X S,JU Y W,HOU Q L,et al. Response of macromolecular structure to deformation in tectonically deformed coal[J]. Acta Geologica Sinica(English Edition),2013,87(1):82-90.
[33]张小兵,王蔚,张玉贵,等.构造煤微晶取向生长机制探讨[J].煤炭学报,2016,41(3):712-718.ZHANG X B,WANG Y,ZHANG Y G,et al. The mechanism study of microcrystalline orientation growth of structural coal[J]. Journal of China Coal Society,2016,41(3):712-718.
[2] MARZEC ANNA. Towards an understanding of the coal structure:A review[J]. Fuel Processing Technology,2002,77(25):25-32.
[3] PEPPAS N A,LUCHT L M. Macromolecular structure of coals:I. The organic phase of bituminous coals as a macromolecular network[J]. Chemical Engineering Communications,1984,30(3-5):291-310.
[4] TAKAGI H,MARUYAMA K,YOSHIZAWA N,et al.XRD analysis of carbon stacking structure in coal during heat treatment[J]. Fuel,2004,83(17):2427-2433.
[5] SAIKIA BINOY K,BORUAH R K,GOGOI P K. FT-IR and XRD analysis of coal from Makum coalfield of Assam[J]. Journal of Earth System Science,2007,116(6):575-579.
[6]翁成敏,潘治贵.峰峰煤田煤的X射线衍射分析[J].地球科学,1981(1):218-225.WENG C M,PAN Z G. X-ray diffraction analysis of coal in Fengfeng coal field[J]. Journal of Earth Science,1981(1):218-225.
[7]曲星武,王金城.煤的X射线分析[J].煤田地质与勘探,1980(2):36-43.QU X W,WANG J C. X ray analysis of coal[J]. Coal Geology&Exploration,1980(2):36-43.
[8]张代钧,鲜学福.煤结构的X射线分析[J].西安科技大学学报,1990(3):42-49.ZHANG D J,XIAN X F. X-ray analysis of the coal structure[J]. Journal of Xi’an University of Science and Technology,1990(3):42-49.
[9]罗陨飞,李文华.中低变质程度煤显微组分大分子结构的XRD研究[J].煤炭学报,2004,29(3):338-341.LUO Y F,LI W H. XRD study of macromolecular structure of medium-low metamorphic coal[J]. Journal of China Coal Society,2004,29(3):338-341.
[10]宋党育,张小东.应用XRD对煤微晶结构的研究[C]//中国煤炭学会第三届瓦斯地质专业委员会第九次全国学术年会,2009.SONG D Y,ZHANG X D. The study of coal microcrystalline structure by XRD[J]. The China coal society,2009.
[11]苏现波,司青,王乾.煤变质演化过程中的XRD响应[J].河南理工大学学报(自然科学版),2016,35(4):487-492.SU X B,SI Q,WANG Q. XRD response in the process of coal metamorphism[J]. Journal of Henan Polytechnic University(Natural Science),2016,35(4):487-492.
[12]王崇敬,曹代勇,陈健明,等.聚集型高演化天然固体沥青成因——以湘西脉状碳沥青为例[J].科技导报,2014,32(24):40-45.WANG C J,CAO D Y,CHEN J M,et al. The formation of highly evolved high evolution natural solid bitumen:Taking Xiangxi pulse carbon asphalt as an example[J]. Science&Technology Review,2014,32(24):40-45.
[13]李霞,曾凡桂,王威,等.低中煤级煤结构演化的XRD表征[J].燃料化学学报,2016,44(7):777-783.LI X,CENG F G,WANG W,et al. XRD characterization of the evolution of low and middle coal grade coal structure[J]. Journal of Fuel Chemistry and Technology,2016,44(7):777-783.
[14]姜波,秦勇.高温高压实验变形煤XRD结构演化[J].煤炭学报,1998,23(2):188-193.JIANG B,QIN Y. XRD structure evolution of deformed coal at high temperature and high pressure[J]. Journal of China Coal Society,1998,23(2):188-193.
[15]姜波,秦勇.高煤级构造煤的XRD结构及其构造地质意义[J].中国矿业大学学报,1998(2):115-118.JIANG B,QIN Y. XRD structure of high coal grade coal and its tectonic significance[J]. Journal of China University of Mining&Technology,1998(2):115-118.
[16]白何领,潘结南,赵艳青,等.不同变质程度脆性变形煤的XRD研究[J].煤矿安全,2013,44(11):12-14.BAI H L,PAN J N,ZHAO Y Q,et al. XRD study of brittle deformed coal with different metamorphism[J].Safety in Coal Mines,2013,44(11):12-14.
[17]琚宜文,林红,李小诗,等.煤岩构造变形与动力变质作用[J].地学前缘,2009(1):158-166JU Y W,LIN H,LI X S,et al. Structural deformation and dynamic metamorphism of coal petrography[J].Earth Science Frontiers,2009(1):158-166.
[18]琚宜文,姜波,侯泉林,等.构造煤13C NMR谱及其结构成分的应力效应[J].中国科学,2005,35(9):847-861.JU Y W,JIANG B,HOU Q L,et al. The stress effect of13C NMR spectra and its structural components[J].SCIENCE CHINA PRESS,2005,35(9):847-861.
[19]李小明,曹代勇,张守仁,等.不同变质类型煤的XRD结构演化特征[J].煤田地质与勘探,2003,31(3):5-7.LI X M,CAO D Y,ZHANG S R,et al. Evolution characteristics of XRD structure of different metamorphic types of coal[J]. Coal Geology&Exploration,2003,31(3):5-7.
[20]屈争辉,姜波,汪吉林,等.不同煤级煤大分子结构对应力-应变环境的响应分析[J].中国矿业大学学报,2015,44(4):656-663.QU Z H,JIANG B,WANG J L,et al. The analysis of different large molecular structure of coal in the stressstrain environment[J]. Journal of China University of Mining&Technology,2015,44(4):656-663.
[21] SONIBARE OLUWADAYO O,HAEGER TOBIAS,FOLEY STEPHEN F. Structural characterization of Nigerian coals by X-ray diffraction,Raman and FTIR spectroscopy[J]. Energy,2010,35(12):5347-5353.
[22] BUSTIN R M,ROSS J V,ROUZAUD J N. Mechanisms of graphite formation from kerogen:experimental evidence[J]. International Journal of Coal Geology,1995,28(1):1-36.
[23]曲星武,王金城.煤的X射线分析[J].煤田地质与勘探,1980(2):36-43.QU X W,WANG J C. X ray analysis of coal[J]. Coal Geology&Exploration,1980(2):36-43.
[24] PAN J N,HOU Q L,JU Y W,et al. Coalbed methane sorption related to coal deformation structures at different temperatures and pressures[J]. Fuel,2012,102(6):760-765.
[25] PAN J N,WANG S,JU Y W,et al. Quantitative study of the macromolecular structures of tectonically deformed coal using high-resolution transmission electron microscopy[J]. Journal of Natural Gas Science&Engineering,2015,27:1852-1862.
[26] PAN J N,LI M,BAI H L,et al. Effects of metamorphism and deformation on the coal macromolecular structure by laser Raman spectroscopy[J]. Energy&Fuels,2017,31(2):1136-1146.
[27]王丽,张蓬洲.煤的XRD的结构分析[J].煤炭转化,1997(1):50-53.WANG L,ZHANG P Z. Structural analysis of coal XRD[J]. Coal Conversion,1997(1):50-53.
[28]田承圣,曾凡桂.镜煤与丝炭结构的X射线衍射初步分析[J].太原理工大学学报,2001,32(2):102-105.TIAN C S,CENG F G. The structure analysis of X ray diffraction of vitrain and fusain[J]. Journal of Taiyuan University of Technology,2001,32(2):102-105.
[29]张小东,张鹏.不同煤级煤分级萃取后的XRD结构特征及其演化机理[J].煤炭学报,2014,39(5):941-946.ZHANG X D,ZHANG P. XRD structure characteristics and evolution mechanism of different coal rank after fractionated extraction[J]. Journal of China Coal Society,2014,39(5):941-946.
[30] DE FONTON S,OBERLIN A,INAGAKi M. Characterization by electron microscopy of carbon phases(intermediate turbostratic phase and graphite)in hard carbons when heat-treated under pressure[J]. Journal of Materials Science,1980,15(4):909-917.
[31]姜波,秦勇,宋党育,等.高煤级构造煤的XRD结构及其构造地质意义[J].中国矿业大学学报,1998(2):115-118.JIANG B,QIN Y,SONG D Y,et al. XRD structure of high rank structural coal and its tectonic significance[J]. Journal of China University of Mining&Technology,1998(2):115-118.
[32] LI X S,JU Y W,HOU Q L,et al. Response of macromolecular structure to deformation in tectonically deformed coal[J]. Acta Geologica Sinica(English Edition),2013,87(1):82-90.
[33]张小兵,王蔚,张玉贵,等.构造煤微晶取向生长机制探讨[J].煤炭学报,2016,41(3):712-718.ZHANG X B,WANG Y,ZHANG Y G,et al. The mechanism study of microcrystalline orientation growth of structural coal[J]. Journal of China Coal Society,2016,41(3):712-718.