Molecular structure characterization of middle-high rank coal via^(13)C NMR,XPS,and FTIR spectroscopy

Elemental analysis,nuclear magnetic resonance carbon spectroscopy(^(13)C-NMR),X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)experiments were carried out to determine the existence of aromatic structure,heteroatom structure and fat structure in coal.MS(materials studio)software was used to optimize and construct a 3D molecular structure model of coal.A method for establishing a coal molecular structure model was formed,which was“determination of key structures in coal,construction of planar molecular structure model,and optimization of three-dimensional molecular structure model”.The structural differences were compared and analyzed.The results show that with the increase of coal rank,the dehydrogenation of cycloalkanes in coal is continuously enhanced,and the content of heteroatoms in the aromatic ring decreases.The heteroatoms and branch chains in the coal are reduced,and the structure is more orderly and tight.The stability of the structure is determined by theπ-πinteraction between the aromatic rings in the nonbonding energy EN.Key Stretching Energy The size of EB determines how tight the structure is.The research results provide a method and reference for the study of the molecular structure of medium and high coal ranks.

Structural properties of residual carbon in coal gasification fine slag and their influence on flotation separation and resource utilization:A review

Coal gasification fine slag(FS)is a typical solid waste generated in coal gasification.Its current disposal methods of stockpil-ing and landfilling have caused serious soil and ecological hazards.Separation recovery and the high-value utilization of residual carbon(RC)in FS are the keys to realizing the win-win situation of the coal chemical industry in terms of economic and environmental benefits.The structural properties,such as pore,surface functional group,and microcrystalline structures,of RC in FS(FS-RC)not only affect the flotation recovery efficiency of FS-RC but also form the basis for the high-value utilization of FS-RC.In this paper,the characteristics of FS-RC in terms of pore structure,surface functional groups,and microcrystalline structure are sorted out in accordance with gasification type and FS particle size.The reasons for the formation of the special structural properties of FS-RC are analyzed,and their influence on the flotation separation and high-value utilization of FS-RC is summarized.Separation methods based on the pore structural characterist-ics of FS-RC,such as ultrasonic pretreatment-pore-blocking flotation and pore breaking-flocculation flotation,are proposed to be the key development technologies for improving FS-RC recovery in the future.The design of low-cost,low-dose collectors containing polar bonds based on the surface and microcrystalline structures of FS-RC is proposed to be an important breakthrough point for strengthening the flotation efficiency of FS-RC in the future.The high-value utilization of FS should be based on the physicochemical structural proper-ties of FS-RC and should focus on the environmental impact of hazardous elements and the recyclability of chemical waste liquid to es-tablish an environmentally friendly utilization method.This review is of great theoretical importance for the comprehensive understand-ing of the unique structural properties of FS-RC,the breakthrough of the technological bottleneck in the efficient flotation separation of FS,and the expansion of the field of the high value-added utilization of FS-RC.

Effect of demineralization on pyrolysis characteristics of LPS coal based on its chemical structure

The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupanshui raw coal(LPS-R)and Liupanshui demineralized coal(LPS-D)were analyzed by FTIR and solid-state 13C-NMR.The pyrolysis experiments were carried out by TG,and the pyrolysis kinetics was analyzed by three iso-conversional methods.FTIR and 13C-NMR results suggested that the carbon structure of LPS coal was not altered greatly,while demineralization promoted the maturity of coal and the condensation degree of the aromatic ring,making the chemical structure of coal more stable.The oxygen-containing functional groups with low bond energy were reduced,and the ratio of aromatic carbon with high bond energy was increased,decreasing the pyrolysis reactivity.DTG curve-fitting results revealed that the thermal weight loss of LPS coal mainly came from the cleavage of aliphatic covalent bonds.By pyrolysis kinetics analysis of LPS-R and LPS-D,the apparent activation energies were 76±4 to 463±5 kJ/mol and 84±2 to 758±12 kJ/mol,respectively,under different conversion rates.The reactivity of the demineralized coal was inhibited to some extent,as the apparent activation energy of pyrolysis for LPS-D increased by acid treatment.

Pore structure of low‑permeability coal and its deformation characteristics during the adsorption–desorption of CH4/N2

The pore structure of coal plays a key role in controlling the storage and migration of CH4/N2.The pore structure of coal is an important indicator to measure the gas extraction capability and the gas displacement efect of N2 injection.The deformation characteristic of coal during adsorption–desorption of CH4/N2 is an important factor afecting CH4 pumpability and N2 injectability.The pore structure characteristics of low-permeability coal were obtained by fuid intrusion method and photoelectric radiation technology.The multistage and connectivity of coal pores were analyzed.Subsequently,a simultaneous test experiment of CH4/N2 adsorption–desorption and coal deformation was carried out.The deformation characteristics of coal were clarifed and a coal strain model was constructed.Finally,the applicability of low-permeability coal to N2 injection for CH4 displacement technology was investigated.The results show that the micropores and transition pores of coal samples are relatively developed.The pore morphology of coal is dominated by semi-open pores.The pore structure of coal is highly complex and heterogeneous.Transition pores,mesopores and macropores of coal have good connectivity,while micropores have poor connectivity.Under constant triaxial stress,the adsorption capacity of the coal for CH4 is greater than that for N2,and the deformation capacity of the coal for CH4 adsorption is greater than that for N2 adsorption.The axial strain,circumferential strain,and volumetric strain during the entire process of CH4 and N2 adsorption/desorption in the coal can be divided into three stages.Coal adsorption–desorption deformation has the characteristics of anisotropy and gas-diference.A strain model for the adsorption–desorption of CH4/N2 from coal was established by considering the expansion stress of adsorbed gas on the coal matrix,the compression stress of free gas on the coal matrix,and the expansion stress of free gas on micropore fractures.N2 has good injectability in low-permeability coal seams and has the dual functions of improving coal seam permeability and enhancing gas fow,which can signifcantly improve the efectiveness of low-permeability coal seam gas control and promote the efcient utilization of gas resources.

Time-shift effect of spontaneous combustion characteristics and microstructure difference of dry-soaked coal

The physical and chemical properties of the air-dried residual coal after soaking in the goaf will change,resulting in an increase in its spontaneous combustion tendency.This study aimed to look into the features and mechanism of soaked-dried coal's spontaneous combustion.Five samples of coal were dried to various degrees,and the weight loss features during thermal processing were examined.Based on this,the pore structure and chemical structure characteristics of the coal samples with the highest tendency to spontaneous combustion were quantitatively examined,and the mechanism by which soaking-drying afected the spontaneous combustion heating process of the remaining coal in goaf was investigated in turn.The results show that T1 decreases with the increase of drying time,T2–T6 shows a fuctuating change,and the ignition activation energy of 36-S-Coal is smaller than that of other coal samples.The pore type of 36-S-Coal changes from a oneend closed impermeable pore to an open pore,and the pore group area is large.During the 36 h drying process,the internal channels of the coal were dredged,and a large number of gravels and minerals were precipitated from the pores with the air fow.A large number of gravels were around the pores to form a surface structure that was easy to adsorb various gases.Furthermore,infrared spectroscopy was used to analyze the two coal samples.It was found that soaking and drying did not change the functional group types of coal samples,but the fatty chain degree of 36-S-Coal was reduced to 1.56.It shows that the aliphatic chain structure of coal is changed after 36 h of drying after 30 days of soaking,which leads to the continuous shedding of aliphatic chain branches of residual coal,and the skeleton of coal is looser,which makes the low-temperature oxidation reaction of 36-S-Coal easier.Based on the above results,the coal-oxygen composite mechanism of water-immerseddried coal is obtained,and it is considered that the key to the spontaneous combustion oxidation process of coal is to provide oxygen atoms and accelerate the formation of peroxides.

Structure instability forecasting and analysis of giant rock pillars in steeply dipping thick coal seams

Structure stability analysis of rock masses is essential for forecasting catastrophic structure failure in coal seam mining. Steeply dipping thick coal seams （SDTCS） are common in the Urumqi coalfield, and some dynamical hazards such as roof collapse and mining-induced seismicity occur frequently in the coal mines. The cause of these events is mainly structure instability in giant rock pillars sand- wiched between SDTCS. Developing methods to predict these events is important for safe mining in such a complex environment. This study focuses on understanding the structural mechanics model of a giant rock pillar and presents a viewpoint of the stability of a trend sphenoid fractured beam （TSFB）. Some stability index parameters such as failure surface dips were measured, and most dips were observed to be between 46° and 51°. We used a digital panoramic borehole monitoring system to measure the TSFB＇s height （△H）, which varied from 56.37 to 60.50 m. Next, FLAC^3D was used to model the distribution and evolution of vertical displacement in the giant rock pillars; the results confirmed the existence of a TSFB structure. Finally, we investigated the acoustic emission （AE） energy accumulation rate and observed that the rate commonly ranged from 20 to 40 kJ/min. The AE energy accumulation rate could be used to anticipate impeding seismic events related to structure failure. The results presented provide a useful approach for forecasting catastrophic events related to structure instability and for developing hazard prevention technology for mining in SDTCS.

Constitutive model for methane desorption and diffusion based on pore structure differences between soft and hard coal

This paper aims to improve the accuracy and applicability of gas diffusion mathematical models from coal particles. Firstly, a new constitutive model for gas diffusion from coal particles with tri-disperse pore structure is constructed by considering the difference in characteristics between soft coal and hard coal.The analytical solution is then derived, that is, the quantitative relationship between gas diffusion rate(Qt/Q_∞) and diffusion time(t), The pore structure parameters of soft coal and hard coal from Juji coal mine are determined. Gas diffusion rules are numerically calculated and investigated by physical simulation methods. Lastly, the applicability of this model is verified. The results show that the homogeneous model only applies to the gas diffusion process of hard coal during the initial 10 min. The calculation results from this model and the physical experimental results of soft coal and hard coal are nearly identical during the initial 30 min.

Structure and Pozzolanic Activity of Calcined Coal Gangue during the Process of Mechanical Activation

On the basis of analyzing coal gangue＇s chemical and mineral compositions, the structure change of coal gangue during the mechanical activation was investigated by XRD, FTIR, NMR, and the mechanical strength of the cement doped coal gangue with various specific surface area was tested. The experimental results indicate that, the lattice structure of metakaolin in coal gangue samples calcined at 700 ℃ disorganizes gradually and becomes disordered, and the lattice structure of α-quartz is distorted slightly. The pozzolanic activity of the coal gangue increases obviously with its structural disorganization.

Response of Macromolecular Structure to Deformation in Tectonically Deformed Coal

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.

Prediction of coal structure using particle size characteristics of coalbed methane well cuttings

Severely deformed coal seams barely deliver satisfactory gas production. This research was undertaken to develop a new method to predict the positions of deformed coals for a horizontal CBM well. Firstly, the drilling cuttings of different structure coals were collected from a coal mine and compared. In light of the varying cuttings characteristics for different structure coals, the coal structure of the horizontally drilled coal seam was predicted. And the feasibility of this prediction method was discussed. The result shows that exogenetic fractures have an important influence on the deformation of coal seams. The hardness coefficient of coal decreases with the deformation degree in the order of primary structural, cataclastic and fragmented coal. And the expanding-ratio of gas drainage holes and the average particle size of cuttings increase with the increase of the deformation degree. The particle size distribution of coal cuttings for the three types of coals is distinctive from each other. Based on the particle size distribution of cuttings from X-2 well in a coal seam, six sections of fragmented coal which are unsuitable for perforating are predicted. This method may benefit the optimization of perforation and fracturing of a horizontal CBM well in the study area.

Chemical composition and structure characterization of distillation residues of middle-temperature coal tar

The distillation residues of middle-temperature coal tar(DRMCT) were separated into saturate, aromatic, resin and asphaltene fractions by using the combination of solvent extraction and column chromatography separation.The isolated four fractions have been further characterized through the combination of elemental analysis,Fourier transform infrared(FTIR) spectra, proton nuclear magnetic resonance spectrum(~1H NMR) and molecular weight analysis. The analysis results confirm the view that the saturate fraction from DRMCT was mainly composed of long-chain alkanes and almost all of the heteroatoms(S, N and O) were existed in aromatic structures.The asphaltene fraction had the highest molecular weight, the most amount of heteroatom(especially oxygen)and was the most condensed with shortest alkyl side chains among all the fractions. In addition, for the heavier components, the resin and asphaltene fractions from DRMCT contained lower ratio of H/C, lower molecular weight and higher aromaticity degree when compared with crude oils.

New advances in coal structure model

Although human beings have come to understand and utilize coal for a very long history, no theoretical breakthrough in the study of coal structure has been made, which still needs continuous efforts of coal chemical workers. Based on the viewpoint of ‘vague/clear', the species classification and accurate analysis on coal were conducted by using the natural clustering all-component separation method. A more systematic and detailed coal embedded structure model theory which is suitable for coal of all ranks was developed from the previous one and a more complete theoretical system about the component and structure of coal was constructed. The whole establishment process of the theory was summarized and some of the main support data and analysis test results, including TEM, AFM, FTIR, GC/MS, MALDI/TOF/MS, DART/MSD, fractal analysis and so on were provided. The coal embedded structure theory fully considers both the identity and the particularity of all-rank coal, reflects the coal component and structure in the full range of coal rank, solves the systematic cognitive problem of coal component and structure on macro and micro level, and provides a valuable and meaningful theoretical approach for the coal processing and conversion technology.

Study on seepage and deformation characteristics of coal microstructure by 3D reconstruction of CT images at high temperatures

To study the seepage and deformation characteristics of coal at high temperatures,coal samples from six different regions were selected and subjected to computed tomography(CT)scanning studies.In conjunction with ANSYS software,3 D reconstruction of CT images was used for the establishment of fluidsolid conjugate heat transfer model and coal thermal deformation model based on the microstructures of coal.In addition,the structure of coal was studied in 2 D and 3 D perspectives,followed by the analysis of seepage and deformation characteristics of coal at high temperatures.The results of this study indicated that porosity positively correlated with the fractal dimension,and the connectivity and seepage performances were roughly identical from 2 D and 3 D perspectives.As the porosity increased,the fractal dimension of coal samples became larger and the pore-fracture structures became more complex.As a result,the permeability of coal samples decreased.In the meantime,fluid was fully heated,generating high-temperature water at outlet.However,when the porosity was low,the outlet temperature was very high.The average deformation of coal skeleton with different pore-fracture structures at high temperatures showed a trend of initial increase and subsequent decrease with the increase of porosity and fractal dimension.The maximum deformation of coal skeleton positively correlated with connectivity but negatively correlated with the fractal dimension.

Research on coal structure indices to coal and gas outbursts in Pingdingshan Mine Area,China

According to the feature that coal and gas outbursts is controlled by coal structure in Pingdingshan mine area, based on the study of the distribution law of disturbed coal in Mine Area and the macroscopic characteristics of coal structure, the characteristics and genesis to micro-pore of disturbed coal, the relationship between the type of coal structure and gas parameter, and the structural feature of coal at outbursts sites are mainly explored in this paper. Further, the steps and methods are put forward that coal structure indices applied to forecast coal and gas outbursts.

Methane adsorption behavior on coal having different pore structures

The adsorption of methane onto five dry coal samples was measured at 298 K over the pressure range from 0 to 3.5 MPa using a volumetric method.The isotherm data were fitted to the Langmuir and the Freundlich equations.The kinetic data were fitted to a pseudo second order equation,the linear driving force equation(LDF),and an intra-particle diffusion model.These results showed that higher methane adsorption is correlated with larger micro-pore volumes and specific surface areas.The adsorption was related to the narrow micro-pore size distribution when the previous two parameters are large.The kinetics study showed that the kinetics of methane adsorption onto these five dry coal samples followed a pseudo second order model very well.Methane adsorption rates are controlled by intra-particle diffusion.The faster the intra-particle diffusion,the faster the methane adsorption rate will be.

Coalfield structure and structural controls on coal in China

The occurrence of coal-bearing strata in a variety of coal-bearing basins of China is characterized by late tectonic deformation and remarkable spatial and geochronologic differences.The main controlling factors,which determine the tectonic framework of coalfields,include the geodynamic environment,tectonic evolution,deep structures,tectonic stress,and lithologic combination of the coal measures.The Chinese continent has experienced multi-stage tectonic movements since the Late Paleozoic.The spatial and temporal heterogeneity of its continental tectonic evolution,the complexity of its basement properties,and its stratigraphic configurations control the tectonic framework of its coalfields’present complex and orderly patterns.The concept of coal occurrence structural units is proposed in this paper and is defined as the structural zoning of coal occurrence.China’s coalfields are divided into five coal occurrence structural areas,and the structural characteristics of the coalfields in five main coal occurrence areas throughout the country are summarized.Based on the analysis of the relationship between the structure characteristics and occurrence of coal in these coalfields,the coal-controlling structures are divided into six groups:extensional structural styles,compressional structural styles,shearing and rotational structural styles,inverted structural styles,sliding structural styles,and syn-depositional structural styles.In addition,the distribution of coal-controlling structural styles is briefly summarized in this paper.

Experimental Research on Pore Structure and Gas Adsorption Characteristic of Deformed Coal

The pore structure and gas adsorption property of deformed coal with different degrees of metamorphism were tested by low-temperature nitrogen adsorption and isothermal adsorption experiments. The fractal theory and the Langmuir adsorption theory were used to analyze the experimental data. The test results showed that the deformed coal had more heterogeneous pore structures and open pores, and its specific surface area(SSA) and fractal dimension(D) were higher. There is a polynomial relationship between D and specific surface area as well as gas adsorption capacity(VL). The gas adsorption capacity of deformed coal is influenced by pore structure, coal rank, deformation and stress together, among which the pore structure is the main influencing factor for the adsorption capacity of deformed coal. The test pressure could affect the accuracy of the adsorption constants a and b, so the highest experiment pressure should be greater than the actual pressure of coal seam in order to reduce the deviation of adsorption constants.

Understanding the molecular structure of HSW coal at atomic level:A comprehensive characterization from combined experimental and computational study

In this work,the coal samples from Hongshiwan(HSW)mining area,Ningxia,northwest of China,are characterized by using several modern materials characterization techniques,such as proximate and ultimate analyses,solid state 13C nuclear magnetic resonance(13C NMR),X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy(FT-IR).Then the key information about elements,valence,and chemical bonding for coal molecular structural construction is obtained.The results reveal that the main structure of HSW coal has 75.96%aromatic skeleton in mass.The ratio of aromatic bridge carbon to aromatic peripheral carbon of HSW coal is 0.315,indicating more naphthalene than benzene and anthracene in coal structures.Oxygen predominantly presents in the forms of ether(C–O),carbonyl(C=O)and carboxyl(–COO).Nitrogen presents in the forms of both pyridine and pyrrole.Methyl(–CH_(3))group is predominant in cyclic and aliphatic hydrocarbons.Based on obtained structural information and the approaches of average molecular structure,the single molecular formula of HSW coal is defined as C_(221)H_(148)O_(28)N_(2),with a molecular weight of 3142.32.Also,the 2D and 3D molecular model of HSW coal are built with computeraided modeling.The model is optimized and further verified by FT-IR and^(13)C NMR spectra simulation with quantum chemical calculations.Besides,a more complicated structure of complex model for HSW coal containing 10 single-molecules is also obtained.Therefore,molecular structure of HSW coal has been comprehensively depicted and understood at atomic level from both experimental and quantum chemical approaches in the current work.

Research on Geological Structure Mark of Coal and Gas Outbursts in Pingdingshan Mining Area

Based on the study of regional displaying rules of coal and gas outburst controlled by geological structure in Pingdingshan mining area, the geological structure features in outburst sites were investigated emphatically. The combination type, orientation and least seam thickness in outburst sites were put forward. This research provides a geological mark for forecasting gas outbursts in deep mining.

Research on Full Space Transient Electro-magnetism Technique for Detecting Aqueous Structures in Coal Mines

Based on the transmitting theory of "smoke ring effect", the transient electromagnetism technique was used in coal mines to detect abnormal areas of aquiferous structures in both roofs and floors of coal seams and in front of excavated roadways. Survey devices, working methods and techniques as well as data processing and interpretation are discussed systematically. In addition, the direction of mini-wireframe emission electromagnetic wave of the full space transient electromagnetism technique was verified by an underground borehole for water detection and drainage. The result indicates that this technique can detect both horizontal and vertical development rules of abnormal water bodies to a certain depth below the floor of coal seams and can also detect the abnormal, low resistance water bodies within a certain distance of roofs. Furthermore, it can detect such abnormal bodies in ahead of the excavated roadway front. Limited by the underground environment, the full space transient electromagnetism technique can detect to a depth of only 120 m or so.