The macromolecular structure of tectonically deformed coals(TDC)may be determined by the deformation mechanisms of coal.Alterations of the macromolecular structure change the pore structure of TDC and thereby impact p...The macromolecular structure of tectonically deformed coals(TDC)may be determined by the deformation mechanisms of coal.Alterations of the macromolecular structure change the pore structure of TDC and thereby impact physical properties such as porosity and permeability.This study focuses on structure and properties of TDC from the Huaibei and Huainan coal mining areas of southern North China.Relationships between the macromolecular structure and the pore structure of TDC were analyzed using techniques such as X-ray diffraction,high-resolution transmission electron microcopy,and the low-temperature nitrogen adsorption.The results indicated that the directional stress condition can cause the arrangement of basic structural units(BSU)more serious and closer.And,the orientation is stronger in ductile deformed coal than in brittle deformed coal.Tectonic deformation directly influences the macromolecular structure of coal and consequently results in dynamic metamorphism.Because the size of BSU in brittle deformed coal increases more slowly than in ductile deformed coal,frictional heating and stress-chemistry of shearing areas might play a more important role,locally altering coal structure under stress,in brittle deformed coal.Strain energy is more significant in increasing the ductile deformation of coal.Furthermore,mesopores account for larger percentage of the nano-scale pore volume in brittle deformed coals,while mesopores volume in ductile deformed coal diminishes rapidly along with an increase in the proportion of micropores and sub-micropores.This research also approved that the deformations of macromolecular structures change nano-scale pore structures,which are very important for gas adsorption and pervasion space for gas.Therefore,the exploration and development potential of coal bed methane is promising for reservoirs that are subjected to a certain degree of brittle deformation(such as schistose structure coal,mortar structure coal and cataclastic structure coal).It also holds promise for TDC resulting from展开更多
There is a more consanguineous relation be-tween nano-scale deformation of coal structure and meta-morphic-deformed environment. In different metamor-phic-deformed environments, deformation in the coal struc-ture can ...There is a more consanguineous relation be-tween nano-scale deformation of coal structure and meta-morphic-deformed environment. In different metamor-phic-deformed environments, deformation in the coal struc-ture can occur not only at micro-scale, but also at nano-scale, and even leads to the change of molecular structure and nano-scale pore (<100 nm) structure. The latter is the main space absorbing coalbed methane. Through X-ray diffraction (XRD) and liquid–nitrogen absorption methods, the charac-teristics of macromolecular and nano-scale pore structures of coals in different metamorphic-deformed environments and deformational series of coals have been studied. By combin-ing with high-resolution transmission electron microcopy (HRTEM), the macromolecular and nano-scale pore struc-tures are also directly observed. These results demonstrate that the stacking Lc of the macromolecular BSU in tectonic coals increases quickly from the metamorphic-deformed environment of low rank coals to that of high rank coals. For different deformed tectonic coals, in the same metamor-phic-deformed environment, the difference of Lc is obvious. These changes reflect chiefly the difference of different tem-perature and stress effect of nano-scale deformation in tec-tonic coals. The factor of temperature plays a greater role in the increase of macromolecular structure parameters Lc, the influence of stress factor is also important. With the stress strengthening, Lc shows an increasing trend, and La /Lc shows a decreasing trend. Therefore, Lc and La /Lc can be used as the indicator of nano-scale deformation degree of tectonic coals. With increasing temperature and pressure, especially oriented stress, the orientation of molecular structure be-comes stronger, and ordering degree of C-nets and the ar-rangement of BSU are obviously enhanced. For the deforma-tion of nano-scale pore structure, in the same metamor-phic-deformed environment, along with the strengthening of stress, the ratio of mesopores to its total pores volume of tec-toni展开更多
High-resolution 13C Nuclear Magnetic Resonance (NMR) spectra of different kinds of tectonic coals were obtained using the NMR (CP/MAS+TOSS) method. On the basis of this, after simulation synthesis and division of spec...High-resolution 13C Nuclear Magnetic Resonance (NMR) spectra of different kinds of tectonic coals were obtained using the NMR (CP/MAS+TOSS) method. On the basis of this, after simulation synthesis and division of spectra, the relative contents of carbon functional groups were calculated. Combined with results of Ro, max, XRD testing and element analysis, stress effects on the composition of macromolecular structures in tectonic coals were studied further. The results showed that Ro, max was not only the important index for describing coal rank, but was also effective for estimating the stress effect of tectonic coals. Under tectonic stress ac- tion, Ro, max was the most direct indicator of the coal structure and chemical components. Changes in the stacking Lc of the coal basic structure unit (BSU) and La/Lc parameters could distinguish the temperature and stress effects on metamorphic-deformed environments, and re- flected the degree of structural deformation. Therefore, on the whole, Lc and La/Lc can be used to index of the degree of structural deformation of tectonic coals. In different metamorphic and de- formed environments, different kinds of tectonic coals are formed under structural stress. The changes in characteristics of the macromolecular structure and chemical composition are such that as the increase in structural deformation becomes stronger, from the brittle deformation coal to ductile deformation coal, the ratio of width at the half height of the aromatic carbon and ali- phatic carbon peaks (Hfa/Hfal ) was increased. As carbon aromaticity was raised further, carbon aliphaticity reduced obviously and different compositions of macromolecular structure appeared as a jump and wave pattern except for in wrinkle structure coal, which might result chiefly from stress effects on the macromolecular structure of different kinds of tectonic coals. The macro- moecular changes of wrinkle structure coal are reflected mainly on physical structure. In the metamorphic and deformed environments of the middle and hi展开更多
Coals with different deformation mechanisms(brittle deformation,brittle-ductile deformation,and ductile deformation) repre-sent different ways in macromolecular structure evolution based on the metamorphism.The evolut...Coals with different deformation mechanisms(brittle deformation,brittle-ductile deformation,and ductile deformation) repre-sent different ways in macromolecular structure evolution based on the metamorphism.The evolution of coal structure could affect the occurrence condition of coalbed methane(CBM) because the nanopore structure affected by macromolecular struc-ture is the most important reservoir for CBM.This paper analyzes the evolutions and mechanisms of structure and functional group of tectonically deformed coals(TDCs) collected from Huainan-Huaibei coalfield using X-ray diffraction(XRD),Raman spectroscopy,and Fourier Transform Infrared(FTIR) spectroscopy methods.The results show that the macromolecular struc-ture evolutions of TDC are different from the primary structure coal as a result of the different metamorphic grade and defor-mation mechanisms.The different deformation mechanisms variously affect the process of functional group and polyconden-sation of macromolecular structure.Furthermore,the tectonic deformation leads to secondary structural defects and reduces the structure stability of TDC.The coupled evolution on stacking and extension caused by the changes of secondary structural de-fects results from different deformation mechanisms.We consider that the changes of chemical structure and secondary struc-tural defects are the primary reasons for the various structure evolutions of TDC compared with primary structure coal.展开更多
The structural evolution of tectonically deformed coals （TDC） with different deformational mechanisms and different deformational intensities are investigated in depth through X-ray diffraction （XRD） analysis on 3...The structural evolution of tectonically deformed coals （TDC） with different deformational mechanisms and different deformational intensities are investigated in depth through X-ray diffraction （XRD） analysis on 31 samples of different metamorphic grades （R ： 0.7%-3.1%） collected from the Huaibei coalfield. The results indicated that there are different evolution characteristics between the ductile and brittle deformational coals with increasing of metamorphism and deformation. On the one hand, with the increase of metamorphism, the atomic plane spacing （d002） is decreasing at step velocity, the stacking of the BSU layer （Lc） is increasing at first and then decreasing, but the extension of the BSU layer （La） and the ratio of La/Lc are decreasing initially and then increasing. On the other hand, for the brittle deformational coal, d002 is increasing initially and then decreasing, which causes an inversion of the variation of Lc and La under the lower-middle or higher-middle metamorphism grade when the deformational intensity was increasing. In contrast, in the ductile deformational coals, d002 decreased initially and then increased, and the value of L~ decreased with the increase of deformational intensity. But the value of La increased under the lower-middle metamorphism grade and increased at first and then decreased under the higher-middle metamorphism grade. We conclude that the degradation and polycondensation of TDC macromolecular structure can be obviously impacted during the ductile deformational process, because the increase and accumulation of unit dislocation perhaps transforms the stress into strain energy. Meanwhile, the brittle deformation can transform the stress into frictional heat energy, and promote the metamorphism and degradation as well. It can be concluded that deformation is more important than metamorphism to the differential evolution of the ductile and brittle deformational coals.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.40772135,4097213141030422)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA05030100)National Science and Technology Major Project(No.2011ZX05060-005).
文摘The macromolecular structure of tectonically deformed coals(TDC)may be determined by the deformation mechanisms of coal.Alterations of the macromolecular structure change the pore structure of TDC and thereby impact physical properties such as porosity and permeability.This study focuses on structure and properties of TDC from the Huaibei and Huainan coal mining areas of southern North China.Relationships between the macromolecular structure and the pore structure of TDC were analyzed using techniques such as X-ray diffraction,high-resolution transmission electron microcopy,and the low-temperature nitrogen adsorption.The results indicated that the directional stress condition can cause the arrangement of basic structural units(BSU)more serious and closer.And,the orientation is stronger in ductile deformed coal than in brittle deformed coal.Tectonic deformation directly influences the macromolecular structure of coal and consequently results in dynamic metamorphism.Because the size of BSU in brittle deformed coal increases more slowly than in ductile deformed coal,frictional heating and stress-chemistry of shearing areas might play a more important role,locally altering coal structure under stress,in brittle deformed coal.Strain energy is more significant in increasing the ductile deformation of coal.Furthermore,mesopores account for larger percentage of the nano-scale pore volume in brittle deformed coals,while mesopores volume in ductile deformed coal diminishes rapidly along with an increase in the proportion of micropores and sub-micropores.This research also approved that the deformations of macromolecular structures change nano-scale pore structures,which are very important for gas adsorption and pervasion space for gas.Therefore,the exploration and development potential of coal bed methane is promising for reservoirs that are subjected to a certain degree of brittle deformation(such as schistose structure coal,mortar structure coal and cataclastic structure coal).It also holds promise for TDC resulting from
基金This work was supported by the National Key Development Plan Project of Basic Research(973 Plan)(Grant No.2002CB211704)the National N atural Science Foundation of China(Grant No.40172058)+1 种基金China Postdoctoral Science Foundation(Grant No.200403508)Kuancheng Wang Post-doctoral Research Award Fund of Chinese Academy of Sciences.
文摘There is a more consanguineous relation be-tween nano-scale deformation of coal structure and meta-morphic-deformed environment. In different metamor-phic-deformed environments, deformation in the coal struc-ture can occur not only at micro-scale, but also at nano-scale, and even leads to the change of molecular structure and nano-scale pore (<100 nm) structure. The latter is the main space absorbing coalbed methane. Through X-ray diffraction (XRD) and liquid–nitrogen absorption methods, the charac-teristics of macromolecular and nano-scale pore structures of coals in different metamorphic-deformed environments and deformational series of coals have been studied. By combin-ing with high-resolution transmission electron microcopy (HRTEM), the macromolecular and nano-scale pore struc-tures are also directly observed. These results demonstrate that the stacking Lc of the macromolecular BSU in tectonic coals increases quickly from the metamorphic-deformed environment of low rank coals to that of high rank coals. For different deformed tectonic coals, in the same metamor-phic-deformed environment, the difference of Lc is obvious. These changes reflect chiefly the difference of different tem-perature and stress effect of nano-scale deformation in tec-tonic coals. The factor of temperature plays a greater role in the increase of macromolecular structure parameters Lc, the influence of stress factor is also important. With the stress strengthening, Lc shows an increasing trend, and La /Lc shows a decreasing trend. Therefore, Lc and La /Lc can be used as the indicator of nano-scale deformation degree of tectonic coals. With increasing temperature and pressure, especially oriented stress, the orientation of molecular structure be-comes stronger, and ordering degree of C-nets and the ar-rangement of BSU are obviously enhanced. For the deforma-tion of nano-scale pore structure, in the same metamor-phic-deformed environment, along with the strengthening of stress, the ratio of mesopores to its total pores volume of tec-toni
基金supported by the National Key Basic Research Development Plan Project(973)(Grant No.2002CB211704)the National Natural Science Foundation of China(Grant No.40172058)+1 种基金the China Postdoctoral Science Foundation(Grant No.200403508)Kuancheng Wang Postdoctoral Research AwardFund of the Chinese Academy of Sciences.
文摘High-resolution 13C Nuclear Magnetic Resonance (NMR) spectra of different kinds of tectonic coals were obtained using the NMR (CP/MAS+TOSS) method. On the basis of this, after simulation synthesis and division of spectra, the relative contents of carbon functional groups were calculated. Combined with results of Ro, max, XRD testing and element analysis, stress effects on the composition of macromolecular structures in tectonic coals were studied further. The results showed that Ro, max was not only the important index for describing coal rank, but was also effective for estimating the stress effect of tectonic coals. Under tectonic stress ac- tion, Ro, max was the most direct indicator of the coal structure and chemical components. Changes in the stacking Lc of the coal basic structure unit (BSU) and La/Lc parameters could distinguish the temperature and stress effects on metamorphic-deformed environments, and re- flected the degree of structural deformation. Therefore, on the whole, Lc and La/Lc can be used to index of the degree of structural deformation of tectonic coals. In different metamorphic and de- formed environments, different kinds of tectonic coals are formed under structural stress. The changes in characteristics of the macromolecular structure and chemical composition are such that as the increase in structural deformation becomes stronger, from the brittle deformation coal to ductile deformation coal, the ratio of width at the half height of the aromatic carbon and ali- phatic carbon peaks (Hfa/Hfal ) was increased. As carbon aromaticity was raised further, carbon aliphaticity reduced obviously and different compositions of macromolecular structure appeared as a jump and wave pattern except for in wrinkle structure coal, which might result chiefly from stress effects on the macromolecular structure of different kinds of tectonic coals. The macro- moecular changes of wrinkle structure coal are reflected mainly on physical structure. In the metamorphic and deformed environments of the middle and hi
基金supported by National Natural Science Foundation of China (Grant Nos.40772135,40972131 and 41030422)National Basic Research Program of China (Grant Nos.2009CB219601 and 2006CB202201)Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No.XDA05030100)
文摘Coals with different deformation mechanisms(brittle deformation,brittle-ductile deformation,and ductile deformation) repre-sent different ways in macromolecular structure evolution based on the metamorphism.The evolution of coal structure could affect the occurrence condition of coalbed methane(CBM) because the nanopore structure affected by macromolecular struc-ture is the most important reservoir for CBM.This paper analyzes the evolutions and mechanisms of structure and functional group of tectonically deformed coals(TDCs) collected from Huainan-Huaibei coalfield using X-ray diffraction(XRD),Raman spectroscopy,and Fourier Transform Infrared(FTIR) spectroscopy methods.The results show that the macromolecular struc-ture evolutions of TDC are different from the primary structure coal as a result of the different metamorphic grade and defor-mation mechanisms.The different deformation mechanisms variously affect the process of functional group and polyconden-sation of macromolecular structure.Furthermore,the tectonic deformation leads to secondary structural defects and reduces the structure stability of TDC.The coupled evolution on stacking and extension caused by the changes of secondary structural de-fects results from different deformation mechanisms.We consider that the changes of chemical structure and secondary struc-tural defects are the primary reasons for the various structure evolutions of TDC compared with primary structure coal.
基金supported by the National Natural Science Foundation of China(Grant Nos.41030422, 40972131,40772135 and 41202120)the National Basic Research Program of China(Grant Nos.2009CB219601 and 2006CB202201)the China Postdoctoral Science Foundation Funded Project(2012M510590)
文摘The structural evolution of tectonically deformed coals （TDC） with different deformational mechanisms and different deformational intensities are investigated in depth through X-ray diffraction （XRD） analysis on 31 samples of different metamorphic grades （R ： 0.7%-3.1%） collected from the Huaibei coalfield. The results indicated that there are different evolution characteristics between the ductile and brittle deformational coals with increasing of metamorphism and deformation. On the one hand, with the increase of metamorphism, the atomic plane spacing （d002） is decreasing at step velocity, the stacking of the BSU layer （Lc） is increasing at first and then decreasing, but the extension of the BSU layer （La） and the ratio of La/Lc are decreasing initially and then increasing. On the other hand, for the brittle deformational coal, d002 is increasing initially and then decreasing, which causes an inversion of the variation of Lc and La under the lower-middle or higher-middle metamorphism grade when the deformational intensity was increasing. In contrast, in the ductile deformational coals, d002 decreased initially and then increased, and the value of L~ decreased with the increase of deformational intensity. But the value of La increased under the lower-middle metamorphism grade and increased at first and then decreased under the higher-middle metamorphism grade. We conclude that the degradation and polycondensation of TDC macromolecular structure can be obviously impacted during the ductile deformational process, because the increase and accumulation of unit dislocation perhaps transforms the stress into strain energy. Meanwhile, the brittle deformation can transform the stress into frictional heat energy, and promote the metamorphism and degradation as well. It can be concluded that deformation is more important than metamorphism to the differential evolution of the ductile and brittle deformational coals.
基金supported by the Natural Scientific Foundation of China(21476004,21476003,21476002,51174254)Natural Science Foundation of Anhui Provincial Education Department(KJ2016A808)the Provincial Innovative Group for Processing & Clean Utilization of Coal Resource and the Innovative Group of Anhui University of Technology
