Effect of Physical Nature (Intact and Powder) of Coal on CO2 Adsorption at the Subcritical Pressure Range (up to 6.4 MPa at 298.15 K).

This study examines the influence of subcritical pressure and the physical nature (intact and powder) of coal samples on CO2 adsorption capacity and kinetics in the context of CO2 sequestration in shallow level coal seams. Manometric adsorption experiments were carried out on two anthracite and one bituminous coal samples. Isothermal adsorption experiments were carried out at 298.15 K in two pressure ranges: less than 6.1 MPa and up to 6.4 MPa relevant to gas/liquid adsorption. The adsorption isotherms of intact anthracite and bituminous samples were compared to that of the powdered samples. The powdered samples of the anthracitic samples had a higher adsorption than that of intact samples due to the exposed adsorption sites. The intact and powdered samples of bituminous coal, on the other hand, exhibited comparable adsorption capacities. The comparable adsorption capacity is attributed to the intact samples' channel-like pores and microfractures, where high density CO2 adsorption occurs. The adsorption-desorption hysteresis patterns and the residual amount of CO2 trapped in the pores reinforce the influence of the physical nature of the sample and pressure range on the CO2 adsorption-desorption behavior. The intact 18 ft AB samples showed significantly different adsorption isotherm pattern to that of powdered samples for experiments conducted up to 6.4 MPa equilibrium pressure due to the high-density CO2 adsorbed phase in the intact samples. The adsorption experimental data fit into the theoretical models showed that the BET model fit better than the Langmuir model. The experimental data fit into the pseudo first order, second order, and Bangham pore diffusion kinetic models showed that the rate-determining steps are bulk pore diffusion and surface interaction. Generally, the results obtained from the study demonstrated the significance of conducting experiments with large, intact core samples pertinent to CO2 sequestration in shallow coal seams.

Low Subcritical CO2 Adsorption-Desorption Behavior of Intact Bituminous Coal Cores Extracted from a Shallow Coal Seam.

This study focuses on improving fundamental understanding of low, subcritical CO2 adsorption-desorption behavior of bituminous coals with the aim to evaluate the utility of shallow-depth coal seams for safe and effective CO2 storage. Comprehensive data and a detailed description of coal-CO2 interactions, e.g., adsorption, desorption, and hysteresis behavior of intact bituminous coals at CO2 pressures <0.5 MPa, are limited. Manometric sorption experiments were performed on coal cores (50 mm dia. and 30- or 60-mm length) obtained from a 30 m deep coal seam located at the Upper Silesian Basin in Poland. Experimental results revealed that the adsorption capacities were correlated to void volume and equilibrium time under low-pressure injection (0.5 MPa). The positive deviation, observed in the hysteresis of adsorption-desorption isotherm patterns, and the increased sample mass at the end of the tests suggested CO2 pore diffusion and condensation. This behavior is vital for assessing low-pressure CO2 injection and storage capabilities of shallow coal seams where confining pressure is much lower than that of the deeper seams. Overall, CO2 adsorption depicts a type II adsorption isotherm and a type H3 hysteresis pattern of the IUPAC classification. Experimental results fitted better to the Brunauer-Emmett-Teller model than the Langmuir isotherm model. CO2 adsorption behavior of intact cores was also evaluated by characteristic curves. It was found that Curve I favored physical forces, i.e., the presence of van der Waals/London dispersion forces to describe the coal-CO2 interactions. However, analysis of Curve II indicated that the changing pressure-volume behavior of CO2 in the adsorbed phase, under low equilibrium pressures, cannot be ignored.

Characterisation of inorganic constitutions of condensate and solid residue generated from small-scale ex situ experiments in the context of underground coal gasification.

This paper deals with the characterisation of inorganic constitutions generated at various operating conditions in the context of underground coal gasification (UCG). The ex situ small-scale experiments were conducted with coal specimens of different rank, from the South Wales Coalfield, Wales, UK, and Upper Silesian Coal Basin, Poland. The experiments were conducted at various gaseous oxidant ratios (water: oxygen = 1:1 and 2:1), pressures (20 bar and 36 bar) and temperatures (650°C, 750°C and 850°C). Increasing the amount of water in the oxidants proportionately decreased the cationic elements but increased the concentrations of anionic species. The temperature played minor impact, while the high-pressure experiments at temperature optimum to produce methane-rich syngas (750°C) showed significant reduction in cationic element generation. However, both coal specimens produced high amount of anionic species (F, Cl, SO4 and NO3). The "Hard" bituminous coal from Poland produced less gasification residues and condensates than the South Wales anthracitic coal due to its higher reactivity. The inorganic composition found in the solid residue was used in the theoretical calculation to predict the dissolved product concentrations when the solid residue interacts with deep coal seam water in the event of UCG cavity flooding. It was evident from the solubility products of the Cr, Ni and Zn that changes in the groundwater geochemistry occur; hence, their transportation in the subsurface must be studied further.

Characterization of silver-kaolinite (AgK): an adsorbent for long-lived (129)I species.

Bentonite is a preferred buffer and backfill material for deep geological disposal of high-level nuclear waste (HLW). Bentonite does not retain anions by virtue of its negatively charged basal surface. Imparting anion retention ability to bentonite is important to enable the expansive clay to retain long-lived (129)I (iodine-129; half-life = 16 million years) species that may escape from the HLW geological repository. Silver-kaolinite (AgK) material is prepared as an additive to improve the iodide retention capacity of bentonite. The AgK is prepared by heating kaolinite-silver nitrate mix at 400 °C to study the kaolinite influence on the transition metal ion when reacting at its dehydroxylation temperature. Thermo gravimetric-Evolved Gas Detection analysis, X-ray diffraction analysis, X-ray photo electron spectroscopy and electron probe micro analysis indicated that silver occurs as AgO/Ag2O surface coating on thermally reacting kaolinite with silver nitrate at 400 °C.