High-rank Coals Research Articles

Mechanism of supercritical CO2 on the chemical structure and composition of high-rank coals with different damage degrees

The interaction between carbon dioxide (CO2) and coal plays a vital role in CO2 geological storage enhanced coalbed methane recovery (CO2-ECBM). To investigate the mechanism of supercritical carbon dioxide (SC-CO2) extraction in technically deformed coals under deep coal seam conditions, the chemical composition and structure of technically deformed coals before and after SC-CO2 treatment were analyzed by Fourier transform infrared spectroscopy (FTIR), mass spectrometry (GC–MS) and X-ray diffraction (XRD). The results show that, after SC-CO2 extraction, the absorption peak intensities of weakly polar and non-polar compounds in coal are weakened. With the increase in tectonic deformation degree, the dissolution effect of aromatic compounds increases, while aliphatic compounds show a complementary evolution trend. The dissolution effect of SC-CO2 on carbonate minerals is the most significant, with the highest dissolution amount of 100 %, followed by clay minerals, with the dissolution amount between 1.3 % and 30.5 %, while oxide minerals are relatively stable and hardly react. With the increasing degree of tectonic deformation, the solubility of various minerals tends to increase. In summary, SC-CO2 has a dissolution effect on the organic functional groups and minerals of technically deformed coal, and the effect tends to be significant with the increase of coal tectonic deformation degrees. In view of the important role of mineral and organic composition on the porosity and adsorption of coal, when CO2 is injected into deep coal seams, the response characteristics of porosity, permeability and adsorption caused by the change in mineral and organic composition should also be considered.

The Characteristic Development of Micropores in Deep Coal and Its Relationship with Adsorption Capacity on the Eastern Margin of the Ordos Basin, China

The accurate description of micro-/nanopores in deep coal reservoirs plays an important role in evaluating the reservoir properties and gas production capacity of coalbed methane (CBM). This work studies nine continuous samples of high–rank coal from the Daning–Jixian area of the Ordos Basin. Maceral analysis, proximate analysis, field emission scanning electron microscopy (FE-SEM), low-pressure CO2 adsorption (LPA), low-temperature N2 adsorption (LTA) and high-pressure methane adsorption (HPMA) experiments were conducted for each sample. The fractal dimension (D) of the LPA data was calculated by using the micropore fractal model. The characteristics of the deep coal reservoir pore structure, proximate analysis, relationship between maceral and fractal dimensions, and gas adsorption capacity of the micropores are discussed. The results showed that the combination of LPA with nonlocalized density functional theory (NLDFT) models and LTA with NLDFT models can more accurately determine the pore size distribution of the micropores. The pore volume (PV) and specific surface area (SSA) of the coals were distributed in the ranges of 0.059~0.086 cm3/g and 204.38~282.42 m2/g, respectively. Although the degree of micropore development varies greatly among different coal samples, the pore distribution characteristics are basically the same, and the PV and SSA are the most developed in the pore size range of 0.4–0.7 nm. Ash content (Ad) and mineral composition are two major factors affecting micropore structure, but they have different impacts on the fractal dimension. The higher the vitrinite content, moisture content (Mad) and Ad are, the larger the micropore fractal dimension (D) and the stronger the heterogeneity of the pore structure. Micropores account for 99% of the total SSA in coal, and most methane can be adsorbed in micropores. The fractal dimension of micropores can be used to evaluate the pore structure characteristics. The larger the fractal dimension, the smaller the micro-SSA and micro-PV of the coal sample. Fractal analysis is helpful to better understand the pore structure and adsorption capacity of CBM reservoirs.

Microbiome of High-Rank Coal Reservoirs in the High-Production Areas of the Southern Qinshui Basin.

To study the distribution features of microorganisms in distinct hydrological areas of the southern Qinshui Basin, C-N-S microorganisms were studied using 16S RNA sequencing, metagenome sequencing and geochemical technologies, showing the high sensitivity of microorganisms to the hydrodynamic dynamics of coal. The hydrodynamic intensity of the #3 coal gradually decreased from the runoff areas to the stagnant areas. The stagnant zones have higher reservoir pressure, methane content, δ13CDIC and TDS and lower SO42-, Fe3+ and NO3- concentrations than the runoff areas. C-N-S-cycling microorganisms, including those engaged in methanogenesis, nitrate respiration, fermentation, nitrate reduction, dark oxidation of sulfur compounds, sulfate respiration, iron respiration, chlorate reduction, aromatic compound degradation, denitrification, ammonification and nitrogen fixation, were more abundant in the stagnant areas. The relative abundance of C-N-S functional genes, including genes related to C metabolism (e.g., mcr, mer, mtr, fwd and mtd), N metabolism (e.g., nifDKH, nirK, narGHI, nosZ, amoB, norC and napAB) and sulfur metabolism (e.g., dsrAB and PAPSS), increased in the stagnant zones, indicating that there was active microbiological C-N-S cycling in the stagnant areas. The degradation and fermentation of terrestrial plant organic carbon and coal seam organic matter could provide substrates for methanogens, while nitrogen fixation and nitrification can provide nitrogen for methanogens, which are all favorable factors for stronger methanogenesis in stagnant areas. The coal in the study area is currently in the secondary biogenic gas generation stage because of the rising of the strata, which recharges atmospheric precipitation. The random forest model shows that the abundance of C-N-S microorganisms and genes could be used to distinguish different hydrological zones in coal reservoirs. Since stagnant zones are usually high-gas-bearing zones and high-production areas of CBM exploration, these microbiological indicators can be used as effective parameters to identify high-production-potential zones. In addition, nitrate respiration and sulfate respiration microorganisms consumed NO3- and SO42-, causing a decrease in the content of these two ions in the stagnant areas.

Experimental and DFT Research on the Effects of O2/CO2 and O2/H2O Pretreatments on the Combustion Characteristics of Char.

The use of a coal-based energy structure generates a large amount of CO2 and NOx. The numerous emissions from these agents result in acid rain, photochemical smog, and haze. This environmental problem is considered one of the greatest challenges facing humankind in this century. Preheating combustion technology is considered an essential method for lowering the emissions of CO2 and NO. In this research, the char prepared from O2/CO2 and O2/H2O atmospheres was employed to reveal the effects of the addition of an oxidizing agent on the combustion characteristics of char. The structural features and combustion characteristics of preheated chars were determined by Raman, temperature-programmed desorption (TPD), and non-isothermal, thermo-gravimetric (TGA) experiments. According to the experimental results, the addition of oxidizing agents promoted the generation of smaller aromatic ring structures and oxygen-containing functional groups. The improvement in the surface physicochemical properties enhanced the reactivity of char and lowered its combustion activation energy. Furthermore, the combustion mechanisms of the char prepared from the O2/CO2 and O2/H2O atmospheres were investigated using the density functional theory (DFT). The simulation results illustrated that the combustion essence of char could be attributed to the migration of active atoms, the fracture of the benzene ring structure, and the reorganization of new systems. The addition of oxidizing agents weakened the conjugated components of the aromatic ring systems, promoting the successive decomposition of CO and NO. The results of this study can provide a theoretical basis for regulating the reaction atmosphere in the preheating process and promoting the development of clean combustion for high-rank coals.

Experimental Study of the Fracture Network Expansion Mechanism and Three-Dimensional Reconstruction Characteristic of High-Rank Coal in Guizhou Province, China.

To better understand the fracture propagation characteristics and spatial distribution pattern of a high-rank coal reservoir during hydraulic fracturing, a true triaxial physical simulation device was used to conduct a hydraulic fracturing experiment on large-sized raw coal from Zhijin, Guizhou Province, China. Computed tomography technology was used to scan the three-dimensional morphology of the fracture network before and after fracturing, then AVIZO software was used to reconstruct the internal fractures of the coal sample, and fractal theory was used to quantify the fractures. The results show that (1) the sudden increase of the pump pressure curve and acoustic emission signal is an important identification feature of hydraulic fractures, and the in situ stress difference coefficient plays a leading role in the complexity of coal and rock fractures. (2) When a hydraulic fracture encounters a primary fracture in the process of expansion, the opening of the primary fracture, the penetration, bifurcation, and turning of the hydraulic fracture are the main reasons for the formation of complex fractures, and the existence of a large number of primary fractures is the basis for the formation of complex fractures. (3) The fracture shape of coal hydraulic fracturing can be divided into three categories: complex fracture, plane fracture + cross fracture, and inverted T-shaped fracture. The fracture shape is closely related to the original fracture shape. The research results of this paper provide strong theoretical and technical support for coalbed methane mining design such as Zhijin high-rank coal reservoirs.

Experiment on the Gas Permeability and Gas–Water Relative Permeability in High-Rank Coal with a Self-Developed Device

Water saturation, displacement pressure, and gas type are essential factors affecting the seepage characteristic of fluid in coal due to the swelling induced by gas adsorption. However, the understanding of the seepage behavior of water, CH4, and CO2 in coal seams is still poor owing to the lack of research. In this work, a series of gas permeability and gas–water relative permeability experiments were conducted by our self-developed device. The results can be summarized as follows: (1) with the increase in water saturation, the gas permeability decreased rapidly at first and then reduced sharply again after a period of slow decline; (2) the two-phase flow span showed no significant difference for He–water and CH4–water systems under different displacement pressures, but it increased for CO2-water system. The different behaviors of the two-phase flow span suggested that the effect of displacement pressure on relative permeability properties is dependent on the gas type. (3) The CO2–water relative permeability showed a sizeable two-phase flow span compared to the He–water or CH4–water system under the same displacement pressure, and the gas relative permeability decreased obviously in the following sequence: He > CH4 > CO2. The concept of relative permeability surface was proposed based on the experimental results. A parametric interpolation method was applied to determine the relative permeability surface, which could be used to accurately describe the flow characteristics of fluids in a mixed gas–water system.

Pore Structure Multifractal Characteristics of Coal Reservoirs in the Central and Eastern Qinshui Basin and Influencing Factors

The heterogeneity of the pore structure of coal reservoirs affects the desorption and diffusion characteristics of coalbed methane, and determining its distribution law is conducive to improving the theory of coalbed methane development. The central and eastern parts of the Qinshui Basin are rich in coalbed methane resources, but the heterogeneity characteristics of the pore structure of coal reservoirs are not clear. NMR has the advantages of being fast, non-destructive and full-scale, and multifractal can describe the self-similarity of NMR T2 curve at different scales so as to analyze the complexity of pore distribution. Based on this, 15 samples with different coal ranks were collected from the central and eastern Qinshui Basin (Ro,max between 1.54 and 2.78%), and quantitative pore characterization experiments such as low-field nuclear magnetic resonance (LF-NMR) and low-temperature liquid nitrogen adsorption (LTN2A) were conducted. Based on multifractal theory, the heterogeneity law of pore structure was quantitatively evaluated, and its influencing factors were elucidated. The results showed that the BJH pore volume of coal samples in the study area ranged from 0.0005–0.0028 cm3/g, with an average of 0.0014 cm3/g, and the BET specific surface area was 0.07–2.52 m2/g, with an average of 0.41 m2/g. The NMR T2 spectrum peaked at 0.1–1, 10–100 and 100–1000 ms, and the spectrum was mostly bimodal or trimodal, indicating that pores of different pore sizes were developed. There were great differences in the pore structure of different coal ranks; high-rank coal was dominated by micropores, and the proportion of mesopores and macropores of medium-rank coal was higher. The pore structure of coal samples showed obvious multifractal characteristics, and the fractal characteristics of the sparse region (low-value information) were more significant; they dominated the pore distribution and had a stronger influence on the distribution of pore space. Pore structure heterogeneity is closely related to the degree of coalification, and with the increase in coalification, it is closely related to coal lithotype and quality, and high mineral and inertinite contents lead to the enhancement of pore structure heterogeneity in coal reservoirs, while Ro,max, Mad and vitrinite group contents have opposite effects. The research results provide theoretical guidance for the subsequent exploration and development of coalbed methane in the region.

Enrichment of strategic metals in the Upper Triassic coal from the Nui Hong open-pit mine, Thai Nguyen Coalfield, NE Vietnam

Research on coal-hosted strategic metal ore deposits is an important subject in coal geology and mineral deposit worldwide. However, the related geological characteristics of coals from Vietnam have seldom been investigated, let alone the strategic metals in coals. This paper investigates the mineralogical and geochemical characteristics of the Upper Triassic coal from the Nui Hong open-pit mine, Thai Nguyen Coalfield, NE Vietnam, with emphasis on the enrichment of strategic metals in coal. The Nui Hong coal is low-volatile bituminous with high sulfur organic content. Minerals in the Nui Hong coal is predominantly composed of authigenic quartz, tobelite, pyrite, and calcite, with a small proportion of sphalerite, gypsum and fluorapatite in some coal bench samples. Mo-U-V-Se and Ge-W-Sb-Cs-Tl(-U) strategic metal element assemblages along with As-P toxic element association is significantly enriched in the Nui Hong coal, pointing to a significant economic benefit for Cs, Mo, U, and Ge recovery from the Nui Hong coal. The Ge enrichment in the Nui Hong coal provides a new perspective on prospecting of coal-hosted Ge deposit in high-rank coal. Cesium mostly occurs in K-rich aluminosilicate minerals (tobelite and/or illite), while Mo, Sb, U, Ge, and Tl are predominantly associated with organic matter in the Nui Hong coal. Multistage hydrothermal activities occurring in the marine-influenced S-rich, Fe-poor and clastic-starved anoxic-euxinic coal-forming environment are responsible for the significant enrichment of strategic metal elements in the upper Triassic coals from the Nui Hong open-pit mine, Thai Nguyen Province.

Fractal characteristics and theirs influence on methane adsorption in high-rank coals with NMR

To further understand the pore structure characteristics and their effect on CH4 adsorption capacity for high-rank coals. Based on 11 fresh coal samples from the Zhina coalfield of South China. We analyzed the pore structure characteristics of coal samples by low-temperature liquid-nitrogen adsorption (LP-N2A) measurements. On the basis of nuclear magnetic resonance (NMR), we obtained the fractal dimensions of different types of pores by the new model, studied the relationship between the fractal dimensions, and the characteristic parameters of coals (composition and pore characteristics) and discussed the influence of the fractal dimensions on CH4 adsorption. The results show that according to LP-N2A isotherms, all coals can be classified into three types. The micropores provide the largest proportion of the specific surface area (SSA) of coals. Two fractal dimensions, Da (adsorption pore) and Ds (seepage pore), ranged from 2.471 to 2.805 and from 2.812 to 2.976, which were acquired in the saturated water condition by NMR. Furthermore, Da and Ds have different correlations with ash yield, carbon contents, moisture, SSA and irreducible fluid porosity. The coal composition and pore parameters have much greater control over fractal dimensions. Moreover, the different fractal dimensions have different influences on methane adsorption. With the increase of Da, the methane adsorption capacity is enhanced, but it is weakened with the increase of Ds. The high-rank coals have more SSA with higher Da and provide more adsorption sites for CH4. Langmuir pressure PL has different correlations with fractal dimensions. Da decreases with the increase of PL. The adsorption velocity is faster with higher Da. Thus, the fractal dimensions are the comprehensive reflection of differences among the physical properties of coal and are able to show the effect of coal properties on methane adsorption fully.

Effect of thermal damage on the pore–fracture system during coal spontaneous combustion

Understanding the variation law of pore–fracture system during coal spontaneous combustion (CSC) plays a crucial role in understanding the mechanism of CSC and its prevention as well as control. In this study, three different ranks of coal samples were heat-treated (25–500 °C). Through nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) and uniaxial compression (UC) tests, the changes in the pore-fracture system of different types of coal during CSC were comprehensively summarized. Based on the experimental results, the thermal rupture behavior of coal was simulated using PFC2D software. The results show that During CSC, the pore development of low-rank coal was obvious, the pore development of middle-rank coal was mainly concentrated in the high-temperature stage (T >300 °C), and the pore structure of high-rank coal was more stable. Meanwhile, the heterogeneity of the pore–fracture system of middle- and low-rank coals decreased, and the adsorption and seepage capacities increased. The heterogeneity of the pore–fracture system of high-rank coal was slightly influenced by temperature. The compressive strength of coal decreases with increasing temperature during CSC. The numerical simulation results were similar to the experimental results, i.e., the microcracks in the coal samples increased with temperature during heating; the effect of cracking caused by the high temperature will change the way the sample breaks, and the samples changed from ductile to brittle. The results of this study can serve as a reference for coal-fire control.

Carbon isotopic composition and organic petrography of thermally metamorphosed Antarctic coal: Implications for evaluation of δ13Corg excursions in paleo-atmospheric reconstruction

Large, globally documented negative δ13C excursions that occur across the Permian-Triassic transition are thought to represent the isotopic fingerprint of considerable releases of isotopically light carbon into the atmosphere, with the largest of these excursions (as much as −22.2‰) measured in bulk organic matter in coals and carbonaceous shales from Antarctica. Previous studies have attributed the carbon isotopic excursion (CIE) at the Permian–Triassic boundary to the release of CH4 from organic-rich rocks intruded by dikes and sills associated with the Siberian Traps flood basalts (Russia) and Longwood-Bluff (New Zealand) intrusions. However, any assessment of paleoatmospheric conditions based on this or other δ13Corg excursions must consider the multiple controls on isotopic composition, including maceral content and post-depositional diagenetic and maturation processes. Permian-age coal seams and associated sediments in Antarctica were extensively altered after burial by localized high heat flow and, in some cases, by contact metamorphism associated with Jurassic dikes and sills. Levels of organic maturation reach anthracite, meta-anthracite, and even graphite; such intense thermal alteration had the potential to change the carbon isotopic composition of the bulk organic matter (δ13Corg). To evaluate the Permian–Triassic isotopic excursion in Antarctica, it is important to understand the inherent variability in δ13Corg in Permian-age coal and organic-rich sedimentary rocks prior to the CIE; thus, 128 samples representing pre-boundary coals and shales were selected from the United States Polar Rock Repository for analysis. Petrographic (maceral analysis and vitrinite reflectance), geochemical (C, H, N), and carbon isotopic analyses were performed. Based on the presence of coarse-grained circular and fine-grained lenticular mosaic in the anisotropic cokes found in samples in close proximity to intrusions, the rank of the samples prior to intrusion is estimated to have been medium volatile bituminous (∼1.2% Rmax). These highly altered coals and cokes can have random vitrinite reflectances (Rr) exceeding 6%. Subsequent to intrusion, alteration beyond the contact aureoles continued due to high heat flow, producing high rank coals with Rr > 2%. Values of δ13Corg range between −26.5 and –21.1‰ (5.4‰ difference). Significant relationships (at the 1 and 5% levels) exist between δ13Corg and the level of organic maturity, organic carbon (Corg) content (i.e., size of the carbon reservoir), and total inertinite content, suggesting variability due to these factors should be considered when assessing isotopic excursions and interpretation of Permian-Triassic atmospheric conditions. These findings highlight the importance of incorporating organic petrography into δ13Corg studies.

Graphene oxide obtention via liquid phase exfoliation from high-rank coal: A comparison of mineral matter removal by alkaline bath

Colombia is one of the world's leading exporters of coal and coke, with significant reserves of high-quality coal. Most of the coal exported from Colombia is used for power generation, but there is also a class of coal that is suitable for making coke. Coke is a raw material required for making steel, and it is produced by heating coal to high temperatures in the absence of air. Colombia is the third-largest global exporter of coke, with a significant portion of its exports going to the steel industry in countries such as Brazil, Mexico, and the United States. The country's high-quality coal reserves and proximity to major markets make it an important player in the global coal and coke trade. On the other hand, graphene and its derivative Graphene Oxide (GO) have unique properties that make them suitable for a wide range of commercial applications. Graphene has exceptional mechanical strength and high electrical conductivity, which make it an attractive material for a variety of electronic and structural applications. For example, graphene-based materials are being developed for use in flexible electronic devices, sensors, and high-strength composites. GO, on the other hand, is highly resistive but still retains exceptional mechanical strength. This makes it useful in applications where electrical conductivity is not necessary but mechanical strength and durability are important. Graphene production using current techniques can be expensive and inefficient, which limits its widespread adoption for commercial applications. However, new production methods, such as Liquid Phase Exfoliation (LPE), are being developed to address these challenges. LPE is a method for producing graphene and graphene oxide that involves using a liquid solvent to break apart graphite into individual graphene sheets. This method is more efficient and cost-effective than traditional methods such as mechanical exfoliation and chemical vapor deposition. In recent years, there has been increasing interest in using high-rank coal from Colombia as a raw material for graphene production using LPE. This is because high-rank coal from Colombia is known to have a high carbon content and low impurity levels, which makes it an ideal raw material for graphene production. Researchers have successfully produced GO using the LPE method and high-rank coal from Boavita, Colombia. This has the potential to significantly increase the supply of graphene and graphene oxide, making it more accessible for commercial applications. Additionally, using coal as a raw material for graphene production has the potential to create a new market for coal, which could benefit the Colombianeconomy. In order to synthesize GO, it is important to establish a suitable protocol for the grinding procedure and particle size selection. (i. more than 0.15 mm, ii. 0.15 mm to 0.05 mm, and iii. less than 0.05 mm) were defined. To compare the yield, the mineral matter removal procedure was carried out with a basic leaching bath. Coal oxidation was performed using the modified Hummers process, and GO was then obtained using LPE. This method has the following advantages:•It is feasible to produce GO from high-rank coal with acceptable quality and particulate size smaller than 0.15 mm, yields that are close to 5%, and flakes with fewer than 15 layers.•This approach also could eliminate dependence on graphite as the carbon feedstock for graphene production.•It is an alternative to manufacture GO from coal dust collected from mines.

Development of potentiometric titration method for assessing coals’ oxidation degree

Oxidation of coal leads to some unwanted consequences, such as losses of products quality and increase in proneness to spontaneous combustion. One of the indicators of coals’ oxidation is changing in amount and composition of active functional groups in organic matter. On using a wide number of samples and adjusting the experimental procedure, a method was developed for coals’ oxidation degree evaluation by potentiometric titration based on evaluation of contents of total acidic groups (a sum of phenol and carboxyl groups). It was shown that potentiometric titration is not applicable for determination of phenol and carboxyl groups in coals separately. A phenomenon of appearance of two waves at titration curve was connected with absorption of CO2 from air into the alcohol-alkaline solution. For coals with vitrinite reflectance varying in range of 0.5-0.72 %., total acidic groups amount decrease with rank growth, whereas for higher rank coals such an alteration is less pronounced. It is shown that it is expedient to use the developed method of potentiometric titration together with the petrographic method for determining the oxidation degree. On the basis of the proposed method of coals’ oxidation degree determination by potentiometric titration, a National standard of the Russian Federation GOST R 59012-2020 has been introduced. According to it, the oxidation degree is determined by the increase of the total amount of acidic groups – phenolic and carboxyl hydroxyls in coal as compared to the content of total acidic groups in the control sample, which is used as a seam sample of coal taken outside the oxidation zone, or coal taken when laying the pile, or coal received for benefication, sorting or moving. The research has been carried out in the framework of strategic academic leadership program “Priority 2030”. The paper was written with the participation of E. L. Kossovich, Senior Researcher, Candidate of Physico-mathematical Sciences.

Molecular Simulation of Methane Adsorption Behavior on Coal: Effects of Maturity and Moisture Content

Abstract The adsorption behaviors of multiphase fluids in coal are vital for estimating their transfer and flow mechanisms. In this study, taking the classical coal structures as instances, the impacts of maturities and moisture contents of coal on the methane adsorption capacities and thermodynamic properties were analyzed and determined by molecular simulations. Specifically, the simulated pressures were varied from 0 to 16 MPa, and three temperatures (298 K, 323 K, and 348 K) were considered. In addition, the competitive adsorption capacities of water/methane molecules were evaluated and the critical value of moisture content affecting the isosteric adsorption heat of methane was determined. Furthermore, a quantitative relationship between the gas adsorption amount and adsorption equilibrium pressure under a three-phase “solid–gas–liquid” action was established. The simulated results showed that taking the intermediate-rank coals as examples, the absolute adsorption capacities of methane molecules on different moist coals reduced by 28.3%, 35.1%, 46.9%, and 62.3%, respectively (at uniform pressure–temperature status) in comparison to their dry status. In addition, when the moisture content was lower than 1.4 wt%, the average isosteric adsorption heat remained almost stable. However, when the moisture content exceeded 1.4 wt%, the average isosteric adsorption heat increased sharply with the increase in the water content. Finally, linear function formulas yielded a good fitting accuracy range for the low- and intermediate-rank coals; in comparison, for the high-rank coal, an exponential function formula obtained a better fitting accuracy than a linear one.

PAHs in medium and high rank Bulgarian coals – insights from aromatic indices

The study presents analyses of aromatic components in bitumen extracts from Bulgarian medium and high rank coals. Bulk samples from Balkan, Ro = 0.96%, Dobroudzha, Ro = 1.13%, and Svoge, Ro = 5.20% coal-bearing provinces, were considered. After extensive chromatographic separation and GC-MS study of the aromatic fractions, our attention was focused on polycyclic aromatic hydrocarbons (PAHs) compositions. Aromatic indices, based on quantification of individual compounds, revealed that: (i) the highest amounts of PAHs were present in Balkan and Dobroudzha samples, 219–365 μg/g TOC, and dropped to 3.5 μg/g TOC at Svoge sample; (ii) the alkylated naphthalenes and phenantrenes prevalence confirmed published data; (iii) the relationship between aromatic indices vs. Ro, % is in agreement with the previously obtained results, indicating their decrease with thermal maturity. For some indices only weak correlation was obtained, suggesting that PAH concentrations are not solely affected by coal rank, but also by environmental conditions and vegetation.

Relationship between Dielectric Relaxation Time and Permeability of High-Rank Coal in the Jiaozuo Mining Area.

To evaluate the permeability of coal by the complex resistivity method, the real part of complex resistivity (R), the imaginary part of complex resistivity (X), capacitance (C), permeability (k), and strain (ε) of coal in different directions under variable pressure were measured. Based on the physicochemical structure characteristics of coal and its conductivity and dielectric mechanism, the experimental phenomenon was analyzed and correlated with the permeability of coal. The results demonstrated that (1) the R-X curve is U-shaped. With increasing frequency, the amplitude first decreases and then increases, forming an obvious trough. C decreases with increasing frequency. (2) The R-X curve is affected by pressure and directivity. The absolute value of the R-X curve amplitude gradually decreases and shifts to the left as the pressure increases; meanwhile, it decreases and shifts to the left in the order of the vertical bedding direction (z direction), the vertical main fracture direction in parallel bedding (y direction), and the main fracture direction in parallel bedding (x direction). There is also a related change law for C. (3) The dielectric relaxation time (τ) was optimized as the electrically sensitive parameter of coal. τ continues to decrease as pressure increases and decreases in the order of the z, y, and x directions. (4) The permeability of coal is strongly correlated with the dielectric relaxation time, and the relationship between them conforms to a logarithmic function. The relationship of strain and the dielectric relaxation time verifies the strong correlation between permeability and the dielectric relaxation time. This study provides an experimental basis and theoretical support for the subsequent accurate prediction and evaluation of coal permeability using the dielectric relaxation time.

An Experimental Study on CO2 Displacing CH4 Effects of Different Rank Coals

In order to study the effect of different rank coals on the displacement of CH4 by CO2 and prevent the gas-related disasters, a series of experiments were carried out. For this purpose, we selected low-rank lignite raw from Datong coalfield of Shanxi Province, medium-rank bituminous coal raw from Xutuan coalfield of Anhui Province, and high-rank anthracite raw coal from Yangquan coalfield of Shanxi Province. The results showed that (1) the shape of the displacement adsorption curve of the mixed gas and the shape of the single-dimensional adsorption curve of the pure gas are both steep at the beginning, with the increase of the pressure, the curve becomes more and more gentle. The difference is that it is lower than the single-dimensional gas adsorption curve. (2) The separation factor in the coal samples used in the experiment shows a trend of first decreasing and then increasing with the decrease of coal rank. The displacement factor has the same trend as the separation factor of each coal rank, which is Z i j anthracite > Z i j lignite > Z i j bituminous coal . (3) The amount of displaced CH4 in the displacement/adsorption process has enhanced with the increase in pressure, and the trend for different coals is Q Z bituminous coal > Q Z anthracite > Q Z lignite . In addition, displacement showed the order ƞ lignite > ƞ anthracite > ƞ bituminous coal . The injection ratio of bituminous coal and anthracite decrease with the increase in pressure, while that of lignite increase first and later decreased. (4) In gas injection displacement, on the long time, the displacement effect of high coal rank is better than that of low coal rank.

Experimental Study on the Variation Mechanism of Permeability and Seepage Characteristics of High-Rank Coal with Different Bedding.

In order to understand the variation mechanism of permeability and seepage characteristics of high-rank coal with different bedding, we prepared cylindrical raw coal samples according to the bedding angles of 0, 30, 45, 60, and 90° and conducted permeability tests under two stress paths (stress path 1, unloading confining pressure under constant axial pressure; stress path 2, simultaneous loading axial pressure and unloading confining pressure). The results show that the relationship between the permeability and effective stress of high-rank coal with different bedding in the two stress paths conforms to an exponential function, and the permeability increases gradually with an increase in differential stress. Under the two stress paths, the initial permeability of different bedding under the loading axial pressure and confining pressure shows a pattern of a maximum for parallel bedding coal samples, followed by oblique bedding coal samples, and a minimum for vertical bedding coal samples. Under path 1, the increase in the permeability of the oblique bedding is 21.4 times that of the vertical bedding and 14.94 times that of the parallel bedding, and under path 2, the increase in the permeability of the oblique bedding is 26.45 times that of the vertical bedding and 142.11 times that of the parallel bedding; the coal samples of the oblique bedding suffer the greatest damage. The increase in the permeability of parallel bedding coal samples, oblique bedding coal samples, and vertical bedding coal samples under path 2 is 1.47 times, 13.96 times, and 11.3 times the increase in the permeability of the corresponding coal samples under path 1, respectively, and the damage produced by coal samples under path 2 is greater than that under path 1.

Fractal Analysis and Classification of Pore Structures of High-Rank Coal in Qinshui Basin, China

The influence of high-rank coal’s pore characteristics on the physical properties, gas-bearing properties, and exploitation of coal reservoirs is becoming more and more prominent. How to establish the classification to describe the pore networks combining quantitative and qualitative characteristics has emerged as a major problem, which may offer a scientific foundation to deepen the understanding of this issue. In this research, the structure and fractal characteristics of reservoir pores were determined after analyzing 20 high-rank coal samples from Xinjing Coal Mine in the Qinshui Basin with the application of the high-pressure mercury intrusion method (HPMI) and argon ion polishing–field emission scanning electron microscopy (AIP–FESEM). The results show that the tested coal samples were bipolar distributed, with transitional pores and micropores dominating the pore volume, followed by macropores. The Menger sponge fractal models manifested two or three distinct straight-line segments with demarcation points of 65 nm and 1000 nm. A natural classification with three major pore types of diffusion pores (D-pores), seepage pores (S-pores), and pico pores (P-pores), demarcated by pore size intervals of 65 nm and 1 nm and seven sub-types, was established to relate pores to pore networks based on these fractal characteristics and the kinetic characteristics of methane molecules. This classification scheme can characterize the relationship between pore types and the corresponding major occurrence and transport mechanisms of the gas. In addition, P-pores and D-pores are predominately nanoscale OM pores with three major genetic types of organic constituent interparticle pores (5–200 nm), metamorphic pores (<5 nm), and intermorphic pores (<5 nm). S-pores are more complex in origin and shape features, and the major types include outgas pores, plant tissue residual pores, mineral-related pores, and microfractures. The mean radius (Pa), total pore volume (Vt), apparent porosity (Φ), and volume ratio of macro- and mesopores were positively correlated with the fractal dimension D1 of S-pores (>65 nm). Since fractal analysis is a more comprehensive characterization of reservoir structure and quantitatively reflects the pore structure, undulating state, and roughness of the inner surface, fractal parameters can be used as an important index to describe the pore structure characteristics of high-rank coal reservoirs.

Control mechanism of small organic molecules on methane adsorption capacity of coal

Small organic molecules have a significant influence on methane adsorption of different rank coals. To explore the control mechanism of small organic molecules on methane adsorption capacity of coal, in this paper, based on the relative content of small organic molecules in different rank coals obtained by extraction experiment, the complex models of raw and residual coal with different ranks were constructed. The influence of small organic molecules on the methane adsorption of coal was analyzed by molecular simulation calculation. The control mechanism of small organic molecules on the methane adsorption capacity of coal was further discussed. The results showed that for the low-rank coal with high content of small organic molecules, small organic molecules mainly play the role of blocking and separating so that separate the larger coal pores into more micropores, thereby the methane adsorption capacity of coal pores is increased. For the middle-rank coal with the same high content of small organic molecules, micropores are closed by small organic molecules, so that its methane adsorption capacity is reduced. For the high-rank coal, due to its low content of small organic molecules, few pores are blocked or closed, that the existence of small organic molecules has no significant effect on its methane adsorption capacity. The research results help to reveal the microscopic mechanism of methane adsorption of coal, which has great significance to the development of coalbed seam gas and mine gas disaster prevention.