邯郸-峰峰矿区不同变质程度煤中有机氮的赋存形态

氮是煤中的常见元素之一,煤中氮的赋存形态多样且随煤阶发生变化。以邯郸-峰峰矿区为例,利用X射线光电子能谱（XPS）实验,研究不同变质程度煤（R_ran=1.08%~3.67%）中有机氮的赋存形态,探讨煤中各形态有机氮相对含量随煤阶的变化规律。结果表明:按N 1s XPS谱图分峰峰值的结合能可将煤中氮的形态归为N-6、N-5、N-Q和N-X四种;研究区煤中N-5的相对含量最高,且随着煤阶的增高而降低;N-Q的相对含量随着煤阶的增高而增高;煤中N-6的相对含量随煤阶呈“增-减-稳”的变化规律;N-X的相对含量为9.1%~35.1%,其与煤阶关系不明显;在煤阶R_ran=1.08%~1.47%的范围内,煤的N 1s XPS谱图中缺失N-Q分峰,表明褐煤中相对含量最高的质子化吡啶氮在此阶段已几乎全部去质子化而转化为吡啶氮。不同变质阶段氮的赋存形态变化特征对燃煤发电及煤化工领域煤化学参数选取提供参考。      

Contact angles in CO2-water-coal systems at elevated pressures

Injection of carbon dioxide into coal seams is considered to be a potential method for its sequestration away from the atmosphere. However, water present in coals may retard injection: especially if carbon dioxide does not wet the coal as well as water. Thus contact angles in the coal-water-CO₂ system were measured using CO₂ bubbles in water/coal systems at 40 °C and pressures up to 15 MPa using five bituminous coals. At low pressures, in this CO₂/water/coal system, receding contact angles for the coals ranged between 80° to 100°; except for one coal that had both high ash yield and low rank, with a contact angle of 115°, indicating that it was hydrophilic. With increasing pressure, the receding contact angles for the different coals decreased, indicating that they became more CO₂-wetting. The relationship between contact angle and pressure was approximately linear. For low ash or high rank coals, at high pressure the contact angle was reduced to 30-50°, indicating the coals became strongly CO₂-wetting; that is CO₂ fluids will spontaneously penetrate these wet coals. In the case of the coal that was both high ash and hydrophilic, the contact angle did not drop to 90° even at the highest pressures used. These results suggest that CO₂ will not be efficiently adsorbed by all wet coals equally well, even at high pressure. It was found that at high pressures (> 2 MPa) the rate of penetration of carbon dioxide into the coals increased rapidly with decreasing contact angle, independently of pressure. Injecting CO₂ into wet coals that have both low rank and high ash will not trap CO₂ as well as injecting it into high rank or low ash coals.     

A microscopic study of the combustion residues of subbituminous and bituminous coals from Alberta, Canada

Chars produced by the combustion of a set of three coals from Alberta, Canada, were classified morphologically using reflected light microscopy. Produced chars are different in morphological features, pore thickness, anisotropy and degree of reactivity, because of differences in the vitrinite and inertinite contents.The subbituminous A coal produced the highest percentage of unreactive or slightly reactive components due to its high inertinite content (20.0%), followed by isotropic cenospheres. Isotropic cenospheres, both thin- and thick-walled, and exploded cenospheres are the characteristic chars produced by the high-voltile bituminous B coal, whereas the low-volatile bituminous coking coal produced cenospheres with granular anisotropy (mosaic) on the walls and abundant coke fragmentsOptical microscopy is useful in differentiating the performance of a series of coals during combustion based on petrographic composition and rank and can aid in understanding the relationship between ‘reactive’ and ‘non-reactive’ coal macerals to burnout performance.     

Methane and CO2 sorption and desorption measurements on dry Argonne premium coals: pure components and mixtures

Sorption and desorption behaviour of methane, carbon dioxide, and mixtures of the two gases has been studied on a set of well-characterised coals from the Argonne Premium Coal Programme. The coal samples cover a maturity range from 0.25% to 1.68% vitrinite reflectance. The maceral compositions were dominated by vitrinite (85% to 91%). Inertinite contents ranged from 8% to 11% and liptinite contents around 1% with one exception (Illinois coal, 5%). All sorption experiments were performed on powdered (−100 mesh), dry coal samples.Single component sorption/desorption measurements were carried out at 22 °C up to final pressures around 51 bar (5.1 MPa) for CO₂ (subcritical state) and 110 bar (11 MPa) for methane.The ratios of the final sorption capacities for pure CO₂ and methane (in molar units) on the five coal samples vary between 1.15 and 3.16. The lowest ratio (1.15) was found for the North Dakota Beulah-Zap lignite (VR_r=0.25%) and the highest ratios (2.7 and 3.16) were encountered for the low-rank coals (VR_r 0.32% and 0.48%) while the ratio decreases to 1.6–1.7 for the highest rank coals in this series.Desorption isotherms for CH₄ and CO₂ were measured immediately after the corresponding sorption isotherms. They generally lie above the sorption isotherms. The degree of hysteresis, i.e. deviation of sorption and desorption isotherms, varies and shows no dependence on coal rank.Adsorption tests with CH₄/CO₂ mixtures were conducted to study the degree of preferential sorption of these two gases on coals of different rank. These experiments were performed on dry coals at 45 °C and pressures up to 180 bar (18 MPa). For the highest rank samples of this sequence preferential sorption behaviour was “as expected”, i.e. preferential adsorption of CO₂ and preferential desorption of CH₄ were observed. For the low rank samples, however, preferential adsorption of CH₄ was found in the low pressure range and preferential desorption of CO₂ over the entire pressure range.Follow-up tests for single gas CO₂ sorption measurements consistently showed a significant increase in sorption capacity for re-runs on the same sample. This phenomenon could be due to extraction of volatile coal components by CO₂ in the first experiment. Reproducibility tests with methane and CO₂ using fresh sample material in each experiment did not show this effect.     

The occurrence of anthracites in an area characterized by lower rank coals in the Upper Silesian Coal Basin of Poland

The results of petrographical-geological and chemical examinations on anthracites, semianthracites and medium-low volatile bituminous coals from Jastrzebie in the Upper Silesian Coal Basin of Poland are presented. The coking coals mined in this region exhibit volatile matter V^daf = 18–26%, free swelling index FSI = 3–8 and reflectance R_m = 1.10–1.35% and are inertiniterich coals (I = 25–63%).Coal Seam 504 of the Anticlinal beds (Namurian B) has been affected by thermal metamorphism and contains both coking coals and coals of higher rank. According to the criterion of Polish Standards this coal seam varies from anthracite (V^daf <10%) to semianthracite (V^daf = 10–14%) in rank. The carbon content is slightly lower and the hydrogen content a little higher than those of typical anthracites and semianthracites. The reflectance values (R_m = 1.56–2.62%) are generally lower than the R_m values proposed by the International Committee for Coal Petrology as boundary values for anthracites and bituminous coal. The magnitude of anisotropy and microhardness were also examined. Examinations of optical properties prove that the metamorphism exhibited by the coals is the result of elevated temperature and variable pressure. The analyses of the maceral composition indicate that there is a decrease in the inertinite content in anthracites. Vitrinite exhibits the features of thermally altered coal. The micrinite content shows a little variation. In coking coals, a strongly fluorescing bituminous substance with the optical features of exsudatinite was found. The constructed geological section of Coal Seam 504 shows distinct regular changes in chemical and physical properties as well as the petrographic composition which may be caused by the heat flux of a magma intrusion, not localized so far.     

煤中氮的赋存状态与含量分布研究进展

综述了煤中氮的赋存状态与氮含量的分布特征方面的研究现状及存在问题。认为,煤中的氮几乎全部以有机物的形式存在,其赋存状态主要有4种类型:吡咯型氮（N-5）、吡啶型氮（N-6）、季氮（N-Q）和氮氧化物（N-X）,且这四种含氮官能团的分配比例受煤阶和煤热解程度的影响。煤中氮的质量分数一般在0.5%~2.5%,其变化与煤级、成煤期、沉积环境、原始成煤植物、煤岩组成及岩浆侵入等因素有关。目前有关影响氮含量变化因素的研究主要集中在探讨氮的含量与煤级的关系上,并认为氮的含量随煤级升高而增大,但在煤化作用后期迅速降低。有关氮的研究可丰富煤的元素地球化学研究,并为煤的环境污染治理提供更多的科学依据。      

Supercritical gas sorption on moist coals

The effect of moisture on the CO₂ and CH₄ sorption capacity of three bituminous coals from Australia and China was investigated at 55 °C and at pressures up to 20 MPa. A gravimetric apparatus was used to measure the gas adsorption isotherms of coal with moisture contents ranging from 0 to about 8%. A modified Dubinin–Radushkevich (DR) adsorption model was found to fit the experimental data under all conditions. Moisture adsorption isotherms of these coals were measured at 21 °C. The Guggenheim–Anderson–de Boer (GAB) model was capable of accurately representing the moisture isotherms over the full range of relative pressures.Moist coal had a significantly lower maximum sorption capacity for both CO₂ and CH₄ than dry coal. However, the extent to which the capacity was reduced was dependent upon the rank of the coal. Higher rank coals were less affected by the presence of moisture than low rank coals. All coals exhibited a certain moisture content beyond which further moisture did not affect the sorption capacity. This limiting moisture content was dependent on the rank of the coal and the sorbate gas and, for these coals, corresponded approximately to the equilibrium moisture content that would be attained by exposing the coal to about 40–80% relative humidity. The experimental results indicate that the loss of sorption capacity by the coal in the presence of water can be simply explained by volumetric displacement of the CO₂ and CH₄ by the water. Below the limiting moisture content, the CO₂ sorption capacity reduced by about 7.3 kg t^− 1 for each 1% increase in moisture. For CH₄, sorption capacity was reduced by about 1.8 kg t^− 1 for each 1% increase in moisture.The heat of sorption calculated from the DR model decreased slightly on addition of moisture. One explanation is that water is preferentially attracted to high energy adsorption sites (that have high energy by virtue of their electrostatic nature), expelling CO₂ and CH₄ molecules.     

The elemental and isotopic composition of sulfur and nitrogen in Chinese coals

Coal combustion is an important atmospheric pollution source in most Chinese cities, so systematic studies on sulfur and nitrogen in Chinese coals are needed. The sulfur contents in Chinese coals average 0.9 ± 1.0%, indicating that most Chinese coals are low in sulfur. A nearly constant mean δ³⁴S value is observed in low sulfur (TS < 1) Chinese coals of different ages (D, P₁, T₃ and J₃). High sulfur Chinese coals (OS > 0.8%), often found at late Carboniferous (C₃) and late Permian (P₂) in southern China, had two main sulfur sources (original plant sulfur and secondary sulfur). The wide variety of δ³⁴S values of Chinese coals (−15‰ to +50‰) is a result of a complex sulfur origin. The δ¹⁵N values of Chinese coals ranged from −6‰ to +4‰, showing a lack of correlation with coal ages, whereas nitrogen contents are higher in Paleozoic coals than in Mesozoic coals. This may be related to their original precursor plant species: high nitrogen pteridophytes for the Paleozoic coals and low nitrogen gymnosperms for the Mesozoic coals. Different to δ³⁴S values, Chinese coals showed higher δ¹⁵N values in marine environments than in freshwater environments.     

Polycyclic aromatic hydrocarbons (PAHs) in Chinese coal: occurrence and sorption mechanism

Elevated polycyclic aromatic hydrocarbon (PAH) concentrations were determined in different Chinese coals, with the highest concentrations in bituminous coals. Phenanthrene (Phen) was chosen as the probe compound for PAHs to study the sorption behavior of coal. No native Phen was detected in desorption experiments indicating irreversible sorption–desorption behavior of PAHs in raw coal samples. Sorption mechanism was further studied under varying conditions of pH value and ionic strength. Different ranks of coal showed different sorption behavior under acidic, neutral, and alkaline conditions. Batch experiments were further processed for the selected coals at pH values from 3 to 11 at a constant aqueous concentration. Sorption capacities of all coals decreased with increased pH except for YJ coal. Furthermore, although DOC-associated Phen mass contributed little to the total Phen mass under different pH values, the significant negative correlations between M _DOC and log K _OC values were observed for all coal samples, indicating a significant role played by DOC in the coal sorption. In addition, sorption experiments under varying ionic strength showed that the ionic strength influence was more obvious in sorption isotherms for higher rank coals with increasing ionic strength, and this effect was most significant when ionic strength increased from 0 to 0.15 M, especially at relatively low aqueous concentrations.     

Petrology, rank and evidence for petroleum generation, Upper Triassic to Middle Jurassic coals, Central Alborz Region, Northern Iran

Upper Triassic to Middle Jurassic coals from the Alborz region of northern Iran were analyzed by reflected light-fluorescence microscopy and Rock Eval 6® pyrolysis to evaluate their regional rank variation, degree of hydrothermal alteration, and petroleum generative potential. The coal ranks in the region range from a low of 0.69%Ro_R in the Glanddeh-Rud area to a high of 1.02%Ro_R in the Gajereh area. T_max (°C) values (Rock Eval 6 pyrolysis) also increase progressively with increasing vitrinite %Ro values, however T_max is suppressed lower than would be expected for each rank ranging from 428 °C for the Glandeeh coal to 438 °C for the Gajereh coal. T_max suppression may be caused by maceral composition and soluble organics within the coal. Moderately high hydrogen indices, persistent and oily exudations from the coals during UV exposure, and traces of hydrocarbon fluid inclusions suggest that liquid petroleum was likely generated within some of the coals.     

Properties of thermally metamorphosed coal from Tanjung Enim Area, South Sumatra Basin, Indonesia with special reference to the coalification path of macerals

Thermally metamorphosed Tertiary age coals from Tanjung Enim in South Sumatra Basin have been investigated by means of petrographic, mineralogical and chemical analyses. These coals were influenced by heat from an andesitic igneous intrusion. The original coal outside the metamorphosed zone is characterized by high moisture content (4.13–11.25 wt.%) and volatile matter content (> 40 wt.%, daf), as well as less than 80 wt.% (daf) carbon and low vitrinite reflectance (VR_max = 0.52–0.76%). Those coals are of subbituminous and high volatile bituminous rank. In contrast the thermally metamorphosed coals are of medium-volatile bituminous to meta-anthracite rank and characterized by low moisture content (only < 3 wt.%) and volatile matter content (< 24 wt.%, daf), as well as high carbon content (> 80 wt.%, daf) and vitrinite reflectance (VR_max = 1.87–6.20%). All the studied coals have a low mineral matter content, except for those which are highly metamorphosed, due to the formation of new minerals.The coalification path of each maceral shows that vitrinite, liptinite and inertinite reflectance converge in a transition zone at VR_max of around 1.5%. Significant decrease of volatile matter occurs in the zone between 0.5% and 2.0% VR_max. A sharp bend occurs at VR_max between 2.0% and 2.5%. Above 2.5%, the volatile matter decreases only very slightly. Between VR_r = 0.5% and 2.0%, the carbon content of the coals is ascending drastically. Above 2.5% VR_r, the carbon content becomes relatively stable (around 95 wt.%, daf).Vitrinite is the most abundant maceral in low rank coal (69.6–86.2 vol.%). Liptinite and inertinite are minor constituents. In the high rank coal, the thermally altered vitrinite composes 82.4–93.8 vol.%. Mosaic structures can be recognized as groundmasss and crack fillings. The most common minerals found are carbonates, pyrite or marcasite and clay minerals. The latter consist of kaolinite in low rank coal and illite and rectorite in high rank coal. Change of functional groups with rank increase is reflected most of all by the increase of the ratio of aromatic C–H to aliphatic C–H absorbances based on FTIR analysis. The Oxygen Index values of all studied coals are low (OI < 5 mg CO₂/g TOC) and the high rank coals have a lower Hydrogen Index (< 130 mg HC/g TOC) than the low rank coals (about 300 mg HC/g TOC). T_max increases with maturity (420–440 °C for low rank coals and 475–551 °C for high rank coals).Based on the above data, it was calculated that the temperature of contact metamorphism reached 700–750 °C in the most metamorphosed coal.     

The role of coal petrographic characteristics in evaluating the non-coking nature of the coals of ramagundam and Kothagudem coalfields,Godavari Valley Basin,Andhra Pradesh,India

The maceral and microlithotype compositions of coals representative of the different coal seams of the Ramagundam and Kothagudem coalfields, Godavari Valley Basin, are compared with those of the Ib River, Talcher, South Karanpura, Hura, and Brahmani coalfields. The vitrite + clarite—“Intermidiates”—durite + fusite + shale (<20%) triangular diagram places these coals in the area of non-coking coals, clearly distinct from the coking and semi-coking coals. The vitrinite reflectance is low (R_ormoil^aver: 0.38–0.71%), far below the coking-coal range. Thus, based on petrographic composition and rank, these coals are of non-coking nature. A triangular diagram is proposed delineating the coking, semi-coking and non-coking coal areas for the Gondwana coals of India.     

Studies of the relationship between coal petrology and grinding properties

The maceral and microlithotype composition of selected coals has been investigated with respect to the grinding properties, specifically Hardgrove grindability index (HGI), of the coals. The study expands upon previous investigations of HGI and coal petrology by adding the dimension of the amount and composition of the microlithotypes. Coal samples, both lithotypes and whole channels, were selected from restricted rank ranges based on vitrinite maximum reflectance: 0.75–0.80% R_max, 0.85–0.90% R_max and 0.95–1.00% R_max. In this manner, the influence of petrographic composition can be isolated from the influence of rank. Previous investigations of high volatile bituminous coals demonstrated that, while rank is an important factor in coal grindability, the amount of liptinite and liptinite-rich microlithotypes is a more influential factor. In this study, we provide further quantitative evidence for the influence of microlithotypes on HGI and, ultimately, on pulverizer performance.     

Role of coal type and rank on methane sorption characteristics of Bowen Basin, Australia coals

The effect of coal composition, particularly the organic fraction, upon gas sorption has been investigated for Bowen Basin and Sydney Basin, Australia coals. Maceral composition influences on gas retention and release were investigated using isorank pairs of hand-picked bright and dull coal in the rank range of high volatile bituminous (0.78% R_{o max}) to anthracite (3.01% R_{o max}). Adsorption isotherm results of dry coals indicated that Langmuir volume (V_L) for bright and dull coal types followed discrete, second-order polynomial trends with increasing rank. Bright coals had a minimum V_L at 1.72% R_{o max} and dull coals had a minimum V_L at 1.17% R_{o max}. At low rank, V_L was greater in bright coal by about 10 cm³/g, but as rank increased, the bright and dull trends converged and crossed at 1.65% R_{o max}. At ranks higher than 1.65% R_{o max}, both bright and dull coals followed similar trends. These competing trends mean that the importance of maceral composition on V_L varies according to rank. In high volatile bituminous coals, increases in vitrinite content are associated with increases in adsorption capacity. At ranks higher than medium to low volatile bituminous, changes in maceral composition may exert relatively little influence on adsorption capacity. The Langmuir pressure (P_L) showed a strong relationship of decreasing P_L with increasing rank, which was not related to coal type. It is suggested that the observed trend is related to a decrease in the heterogeneity of the pore surfaces, and subsequent increased coverage by the adsorbate, as coal rank increases. Desorption rate studies on crushed samples show that dull coals desorb more rapidly than bright coals and that desorption rate is also a function of rank. Coals of lower rank have higher effective diffusivities. Mineral matter was found to have no influence on desorption rate of these finely crushed samples. The evolution of the coal pore structure with changing rank is implicated in diffusion rate differences.     

Inertinite-rich Tertiary coals from the Zeya–Bureya Basin, Far Eastern Russia

Selected Tertiary coals from the Zeya–Buryea Basin, Far Eastern Russia, were investigated for aspects of their coal type, rank, depositional environment and post-depositional history. The coals have been examined in outcrop (lithotype logging), microscopically (maceral, reflectance and fluorescence), and geochemically (proximate analysis).Two laterally extensive coal-bearing horizons occur: one of Palaeocene age and the other of early Miocene age. The Palaeocene coals were investigated in active open-cut mines at Raichikhinsk and Yerkovtsi and the early Miocene deposit in an abandoned open-cut mine at Cergeyevka.Palaeocene coals at Raichikhinsk and Yerkovtsi were indistinguishable from each other macroscopically, microscopically, and geochemically. The deposits were sufficiently coalified that brightness logging could be undertaken. Dull coals, with numerous fusainous wisps, were dominant. Four dulling-up sequences, which represent stacked peat deposits, were observed at Raichikhinsk. At Yerkovtsi, only a small section of the middle of the seam, which was mostly dull and muddy coal, was investigated. Petrographically, these coals were dominated by inertinite group macerals, which is unusual in non-Gondwanan coals and rare in the Tertiary. Rank classification was problematic with volatile matter (VM) content of vitrain (daf), macroscopic appearance, and microscopic textures suggesting subbituminous B rank, but carbon content, moisture content and specific energy indicating a lignite rank.Notwithstanding complications of rank, estimates of the maximum-range burial depths were calculated. Taking the VM (daf) content of vitrain as 48%, burial depth estimates range from 900 m for a high geothermal gradient and long heating time to a maximum of 3300 m for a low geothermal gradient and short heating time. These estimates are maxima as the coal rank may be lower than implied by the VM.The Cergeyevka deposit is a soft brown coal. Limited sampling of the upper-most portion indicated a high moisture content (75% daf) and an unusual, hydrogen-rich geochemistry. Lack of identifiable liptinites using either reflected light or fluorescence microscopy suggested a significant bituminite component. Otherwise, the coals appear to be typical for the Tertiary. An estimate of 125 m maximum burial depth was obtained using the bed-moisture content of the coal, which is around the present burial depth.Comparison of present-day thicknesses with inferred burial depths suggests that at least 500 m of section is missing between the Palaeocene coals and the early Miocene coals.Palaeoenvironmental considerations suggest that fire played a significant role in the accumulation of the peats at Raichikhinsk and Yerkovtsi. At Cergeyevka, peat accumulation ended by drowning of the mire.Two tuff beds were recognised within the seam at Raichikhinsk and one in the seam at Yerkovtsi. Correlation of the tuff beds is uncertain but they should prove useful in regional coal seam correlation and interpreting coal depositional environments. Geochemical analysis by XRF was complicated by high loss-on-ignition (LOI) values. Despite extensive alteration, an acid igneous source is implied from the presence of free quartz and TiO₂/Al₂O₃ ratios of 0.02 to 0.05.     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

Assessment of shrinkage–swelling influences in coal seams using rank-dependent physical coal properties

Characterization of coal reservoirs and determination of in-situ physical coal properties related to transport mechanism are complicated due to having lack of standard procedures in the literature. By considering these difficulties, a new approach has been developed proposing the usage of relationships between coal rank and physical coal properties. In this study, effects of shrinkage and swelling (SS) on total methane recovery at CO₂ breakthrough (TMRB), which includes ten-year primary methane recovery and succeeding enhanced coalbed methane (ECBM) recovery up to CO₂ breakthrough, and CO₂ sequestration have been investigated by using rank-dependent coal properties. In addition to coal rank, different coal reservoir types, molar compositions of injected fluid, and parameters within the extended Palmer & Mansoori (P&M) permeability model were considered. As a result of this study, shrinkage and swelling lead to an increase in TMRB. Moreover, swelling increased CO₂ breakthrough time and decreased displacement ratio and CO₂ storage for all ranks of coal. Low-rank coals are affected more negatively than high-rank coals by swelling. Furthermore, it was realized that dry coal reservoirs are more influenced by swelling than others and saturated wet coals are more suitable for eliminating the negative effects of CO₂ injection. In addition, it was understood that it is possible to reduce swelling effect of CO₂ on cleat permeability by mixing it with N₂ before injection. However, an economical optimization is required for the selection of proper gas mixture. Finally, it is concluded from sensitivity analysis that elastic modulus is the most important parameter, except the initial cleat porosity, controlling SS in the extended P&M model by highly affecting TMRB.     

Organic nitrogen chemistry during low-grade metamorphism

Most of the organic nitrogen (N_org) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil N_org within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of N_org and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of N_org a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of N_org speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in N_org speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset N_org is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much N_org is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for N_org elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate N_org along a progressing reaction front, without causing nitrogen isotope fractionation in the residual N_org in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core N_org chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized π-electron systems (nitrogen atoms substituting for “graphitic” carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade.     

Physical properties of selected block Argonne Premium bituminous coal related to CO2, CH4, and N2 adsorption

CO₂, CH₄, and N₂ adsorption and gas-induced swelling were quantified for block Blind Canyon, Pittsburgh #8 and Pocahontas Argonne Premium coals that were dried and structurally relaxed at 75 °C in vacuum. Strain measurements were made perpendicular and parallel to the bedding plane on ~ 7 × 7 × 7 mm³ coal blocks and gravimetric sorption measurements were obtained simultaneously on companion coal blocks exposed to the same gaseous environment. The adsorption amount and strain were determined after equilibration at P  ≤ 1.8 MPa. There is a strong non-linear correlation between strain and the quantity of gas adsorbed and the results for all gases and coals studied follow a common pattern. The dependence of the coal matrix shrinkage/swelling coefficient (C_gc) on the type and quantity of gas adsorbed is seen by plotting the ratio between the strain and the adsorbate concentration against the adsorbate concentration. In general, C_gc increases with increasing adsorbate concentration over the range of ~ 0.1 to 1.4 mmol/g. Results from the dried block coals are compared to CO₂ experiments using native coals with an inherent level of moisture as received. The amount of CO₂ adsorbed using native coals (assuming no displacement of H₂O by CO₂) is significantly less than the dried coals. The gas-induced strain (S) and adsorption amount (M) were measured as a function of time following step changes in CO₂, CH₄, and N₂ pressure from vacuum to 1.8 MPa. An empirical diffusion equation was applied to the kinetic data to obtain the exponent (n) for time dependence for each experiment. The data for all coals were pooled and the exponent (n) evaluated using an ANOVA statistical analysis method. Values for (n) near 0.5 were found to be independent on the coal, the gas or type of measurement (e.g., parallel strain, perpendicular strain, and gas uptake). These data support the use of a Fickian diffusion model framework for kinetic analysis. The kinetic constant k was determined using a unipore diffusion model for each experiment and the data were pooled for ANOVA analysis. For dry coal, statistically significant differences for k were found for the gases (CO₂ > N₂ > CH₄) and coals (Pocahontas >Blind Canyon > Pittsburgh #8) but not for the method of the kinetic measurement (e.g., strain or gas uptake). For Blind Canyon and Pittsburgh #8 coal, the rate of CO₂ adsorption and gas-induced strain for dry coal was significantly greater than that of the corresponding native coal. For Pocahontas coal the rates of CO₂ adsorption and gas-induced strain for dry and native coal were indistinguishable and may be related to its low native moisture and minimal amount of created porosity upon drying.     

Predicted CO2 emissions from maceral concentrates of high volatile bituminous Kentucky and Illinois coals

A large collection of well-characterized coals, documented in the Center for Applied Energy Research's (CAER) database, was used to estimate the CO₂ content of maceral concentrates from Kentucky and Illinois high volatile bituminous coals. The data showed no correlation between CO₂ versus coal ranks and between CO₂ versus maceral content. Subsequently, eight sets of low-ash density-gradient centrifugation (DGC) maceral concentrates from five coal beds were examined, spanning in the high volatile rank range. Heating value was not determined on the concentrates, but instead was calculated using the Mott–Spooner formula. There was a good correlation between predicted CO₂ and maceral content for the individual iso-rank (based on vitrinite reflectance, analyzed on whole (parent) coal) sets. In general, the predicted CO₂ increases from liptinite-rich through vitrinite-rich to inertinite-rich concentrates (note: no “concentrates” are absolutely monomaceral).