Chemical leaching of an Indian bituminous coal and characterization of the products by vibrational spectroscopic techniques

High volatile bituminous coal .was demineralized by a chemical method. The vibrations of the ＂aromatics＂ structure of graphite, crystalline or non-crystalline, were observed in the spectra at the 1600 cm-1 region. The band at 1477 cm-1 is assigned as VR band, the band at 1392 cm-1 as VL band and the band at 1540 cm-1 as GR band. Graphite structure remains after chemical leaching liberates oxygenated functional groups and mineral groups. The silicate bands between 1010 and 1100 cm-1 are active in the infrared （IR） spec^urn but inactive in the Raman spectrum. Absorption arising from C-H stretching in alkenes occurs in the region of 3000 to 2840 cm-~. Raman bands because of symmetric stretch of water molecules were also observed in the spectrum at 3250 cm-1 and 3450 cm-1. Scanning electron microscopy analy- sis revealed the presence of a graphite layer on the surface. Leaching of the sample with hydrofluoric acid decreases the mineral phase and increases the carbon content. The ash content is reduced by 84.5wt% with leaching from its initial value by mainly removing aluminum and silicate containing minerals.

Effects of sub-/super-critical CO_(2)on the fracture-related mechanical characteristics of bituminous coal

Injecting carbon dioxide CO_(2)into a coal seam is an important way to improve coalbed methane recovery and to store geological carbon.The fracture mechanical characteristics of bituminous coal determine the propagation and evolution of cracks,which directly affect CO_(2)storage in coal seams and the efficiency of resource recovery.This study applied CO_(2)adsorption and three-point bending fracture experiments using bituminous coal samples in a gaseous state(4 MPa),subcritical state(6 MPa),and supercritical state(8 and 12 MPa)to investigate the influence of CO_(2)state and anisotropy on the fracture-related mechanical response of bituminous coal.The results show that the change in mechanical properties caused by CO_(2)adsorption is CO_(2)state-dependent.The supercritical CO_(2)adsorption at 8 MPa causes the largest decrease in the mode-I fracture toughness(KIC),which is 63.6%lower than the toughness before CO_(2)adsorption.The instability characteristics of bituminous coal show the transformation trend of“sudden-gradual-sudden fracture”.With or without CO_(2)adsorption,the order of the KIC associated with three types of bituminous coal specimens is crack-divider type>crack-arrester type>crack-short transverse type.Phenomenologically,the fracture toughness of bituminous coal is positively correlated with its specific surface area and total pore volume;the toughness is negatively correlated with its average pore size.

Major elements analysis in bituminous coals under different ambient gases by laser-induced breakdown spectroscopy with PLS modeling

Three major elements, carbon, hydrogen, and nitrogen, in twenty-four bituminous coal samples, were measured by laser-induced breakdown spectroscopy. Argon and helium were applied as ambient gas to enhance the signals and eliminate the interference of nitrogen from surrounding air. The relative standard deviation of the related emission lines and the performance in the partial least squares （PLS） modeling were compared for different ambient environments. The results showed that argon not only improved the intensity, but also reduced signal fluctuation. The PLS model also had the optimal performance in multi-element analysis using argon as ambient gas. The root mean square error of prediction of carbon concentration decreased from 4.25% in air to 3.49% in argon, while the average relative error reduced from 4.96% to 2.98%. Hydrogen line demonstrated similar improvement. Yet, the nitrogen lines were too weak to be detected even in an argon environment which suggested the nitrogen signal measured in air come from the breakdown of nitrogen molecules in the atmosphere.

Pore size distribution of high volatile bituminous coal of the southern Junggar Basin: a full-scale characterization applying multiple methods

Studying on the pore size distribution of coal is vital for determining reasonable coalbed methane development strategies.The coalbed methane project is in progress in the southern Junggar Basin of northwestern China,where high volatile bituminous coal is reserved.In this study,with the purpose of accurately characterizing the full-scale pore size distribution of the high volatile bituminous coal of the southern Junggar Basin,two grouped coal samples were applied for mercury intrusion porosimetry,low-temperature nitrogen adsorption,low-field nuclear magnetic resonance,rate-controlled mercury penetration,scanning electron microscopy,and nano-CT measurements.A comprehensive pore size distribution was proposed by combining the corrected mercury intrusion porosimetry data and low-temperature nitrogen adsorption data.The relationship between transverse relaxation time(T2,ms)and the pore diameter was determined by comparing the T2 spectrum with the comprehensive pore size distribution.The macro-pore and throat size distributions derived from nano-CT and rate-controlled mercury penetration were distinguishingly analyzed.The results showed that:1)comprehensive pore size distribution analysis can be regarded as an accurate method to characterize the pore size distribution of high volatile bituminous coal;2)for the high volatile bituminous coal of the southern Junggar Basin,the meso-pore volume was the greatest,followed by the transition pore volume or macro-pore volume,and the micro-pore volume was the lowest;3)the relationship between T2 and the pore diameter varied for different samples,even for samples with close maturities;4)the throat size distribution derived from nano-CT was close to that derived from rate-controlled mercury penetration,while the macro-pore size distributions derived from those two methods were very different.This work can deepen the knowledge of the pore size distribution characterization techniques of coal and provide new insight for accurate pore size distribution characterization of high volatile bituminous coal.

Mechanism of micro-wetting of highly hydrophobic coal dust in underground mining and new wetting agent development

The internal mechanism of the high hydrophobicity of the coal samples from the Pingdingshan mining area was studied through industrial,element,and surface functional group analysis.Laboratory testing and molecular dynamics simulations were employed to study the impact of three types of surfactants on the surface adsorption properties and wettability of highly hydrophobic bituminous coal.The results show that the surface of highly hydrophobic bituminous coal is compact,rich in inorganic minerals,and poorly wettable and that coal molecules are dominated by hydrophobic functional groups of aromatic rings and aliphatic structures.The wetting performance of surfactants as the intermediate carrier to connect coal and water molecules is largely determined by the interaction force between surfactants and coal(Fs-c)and the interaction force between surfactants and water(Fs-w),which effectively improve the wettability of modified coal dust via modifying its surface electrical properties and surface energy.A new type of wetting agent with a dust removal rate of 89%has been developed through discovery of a compound wetting agent solution with optimal wetting and settling performance.This paper provides theoretical and technical support for removing highly hydrophobic bituminous coal dust in underground mining.

Wavelength Dependence in the Analysis of Carbon Content in Coal by Nanosecond 266 nm and 1064 nm Laser Induced Breakdown Spectroscopy

The wavelength dependence of laser induced breakdown spectroscopy （LIBS） in the analysis of the carbon contents of coal was studied using 266 nm and 1064 nm laser radiations. Compared with the 1064 nm wavelength laser ablation, the 266 nm wavelength laser ablation has less thermal effects, resulting in a better crater morphology on the coal pellets. Besides, the 266 nm wavelength laser ablation also provides better laser-sample coupling and less plasma shielding, resulting in a higher carbon line intensity and better signal reproducibility. The carbon contents in the bituminous coal samples have better linearity with the line intensities of atomic carbon measured by the 266 nm wavelength than those measured by the 1064 nm wavelength. The partial least square （PLS） model was established for the quantitative analysis of the carbon content in coal samples by LIBS. The results show that both of the 266 nm and 1064 nm wavelengths are capable of achieving good performance for the quantitative analysis of carbon content in coal using the PLS method.

Formation mechanism of methane during coal evolution:A density functional theory study

The formation mechanism of methane （CH4） during coal evolution has been investigated by density functional theory （DFT） of quantum chemistry. Thermogenic gas, which is generated during the thermal evolution of medium rank coal, is the main source of coalbed methane （CBM）. Ethylbenzene （A） and 6,7-dimethyl-5,6,7,8-tetrahydro-1-hydroxynaphthalene （B） have been used as model compounds to study the pyrolysis mechanism of highly volatile bituminous coal （R）, according to the similarity of bond orders and bond lengths. All possible paths are designed for each model. It can be concluded that the activation energies for H-assisted paths are lower than others in the process of methane formation; an H radical attacking on β-C to yield CH4 is the dominant path for the formation of CH4 from highly volatile bituminous coal. In addition, the calculated results also reveal that the positions on which H radical attacks and to which intramolecular H migrates have effects on methyl cleavage.

Molecular simulation studies of hydrocarbon and carbon dioxide adsorption on coal

Sorption isotherms of hydrocarbon and carbon dioxide （CO2） provide crucial information for designing processes to sequester CO2 and recover natural gas from unmineable coal beds. Methane （CH4）, ethane （C2H6）, and CO2 adsorption isotherms on dry coal and the temperature effect on their maximum sorption capacity have been studied by performing combined Monte Carlo （MC） and molecular dynamics （MD） simulations at temperatures of 308 and 370 K （35 and 97 ~C） and at pressures up to 10 MPa. Simulation results demonstrate that absolute sorption （expressed as a mass basis） divided by bulk gas density has negligible temperature effect on CH4, C2H6, and CO2 sorption on dry coal when pressure is over 6 MPa. CO2 is more closely packed due to stronger interaction with coal and the stronger interaction between CO2 mole- cules compared, respectively, with the interactions between hydrocarbons and coal and between hydrocarbons. The results of this work suggest that the ＂a＂ constant （pro- portional to TcPc） in the Peng-Robinson equation of state is an important factor affecting the sorption behavior of hydrocarbons. CO2 injection pressures of lower than 8 MPa may be desirable for CH4 recovery and CO2 sequestration. This study provides a quantitative under- standing of the effects of temperature on coal sorptioncapacity for CH4, C2H6, and CO2 from a microscopic perspective.

Geology, Palaeodeposition and the Involvement of Rhyolite Melts in the Petrogenesis of the Tabenken Coal Seam in the North West Region of Cameroon

The discovery of patches of a coal deposit and other associated sedimentary and volcanic rocks in Tabenken North West Cameroon has raised the question of the geology and palaeoenvironment of that area. This Region, which is predominantly characterized by a granitoid basement of Precambrian age is in most parts overlain by Cenozoic basalts, hawaite, mugearite, trachyte and rhyolites. Volcanic outpours modified the geomorphology of the area into a series of hills and valleys. We investigated the geological setting in view of reconstituting the palaeodepositional environment of the Tabenken Coal Seam. Field studies show that the coal occurs in form of inclusions within sandstones, high grade coal bed, massive beds exposed by landslides and in alkali rhyolites. The results of Ultimate analyses of the coal indicate bituminous coal with 58% Carbon, sulfur content as low as 0.12% and ash content of 17%. The occurrence of a well stratified dark volcanic ash bed in the area is interpreted to be an interactive product of the explosive volcanic activity and weathering. Field examination of the area suggests that it was a micro-continental sedimentary palaeo-basin which was later infilled with Cenozoic volcanic outpours which probably modified the chemistry of the coal to meta-anthracites. The actual ages of the coal as well as the associated sedimentary units have not been established, meanwhile, the volcanism started some 31 ma ago.

Hierarchical porous carbon derived from coal-based carbon foam for high-performance supercapacitors

Hierarchical porous carbon(HPC)from bituminous coal was designed and synthesized through pyrolysis foaming and KOH activation.The obtained HPC(NCF-KOH)were characterized by a high specific surface area(S_(BET))of 3472.41 m^(2)/g,appropriate mesopores with V_(mes)/V_(total)of 57%,and a proper amount of surface oxygen content(10.03%).This NCF-KOH exhibited a high specific capacitance of 487 F/g at 1.0 A/g and a rate capability of 400 F/g at 50 A/g based on the three-electrode configuration.As an electrode for a symmetric capacitor,a specific capacitance of 299 F/g at 0.5 A/g was exhibited,and the specific capacitance retained 96%of the initial capacity at 5 A/g after 10,000 cycles.Furthermore,under the power density of 249.6 W/kg in 6 mol/L KOH,a high energy density of 10.34 Wh/kg was obtained.The excellent charge storage capability benefited from its interconnected hierarchical pore structure with high accessible surface area and the suitable amount of oxygen-containing functional groups.Thus,an effective strategy to synthesize HPC for high-performance supercapacitors serves as a promising way of converting coal into advanced carbon materials.