Research on Permeability of Multiphase Medium of Middle to High-Rank Coals

The permeability of coal of middle to high ranks were tested using He,CH 4 and H 2O in single phase medium and using CH 4 and H 2O in double phase medium. The relation between adsorption and permeability of those media was discussed, and the seepage flow characteristics of methane-water medium in coals were analyzed. The result shows that the coalbed methane resource of high-rank coal reservoirs in China is still recoverable.

Jumpy evolution of EPR response of Chinese high-rank coals and its implication to geochemistry

Based upon a series of the coal graphite samples collected from China, the jumpy evolution of the EPR response of the high rank coals was found and its geochemical mechanism was further inquired. The results showed that the makingup, which is activated notably at about 6.0% maximum vitrinite reflectance, might play a principal role in the development of the macromolecular basic structural units in the coals being in the middle to late stage of high rank coalification and that the homologisation of the chemical bonds in the macro molecular structure might provide a geochemical microenvironment for the realization of the makingup.

Features of rare earth elements geochemistry in coals of Central Kazakhstan

This research presents the results of a comprehensive study of mineralogical and geochemical features of REE distribution in coals of Central Kazakhstan deposits—Karaganda coal basin and Shubarkol deposit,which have large hard coal reserves and are industrially important for the coal industry of Kazakhstan;the research is based on 205 samples of clayey interlayers and coal seams.It shows basic patterns of distribution and features of concentration for impurity elements,gives an estimate of the impurity elements concentration,including REE,defines conditions and factors of their accumulation,and studies features of their forms in coal and coal-bearing rocks,which allows estimating the mechanisms of their migration and conditions of accumulation.According to the results of geochemical indicators,the article establishes the factors of REE dislocation,reveals the composition of margin rocks that have influenced REE concentration in coal seams,and the presented latest data on mineralogy allowed to establish the ways of their transportation to the paleobasin during the synand epigenetic periods of formation of the coal deposits of Central Kazakhstan being researched.It was found that the coals are insignificantly enriched with heavy lanthanides from Ho to Lu.The distribution curves of UCC normalized REE values in the coals are similar and coincide,but they are less than the average value for world coal,and amount to only one-third of the UCC.It was found that the highest concentrations of all REE are characteristic of clayey interlayers and oxidized coals.The La/Yb ratio in this case increases upwards along the section,indicating mainly clastogenic mechanism of REE delivery to the coals.In coal and clay samples,the predominant mineral form of REE is light lanthanide phosphates.Identified particles of REE from minerals and their composition peculiarities suppose autigene nature of their formation.The formation of the bulk of autigene minerals occurred during the maturation of brown coals and their transformation into hard ones.

Microwave irradiation-induced alterations in physicochemical properties and methane adsorption capability of coals:An experimental study using carbon molecular sieve

In order to comprehend the applicability of microwave irradiation for recovering coalbed methane,it is necessary to evaluate the microwave irradiation-induced alterations in coals with varying levels of metamorphism.In this work,the carbon molecular sieve combined with KMnO_(4)oxidation was selected to fabricate carbon molecular sieve with diverse oxidation degrees,which can serve as model substances toward coals.Afterwards,the microwave irradiation dependences of pores,functional groups,and highpressure methane adsorption characteristics of model substances were studied.The results indicated that microwave irradiation causes rearrangement of oxygen-containing functional groups,which could block the micropores with a size of 0.40-0.60 nm in carbon molecular sieve;meanwhile,naphthalene and phenanthrene generated by macro-molecular structure pyrolysis due to microwave irradiation could block the micropores with a size of 0.70-0.90 nm.These alterations in micropore structure weaken the saturated methane adsorption capacity of oxidized carbon molecular sieve by 2.91%-23.28%,suggesting that microwave irradiation could promote methane desorption.Moreover,the increased mesopores found for oxidized carbon molecular sieve after microwave irradiation could benefit CH4 diffusion.In summary,the oxidized carbon molecular sieve can act as model substances toward coals with different ranks.Additionally,microwave irradiation is a promising technology to enhance coalbed methane recovery.

Study of methane and carbon dioxide adsorption-desorption hysteresis in coals from Sydney Basin:A theoretical and experimental approach

Methane(CH_(4))and carbon dioxide(CO_(2))are primary components of coal seam gas(CSG).Understanding their adsorption-desorption hysteresis characteristics,along with the fundamental mechanism,is crucial for CSG exploitation and related hazards mitigation.This research focused on the representative Bulli coal seam in the Sydney Basin,Australia.Through the purpose-built indirect gravimetric high-pressure isothermal adsorption-desorption hysteresis experiment,a novel Langmuir-based desorption model,incorporating hysteresis effect and residual gas,was proposed.Quantitative characterization of the adsorption-desorption hysteresis degrees of CO_(2)and CH_(4)i n coal particles of various sizes and inΦ50mm 100 mm intact coal samples were achieved using the improved hysteresis index(IHI).The experimental findings validated that the proposed desorption model accurately describes the desorption behavior of CO_(2)and CH_(4)in coal(R^(2)>0.99).Based on the adsorption-desorption properties of inkbottle-shaped micropores and pore deformation caused by gas adsorption-induced coal expansion,the occurrence mechanism of adsorption–desorption hysteresis and the fundamental reasons for the presence of residual gas were elucidated.Furthermore,the study explored the impact of CO_(2)and CH_(4)adsorption-desorption hysteresis effects on coal and gas outbursts,suggesting that coal seams rich in CO_(2)do not have a higher propensity for outbursts than those rich in CH_(4).

Characteristics of high-rank coal structure parallel and perpendicular to the bedding plane via NMR and X-ray CT

Pores and fractures and their connectivity play a significant role in coalbed methane production.To investigate the growth characteristics and connectivity of pores and fractures in coal parallel and perpendicular to the bedding plane,the pores and fractures of high-rank coal samples collected from the southern Qinshui Basin were measured by low-field nuclear magnetic resonance,X-ray-computed tomography and field emission scanning electron microscopy.Then,the determinants of their connectivity were further discussed.The results show that the high-rank coal samples have similar pore size distributions both parallel and perpendicular to the bedding plane.They primarily contain mesopores(2-50 nm in width),followed by macrospores(> 50 nm in width).The research indicated that the high-rank coal connectivity parallel to the bedding plane is significantly better than that perpendicular to the bedding plane.The connectivity of high-rank coal is mainly determined by throats,and the orientation of the pores and fractures.The two connectivity modes in high-rank coal are "pore connectivity," in which the throats are mainly pores with a low coordination number,and "microfissure connectivity",in which the throats are mainly microfissures with a high coordination number.

Structure and production fluid flow pattern of post-fracturing high-rank coal reservoir in Southern Qinshui Basin

Field geological work, field engineering monitoring, laboratory experiments and numerical simulation were used to study the development characteristics of pore-fracture system and hydraulic fracture of No.3 coal reservoir in Southern Qinshui Basin. Flow patterns of methane and water in pore-fracture system and hydraulic fracture were discussed by using limit method and average method. Based on the structure model and flow pattern of post-fracturing high-rank coal reservoir, flow patterns of methane and water were established. Results show that seepage pattern of methane in pore-fracture system is linked with pore diameter, fracture width, coal bed pressure and flow velocity. While in hydraulic fracture, it is controlled by fracture height, pressure and flow velocity. Seepage pattern of water in pore-fracture system is linked with pore diameter, fracture width and flow velocity. While in hydraulic fracture, it is controlled by fracture height and flow velocity. Pores and fractures in different sizes are linked up by ultramicroscopic fissures, micro-fissures and hydraulic fracture. In post-fracturing high-rank coal reservoir, methane has level-three flow and gets through triple medium to the wellbore; and water passes mainly through double medium to the wellbore which is level-two flow.

Rare Earth Element Geochemistry of Late Palaeozoic Coals in North China

Abstract: Instrumental Neutron Activation Analysis (INAA) was done to determine the abundances of rare earth elements (REE) of 58 samples of Late Palaeozoic Carboniferous-Permian coals and related rocks in North China. Detailed study of REE geochemistry shows that the ?REE of most coals studied in this paper is in a normal range between 30×10?6 and 80×10?6 with a mean of 56×10?6. The REE in the Taiyuan Formation in the northern part of North China are much richer than those in the southern part. This is due to the shorter distance to the source area in the north. Moreover, the ?REE is in positive correlation to coal ash, especially closely related to the content of clay minerals <2 μm in size. This reveals that most REE were carried by terrigenous clastic materials, especially fine clay minerals. In the coals the light REE (LREE) are much richer than the heavy REE (HREE), and the LREE/HREE ratio in coals generally varies from 2 to 8. The LREE/HREE ratio of high-ash, low-sulphur coals is higher than that of low-ash, high-sulphur coals, and is even higher in the roof and floor rocks, reaching 12 with the highest (up to 21) in pyrite concretions, which shows that the HREE have a stronger affinity to organic matter in a reducing environment influenced by seawater. Furthermore, Eu is generally depleted in coals. The REE chondrite-normalized distribution patterns are very similar in coals of the whole of North China. From the REE geochemical characteristics it can be concluded that during the formation of Late Palaeozoic Carboniferous-Permian coals in North China, the supply of terrigeneous materials remained quite stable. The ?REE in low-ash, high-sulphur coals is relatively low and the REE are mainly carried by fine-grained minerals and organic matter and a certain percentage of REE are adsorbed by organic matter; while the ?REE in high-ash, low-sulphur coals is higher and the REE are mainly present in detritus. The ?REE of magmatism-influenced coals is the highest, which suggests that the introduction of magmatic substances may increase the ?REE, thus causing the REE distribution patterns to show an abnormal feature. Moreover, some harmful elements such as U, W and As usually increase when the coals are influenced by magmatism.

Paleo-fires and Atmospheric Oxygen Levels in the Latest Permian:Evidence from Maceral Compositions of Coals in Eastern Yunnan,Southern China

Inertinite maceral compositions of the Late Permian coals from three sections in the terrestrial and paralic settings of eastern Yunnan are analyzed in order to reveal the paleo-fire events and the atmospheric oxygen levels in the latest Permian. Although the macerals in the studied sections are generally dominated by vitrinite, the inertinite group makes up a considerable proportion. Its content increases upward from the beginning of the Late Permian to the coal seam near the Permian- Triassic boundary. Based on the microscopic features and the prevailing theory that inertinite is largely a by-product of paleo-fires, we suggest that the increasing upward trend of the inertinite abundance in the latest Permian could imply that the Late Permian peatland had suffered from frequent wildfires. Since ignition and burning depend on sufficient oxygen, a model-based calculation suggests that the 02 levels near the Wuchiapingian/Changhsingian boundary and the Permian-Triassic boundary are 27% and 28% respectively. This output adds supports to other discoveries made in the temporal marine and terrestrial sediments, and challenges the theories advocating hypoxia as a mechanism for the PermianTriassic boundary crisis.

Micro-structural evolution and their effects on physical properties in different types of tectonically deformed coals

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 wrinkle structure coal of low ductile deformation and later superimposed by brittle deformation.Other kinds of TDC suffering from strong brittle-ductile and ductile deformation,such as scale structure coal and mylonitic structure coal,are difficult problems to resolve.

Co-pyrolysis characteristics and interaction route between low-rank coals and Shenhua coal direct liquefaction residue

To reasonably utilize the coal direct liquefaction residue(DLR), contrasting research on the co-pyrolysis between different low-rank coals and DLR was investigated using a TGA coupled with an FT-IR spectrophotometer and a fixed-bed reactor. GC–MS, FTIR, and XRD were used to explore the reaction mechanisms of the various co-pyrolysis processes. Based on the TGA results, it was confirmed that the tetrahydrofuran insoluble fraction of DLR helped to catalyze the conversion reaction of lignite. Also, the addition of DLR improved the yield of tar in the fixed-bed, with altering the composition of the tar. Moreover, a kinetic analysis during the co-pyrolysis was conducted using a distributed activation energy model. The co-pyrolysis reactions showed an approximate double-Gaussian distribution.

Microstructural relation of macerals with mineral matter in coals from Ib valley and Umaria, Son-Mahanadi basin, India

Coal petrology provides significant inputs for the industrial utilisation of coal and for broad understanding the coal formation and diagenesis. The present paper entails the results of the investigations carded out on the selected coal samples, from Ib valley and Umaria coalfield, using scanning electron microscope （SEM） and X-ray diffraction （XRD） to study the surface microstructures and minerals present in them and the relationship of the finely dispersed mineral matter with the organic constituents. This would further help in evaluating the distribution and chemical character of the mineral matter occurring within the maceral types. Ib valley and Umaria coals are typical Indian （Lower Gondwana） non-coking coals and only scanty data is available on SEM study of these coals. Under SEM examination, it manifests that, the mineral matters of these coal occur as deep intergrowth, massive impregnation, superficial mounting, filling and depletion of micropores, mechanical cavity filling and fusinitic cavity filling.

Feasibility studies on cleaning of high sulfur coals by using ionic liquids

Coal has been used as an energy resource around the world, primarily for the generation of electricity. The cleaning of coal by removing its unwanted sulfur and mineral matter components is utmost essential before their gainful utilizations. The ionic liquids （ILs） are considered as non-toxic solvents for using in different industrial processes. The effect of two ILs namely, 1-n-butyl, 3-methylimidazolium tetrafluoro borate （ILl） and 1-n-butyl, 3-methylimidazolium chloride （IL2） in oxidative de-sulfurization and de-ashing of two industrially important high sulfur coal samples from Meghalaya （India） is discussed in this paper. The maximum removal of total sulfur, pyritic sulfur, sulfate sulfur and organic sulfur are observed to be 37.36 %, 62.50 %, 83.33 % and 31.63 % respectively during this oxidative process. The quantitative diffuse reflectance Fourier transform-infrared spectroscopy analysis supports the formation of sulfoxides （S--O） and sulfones （-SO2） and their subsequent removal during the oxidation of the coals in presence of ILs. The X-ray fluorescence combined with near edge X-ray absorption fine structure and scanning electron microscopic studies reveal the removal of mineral matters （ash yields） from the coal samples. The thermogravimetric analysis of the raw and clean coals indicates their high combustion efficiencies and suitability for using in thermal plants. The method is partially green and the ILs could be recovered and reused in the process.

Gas desorption characteristics of the high-rank intact coal and fractured coal

The objective of this work is to study the gas desorption characteristics of the high-rank intact coal and fractured coal.The gas adsorption,mercury porosimetry and gas desorption experiments were carried out in this study.Then,the theories of thermodynamics,diffusion mechanism and desorption kinetics were used to estimate the gas desorption characteristics.The results of gas adsorption experiments show that the initial isosteric adsorption heat of the intact coal is greater than that of the fractured coal,indicating that the gas molecules desorb more easily from fractured coal than intact coal.Using the mercury porosimetry,we find that the diffusion channels of fractured coal are more developed than those of intact coal.The difficult diffusion form dominates in the intact coal during the gas diffusing,while the easy diffusion form dominates in the fractured coal.The results of gas desorption experiments show that the initial gas desorption volume and velocity of the fractured coal are both greater than those of the intact coal.Using the Fick diffusion law,the study calculates the gas diffusion coefficients of the intact coal and fractured coal.The diffusion coefficients of the fractured coal are 2 times and 10 times greater than those of the intact coal at the time of 0-120 and 0-10 min,respectively.

A Carbon Isotopic Stratigraphic Pattern of the Late Palaeozoic Coals in the North China Platform and Its Palaeoclimatic Implications

This paper gives the stable carbon isotopic data in coals from the Late Namurian to Kazanian stages in the Serteng Mt., Xishan and Huainan coalfields of the North China Platform. Its stratigraphic pattern shows that several isotopic shifts are apparent, and the large δ13C negative shifts (approximately 2.5 to 3.0 %%) occurred during the Stephanian, Artinskian and Kazanian are observed in three Permo-Carboniferous coalfields. Those negative shifts are neither related to the coal rank and coal macerals, nor caused by the variety of peat-forming plants. The general decrease in the δ13C values of the Stephanian, Artinskian and Kazanian coals is consistent with an overall decrease in the δ13C values of ambient atmospheric CO2 and/or a relative increase in atmospheric Pco2 during the coal-forming periods. Therefore the authors postulate that the oxidation of peat, and the δ13C-depleted CO2 flux into the atmosphere during the above stages may have contributed to coeval palaeoclimatic warming by way of the greenhouse effect.

Application of thermally stimulated acoustic emission method to assess the thermal resistance and related properties of coals

Traditional methods of coal thermal resistance characterization are informative but considerably timeconsuming and require utilization of a complex and expensive equipment. This limits the effectiveness of their application. In this paper, authors experimentally investigated potential application of thermally stimulated acoustic emission method for developing of relatively simple and rapid coals thermal resistance assessment method. Features of thermally stimulated acoustic emission of anthracite, lignites and bituminous coal samples subject to cyclic thermal loading have been experimentally investigated.For the first time, it has been shown that there exists a relationship of such patterns with structural parameters and properties of the coal samples, as well as their thermal resistance. The results indicate the possibility of applying the method of thermally stimulated acoustic emission to control processes of cryogenic disintegration and thermal resistance of fossil coals. The description of the equipment and methodological support needed for the implementation of this method have been provided.

Surface microtopography and micromechanics of various rank coals

For a long time,coalbed gas has brought about various problems to the safety of coal mine production.In addition,the mining of gas and coalbed methane(CBM)has attracted much attention.The occurrence and migration of CBM are believed to be closely related to the micro-surface properties of coal.To further explore the characteristics of CBM occurrence and migration,in this study,the micro-surface topography,adhesion,and elastic modulus of five metamorphic coals were measured by atomic force microscopy(AFM).The results show that the microtopography of coal fluctuates around 40 nm,reaching a maximum of 66.5 nm and the roughness of the surface decreases with the increase of metamorphism.The elastic modulus of coal micro-surface varies from 95.40 to 9626.41 MPa,while the adhesion varies from 15.08 to 436.22 nN,and they both exhibit a trend of"M"shape with the increase of metamorphism.Furthermore,a high correlation exists between adhesion and microtopography fluctuation.In most cases,the adhesion is larger in the concavity area and smaller in the convexity area.The research results may provide a new method for revealing the occurrence and migration of CBM and ensure efficient and safe CBM exploitation.

Organic petrology and geochemistry of Triassic and Jurassic coals of the Tabas Basin, Northeastern/Central Iran

Jurassic and Triassic coals and organic matter-rich shales of the Tabas Basin, Iran, were investigated with respect to their thermal maturation and petrographic composition. The Triassic coals of the Parvadeh coal field range in vitrinite reflectance between 1.17% and 1.37% and the Jurassic coals of the Mazino coal field between 2.08% and 2.29% VRr. Maceral analysis revealed a predominance of vitrinite in all samples, with slightly higher percentages of inertinite in the Jurassic samples. Rock-Eval analyses confirm the presence of type III kerogen in the Triassic coals, while the Jurassic coals contain strongly carbonized residual kerogen. The range of sulfur contents for coals from the Parvadeh coal field (0.37% to 4.64%) and Mazino coal field (0.45% to 2.92%) is related to the effect of marine water in peat. The studied samples are characterized by the predominance of short- over long-chained n-alkanes. The relatively high Pr/Ph ratios indicate predominance of terrestrial organic matter whereas Pr/n-C17 and Ph/n-C18 ratios prove oxic conditions during deposition. In addition, the DBT/Phen ratio shows that these coals formed in fluvial/deltaic environments. Molecular geochemical parameters such as carbon preference index (CPI, 0.99-1.04), methyl phenanthrene index (MPI, 1.20-1.60), methyl naphthalene ratio (MNR, 1.61-3.45), and ethyl naphthalene ratio (ENR, 4-6.78) confirm the high maturity of the samples. Burial and thermal history reconstruction indicates necessity of an erosional thickness of about 4000 m in the Parvadeh area. Towards the Mazino area, a higher basal heat flow up to 80 mW m^-2 is assumed for the Paleogene leading to higher maturities.

Composition and mode of occurrence of minerals in Late Permian coals from Zhenxiong County,northeastern Yunnan,China

Minerals in the Late Permian coals from the Niuchang-Yigu mining area,Zhenxiong County,northeastern Yunnan,China,were investigated using optical microscopy and low temperature ashing plus X-ray diffraction(LTA?XRD).The results showed that minerals in the coal LTAs are mainly quartz,kaolinite,chamosite,mixed-layer illite/smectite(I/S),pyrite,and calcite,with trace amounts of marcasite,dolomite,and bassanite.The authigenic quartz generally occurs in collodetrinite or as a filling in cleats or cell cavities.This silica was mainly derived from aqueous solutions produced by the weathering of basaltic rocks in the Kangdian Upland and from hydrothermal fluids.The presence of b-quartz paramorph grains in collodetrinite probably indicates that these grains were detrital and came from a volcanic ash.Clay minerals are generally embedded in collodetrinite and occur as cell-fillings.Pyrite occurs as framboidal,anhedral,and euhedral grains and a cell-filling.The coals are high in pyrite and the high pyrite content probably results from seawater invading during the stage of peat accumulation.Calcite generally occurs as vein-fillings,indicating an epigenetic origin.

A new apparatus to establish the spontaneous combustion propensity of coals and coal-shales

Coal and coal-shale both tend to undergo spontaneous combustion under favourable atmospheric conditions. The Wits-Ehac index has been developed in South Africa since the late 1980's to test the spontaneous combustion liability of coal. However, in some cases, the Wits-Ehac index fails to produce tangible results when testing coal-shales. To overcome this problem, a new apparatus has been developed to test carbonaceous materials such as coal and coal-shale under chemical reactions with oxygen and an index has been obtained. This index is called the Wits-CT index. The equipment emulates the influence of oxygen adsorption on carbonaceous material for a period of 24 h without a heating system.The Wits-CT index uses the total carbon content of the sample and the temperature variations obtained from the samples during reaction with oxygen to predict the spontaneous combustion liability. Eighteen samples have been analyzed using both indices and the results are in-line. It was found that coals and coal-shales with higher values of the Wits-CT index are more liable to spontaneous combustion.Further research on different coal-shales is underway in order to establish an extensive database for coal and coal-shales, together with known incidences of self-heating.