N2 Adsorption Method Research Articles

Study on the variability of oxygen adsorption behavior in coal gangue based on pore size structure

To investigate the adsorption and migration behavior of oxygen in coal gangue with different pore sizes, this study characterizes the multiscale morphology of coal gangue pores and fractures using SEM NMR, and low-temperature N2 (77 K) adsorption methods. As well, the study simulates the adsorption and diffusion behavior of O2 within the pore structures of coal gangue based on GCMC and MD methods. The study examines the oxygen adsorption characteristics across different pore sizes and analyzes the mass transfer mechanisms during oxygen diffusion. Results indicate that the pores in coal gangue are predominantly micropores within the 1–10 nm range. As pore size increases, the absolute adsorption amount of oxygen increases while the isosteric heat of adsorption decreases. The isosteric heat of adsorption in coal gangue models with different pore sizes is less than 42 kJ/mol, indicating the physical adsorption of oxygen within the pores. Oxygen shows adsorption layering perpendicular to the coal gangue surface, with adsorption density distribution differences decreasing and adsorption capacity weakening as pore size increases. The O2 adsorption isotherms in coal gangue follow Langmuir adsorption principles, with oxygen saturation adsorption decreasing as absolute adsorption increases. The confinement effect of coal gangue on oxygen weakens as pore size increases, and the impact of increasing pore size on oxygen diffusion is stronger than adsorption. These findings are significant for understanding the microscopic adsorption and diffusion behavior of O2 in coal gangue pores and fractures and are crucial for accurately preventing and managing spontaneous combustion in coal gangue piles.

Reduction of Trinitrobenzene to Amines with Molecular Hydrogen over Chrysocolla-like Catalysts

The cheap non-noble Cu–SiO2-based nanocatalysts are under intensive study in different reactions resulting in useful chemicals, yet their application in environment protection is poorly studied. In the present work, the influence of the Cu loading (3–15 wt%) on the catalytic behavior of Cu/SiO2 materials was first precisely studied in the hydrogenation of hazardous trinitrobenzene to valuable aromatic amines with molecular hydrogen. The catalysts have been synthesized by the method of deposition–precipitation using urea. The catalyst characterization by XRD, TPR-H2, SEM, TEM, and N2 adsorption methods confirmed that they include nanoparticles of the micro-mesoporous chrysocolla-like phase supported in the mesopores of a commercial SiO2 carrier, as well as revealed formation of the highly dispersed CuO phase in the sample with the highest Cu loading. Variation in reaction conditions showed the optimal ones (170 °C, 1.3 MPa H2) resulting in complete trinitrobenzene conversion with a triaminobenzene yield of 65% for the catalyst with a 15% Cu loading, and the best yield of 82% was obtained over the catalyst with 10% Cu calcined at 600 °C. The results show the potential of Cu phyllosilicate-based catalysts for the utilization of trinitroaromatic compounds via catalytic hydrogenation to amines and their possible applications in a remediation treatment system.

Influence of Supercritical Conditions on Isothermal Adsorption Capacity Calculation of Methane and Model Optimization.

The study of isothermal adsorption models for coal and methane under supercritical conditions helps us to understand the gas content distribution in coal seams and improve gas management in coal mines. Coal samples from the Hebi mine and Longshan coal mine were selected for this research. Using the weight method, isothermal adsorption curves of supercritical methane at temperatures of 308, 313, and 318 K were measured. The adsorption phase density of supercritical methane was obtained by using the intercept method and model fitting, and the absolute adsorption capacity of methane was calculated. Simultaneously, the pore volume and specific surface area of the coal samples were tested, and the isothermal adsorption model for supercritical methane was studied and optimized. The results indicate that using mercury intrusion, low-temperature N2, and low-temperature CO2 adsorption methods for testing coal sample pore structures allows for multiscale characterization of the coal pore structure. Based on the Gibbs excess adsorption theory, the phase density of methane obtained from the intercept method and model fitting effectively represent the isothermal adsorption curve of supercritical methane. By combination of the specific surface area and pore volume distribution of the coal with the absolute adsorption capacity of methane, the number of methane adsorption layers on the coal surface was calculated to be between 1.11 and 1.3 layers. This suggests that the isothermal adsorption model for supercritical methane on coal is not solely micropore filling or single molecular layer adsorption but primarily single molecular layer adsorption with concurrent micropore filling adsorption. Based on this adsorption mechanism, an L-DA isothermal adsorption model for supercritical methane on coal was established. The L-DA isothermal model shows good fitting results and effectively explains the adsorption characteristics of supercritical methane on coal.

Pore evolution and reaction mechanism of coal under the combination of chemical activation and autothermal oxidation

Aiming at the limitation problems such as limited scope, high cost and energy consumption of coal bed penetration enhancement technology by traditional physical and chemical methods, a coal seam methane penetration enhancement method based on the combined action of chemical activation and auto thermal oxidation is proposed from the idea of utilizing the in-situ energy of the coal body. In this paper, N2 and CO2 adsorption, XPS and FTIR methods are used to study the pore structure evolution law and the change characteristics of the reactive structure of coal matrix under the effect of chemically activated autothermal oxidation. The synergistic microporous pore volume of chemical activation and auto thermal oxidation was 48.91 cm3/g−1 × 10-3, which was 28.96 % and 22.7 % higher than chemical activation and auto thermal oxidation respectively; The microporous specific surface area was 162.7 m2/g, which was 38 % and 26.6 % higher than chemical activation and auto thermal oxidation respectively. Activated coals expand and merge holes to a deeper degree after oxidative warming, and the complexity of the pore structure in the coal decreases; Highly reactive radicals in coal pores substantially promote the oxidation of coal structure, enhance the aromatic polymerization reaction of activated coal, and improve the maturity and aromaticity of activated coal, and the oxygen-containing functional groups in activated coal are negatively correlated with the oxidation temperature. The results of this study reveal the potential of the auto thermal oxidation-driven penetration enhancement method under chemical activation for coal seam gas penetration enhancement and extraction.

Large‐scale synthesis of nano‐ZIF‐90 from zinc chloride application orientation heat storage materials

AbstractThe paper presents the results of the first research on the synthesis of nano‐ZIF‐90 from zinc chloride. More specifically, the paper also introduces the results of large‐scale pure nano‐ZIF‐90 synthesis with a high specific surface, uniform cubic crystals, and good thermal strength. ZIF‐90 is synthesized from zinc chloride‐containing medium capillaries, which have both a weak acid center and a strong base center. The post‐synthetic ZIF‐90 was also evaluated for heat storage based on its ability to adsorb water, methanol, and ethanol. XRD, FTIR, SEM, TEM, N2 adsorption and desorption methods, TG mass thermal analysis, and NH3‐TPD/CO2‐TPD were used to study the ZIF‐90 crystallization process with modifications of precursors, solvents, additives, and reaction conditions. From this, a large‐scale synthesis of nano‐ZIF‐90 from high‐efficiency zinc chloride has been derived. DSC measurements are used to evaluate the enthalpy adsorption of water, methanol, and ethanol on ZIF‐90.

Influence of hydraulic pressure on pore structure evolution and chloride transport in concrete

To study the influence of hydraulic pressure on pore structure evolution and chloride transport behaviour in concrete, the mass transport depth, chloride concentration and pore characteristics of specimens with different water/cement (w/c) ratios were investigated using silver nitrate spraying, potentiometric titration, mercury intrusion porosimetry, nitrogen adsorption tests and confocal laser scanning microscopy. The results showed that the chloride concentration increased with increases in the hydraulic pressure and w/c ratio. With increasing hydraulic pressure, the transport depths of water and chloride ion transport expanded from 5.2 mm to 25.4 mm. An increase in hydraulic pressure changed the pore structure of the concrete, leading to a surge in the specific surface area, greater porosity and larger average pore diameters. Notably, ink-bottle shaped pores emerged prominently and the proportion of fine mesopores and capillary pores markedly increased after the application of hydraulic pressure. A relationship between the chloride diffusion coefficient and hydraulic pressure was developed and a relationship between the modified permeability coefficient and hydraulic pressure was constructed based on the mesoporous contribution to express the hysteresis effect of chloride.

Indicative significance of the interfacial interactions between pore surface and soluble organic matter on the shale oil mobility

The exploration and exploitation of shale oil resources enhance the necessity to characterize the mobility of the occluded oil in shales. Up to now, the understanding of the controlling factors of shale oil mobility has mainly come from molecular dynamics simulation but lacking in-depth research on actual shales. Therefore, in this study, the effects of mineral composition, soluble organic matter (SOM) composition and wettability on the shale oil mobility were studied by X-ray diffraction, N2 adsorption, mercury intrusion, contact angle, chloroform bitumen and group component detection methods, comprehensively. The results show that: (1) The asphaltene contents and (Asphaltenes × Aromatics)/(Saturates × Resins) negatively and positively correlate with clay and carbonate mineral contents, respectively, while the I/S and illite contents present opposite trend with (Asphaltenes × Aromatics)/(Saturates × Resins). These correlations indicate that the SOM that confined in the pores constructed with carbonate minerals and illite present better flow potential. (2) Both δVt and δSSA negatively correlate with asphaltenes and (Asphaltenes × Aromatics)/(Saturates × Resins). That is, less pores and surfaces can be released by extraction for the shales with more asphaltenes. Therefore, it can be concluded that asphaltene is a negative factor for shale oil seepage. Additionally, the larger pores present better flow condition for shale oil, even for asphaltenes. (3) Pore surface wettability also significantly affects the shale oil mobility. The hydrophobicity of the pore wall greatly inhibits the shale oil flow, especially for the mesopores and macropores. The pattern diagram was established to illustrate the effect of the interactions between pore surfaces and shale oil components on the movable potential. Based on our research, mineral composition, group composition and pore surface wettability are efficient parameters for the shale oil mobility evaluation based on the interfacial interaction theory, and the “sweet spots” for shale oil seepage of the Jiyang Depression are the shales with more illite, carbonate, saturates and relatively low lipophilicity.

Low-carbon shape-stable phase change composite utilizing semi-coke ash for building thermal energy storage

To enhance the efficiency and cost-effectiveness of heating, air-conditioning, and solid waste recycling in buildings, this work proposed the solid waste semi-coke ash as skeleton material and the sodium carbonate as phase-change material to produce shape-stable phase-change composites using the cold compression-hot sintering method for building thermal energy storage. Eight shape-stable phase-change composites were prepared and the detailed chemical compatibility, thermal property, structural and mechanical performance, and micromorphology were investigated by X-ray diffraction, differential scanning calorimetry, laser flash analysis, N2 adsorption and desorption method, constant speed pressurization method, and scanning electron microscopy. Results demonstrated that semi-coke ash is suitable with sodium carbonate for fabricating shape-stable phase-change composites. The optimal mass ratio of semi-coke ash to Na2CO3 powder for sample CC3 was determined to be 52.5:47.5. This particular sample demonstrated a thermal energy storage density of 961.58 J/g and a maximum thermal conductivity of 1.306 W/(m ∙ K). It also exhibited excellent chemical compatibility between its components. Furthermore, sample CC3 displayed a mechanical strength of 23.57 MPa, with elements evenly distributed throughout. Importantly, CO2 emission from the production of sample CC3 was significantly low, indicating great potential for commercialization.

Influence of mineral composition and firing temperature on the micro- and mesoporosity of replicate archaeological ceramics

Abstract The role of micro- and mesopores of archaeological ceramics in preserving ancient biomolecules is not well established. To understand the formation of these nano-sized pores in ceramics, reference pottery briquettes were made using two different clay types (illitic and kaolinitic clays), two different tempers (sand and chalk), and two different firing temperatures (600 and 800°C). The mineral content of the briquettes was determined by quantitative X-ray diffraction, and the micro- and mesopores were characterized with the N2 adsorption method. The Brunauer–Emmett–Teller method, the adsorbed volume near liquefaction, and application of non-local density functional theory (NLDFT) were used on the N2 adsorption data to determine specific surface areas, specific pore volumes, and pore-size distributions. Values of the micro- and mesoporosity parameters of most of the briquettes were approximately proportional to the initial clay content and unrelated to temper; the proportionality factors were much larger for illitic clay than for kaolinitic clay. When chalk-tempered briquettes were fired at the higher firing temperature of 800°C, the parameters were no longer proportional to the initial clay content; they decreased in most briquettes formed of illitic clay due to reaction of the clay with lime, and they increased in briquettes formed of kaolinitic clay due mostly to the porosity of unreacted lime. Micropore volumes in briquettes formed mostly of illitic clay were substantial: of the order of 5 mm3 g−1. The work presented here forms a basis for future studies to establish a plausible mechanism of organic residue absorption and preservation in ancient ceramics.

Preparation of rutin imprinted monolith (RIM) by using porogen containing ion liquid [BMIM]PF6 and its molecular recognition

A [BMIM]PF6 ion liquid (IL)-assisted synthesis of a rutin imprinted monolith (RIM) was carried out in an in-situ polymerization method. Bi-functional monomers and a ternary porogen containing IL was used for the RIM preparation and a L9(33) orthogonal factor design performed. Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR) and N2 adsorption method was for structural characterization of the RIMs. The monolith was directly used as stationary phase in liquid chromatography to test the retention selectivity, adsorption capacity and extraction application. The optimized porogen consists of 900 μL DMF, 144 μL ACN and 216 μL IL. The monolith RIM-13 obtained under the optimized conditions possessed improved adsorption performance, with a dynamic adsorption capacity of 6.695 mg/g, an imprinting efficiency of 4.841 and a selectivity α value of 4.821. Additionally, this monolith had also higher specific surface area, pore volume and permeability than that obtained without IL and the homogeneity of the imprint sites could be improved by using IL. When the RIM-13 was applied to the separation and purification of rutin from tartary buckwheat, a rutin product with a purity higher than 92 % can be obtained by one cycle. This molecular imprint solid-phase extraction (MI-SPE) is of potency to be applied to preparative-scale separation of other natural products.

Salt confined in MIL-101(Cr) - tailoring the composite sorbents for efficient atmospheric water harvesting.

The adsorption method for atmospheric water harvesting (AWH) is considered as a promising heat driven technology for potable water supply in arid regions. This research is focused on the novel composite sorbents based on hygroscopic salts loaded in the pores of MIL-101(Cr) developed for AWH. The composites based on LiCl, LiBr, CaCl2, and Ca(NO3)2 were synthesised and comprehensively studied by SEM, XRD, N2 adsorption, and TG methods. We evidence that the CaCl2/MIL-101(Cr) composite demonstrates a high net water uptake of 0.52-0.59 g_(H2O)/g_(composite) per cycle under conditions of Saudi Arabia and the Sahara Desert as the reference regions with extra-dry climate. It is shown that water adsorption on the composite cannot be presented as a combination of the adsorption on the components, thus indicating on a synergistic effect. A detailed characterization of water coordination, mobility and hydrogen bonding within the confined CaCl2 hydrates and salt solution with solid state 2H NMR has been performed. It is established that pores confinement promotes a prolonged transition to a dynamically melted state of the hydrated salt and a notable decrease of the melting temperature, which facilitates the molecular transport of water and causes the alteration of sorption properties of CaCl2 inside MIL-101 pores.

A novel catalyst based on nickel phyllosilicate for the selective hydrogenation of unsaturated compounds

A new nickel phyllosilicate (Ni-PhySi) catalyst was synthesized and used for the selective hydrogenation of unsaturated compounds to alkenes. Nickel phyllosilicate catalyst was synthesized by deposition-precipitation with urea method and characterized by TPR-H2, N2 adsorption, XRD, FTIR and HRTEM methods. Nickel phyllosilicate showed an enhanced catalytic activity compared with supported nickel oxide and Ni Raney in hydrogenation of unsaturated compounds at mild conditions with the selectivity toward C = C bond formation higher than 86%. Moreover, nickel phyllosilicate demonstrated a great stability during at least seven cycles of reuse.

Effects of Torrefaction Pretreatment on the Structural Features and Combustion Characteristics of Biomass-Based Fuel.

Wheat straw, a typical agricultural solid waste, was employed to clarify the effects of torrefaction on the structural features and combustion reactivity of biomass. Two typical torrefaction temperatures (543 K and 573 K), four atmospheres (argon, 6 vol.% O2, dry flue gas and raw flue gas) were selected. The elemental distribution, compositional variation, surface physicochemical structure and combustion reactivity of each sample were identified using elemental analysis, XPS, N2 adsorption, TGA and FOW methods. Oxidative torrefaction tended to optimize the fuel quality of biomass effectively, and the enhancement of torrefaction severity improved the fuel quality of wheat straw. The O2, CO2 and H2O in flue gas could synergistically enhance the desorption of hydrophilic structures during oxidative torrefaction process, especially at high temperatures. Meanwhile, the variations in microstructure of wheat straw promoted the conversion of N-A into edge nitrogen structures (N-5 and N-6), especially N-5, which is a precursor of HCN. Additionally, mild surface oxidation tended to promote the generation of some new oxygen-containing functionalities with high reactivity on the surface of wheat straw particles after undergoing oxidative torrefaction pretreatment. Due to the removal of hemicellulose and cellulose from wheat straw particles and the generation of new functional groups on the particle surfaces, the ignition temperature of each torrefied sample expressed an increasing tendency, while the Ea clearly decreased. According to the results obtained from this research, it could be concluded that torrefaction conducted in a raw flue gas atmosphere at 573 K would improve the fuel quality and reactivity of wheat straw most significantly.

Ceria‐Modified Copper Phyllosilicate Catalyst for One‐Pot Hydroamination of 5‐HMF with Nitro‐Compounds

AbstractCeria‐modified mineral‐like copper catalyst 12 %Cu/SiO2−CeO2 showed a high activity and selectivity in one‐pot hydroamination of bio‐available 5‐hydroxymethylfurfural with nitro‐aromatic compounds. The catalyst was obtained by conventional deposition‐precipitation method with urea from commercial silica, copper nitrate, and ammonium cerium (IV) nitrate. The synthesized catalyst with a copper phyllosilicate structure formed inside the pores of silica was studied by XRD, N2 adsorption, XPS, SEM and TEM methods. The possible scheme of 5‐hydroxymethylfurfural hydroamination with nitro‐aromatic compounds and an evolution of the catalyst structure during the reaction were proposed. The catalyst can be successfully recycled after calcination procedure. A number of N‐furfurylamines were obtained for the first time over 12 %Cu/SiO2−CeO2 catalyst with the phyllosilicate structure directly from 5‐hydroxymethylfurfural and nitro‐aromatic compounds with the yields up to 85 %.

Pore Structure and Fractal Characteristics of Marine–Continental Transitional Black Shales: A Case Study of the Permian Shanxi Formation in the Eastern Margin of the Ordos Basin

To study the microscopic pore characteristics of marine–continental transitional shale, we studied the Daning–Jixian block of the Shanxi Formation using low-pressure CO2 adsorption (LP-CO2A) and low-temperature N2 adsorption (LT-N2A) methods in conjunction with field emission scanning electron microscopy (FE-SEM), geochemistry, and mineral composition analysis in order to obtain pore structure characteristic parameters. The fractal dimension of the pores was calculated using the Frankel–Halsey–Hill (FHH) model, and the study also discusses the factors that influence the pore structure. The study found that the marine–continental transitional phase shale of the Shanxi Formation has clay mineral contents ranging from 36.24% to 65.21%. The total organic carbon (TOC) contents range from 0.64% to 9.70%. Additionally, the organic matter maturity is high. The FE-SEM and gas adsorption experiments revealed that the transitional shale of the Shanxi Formation possesses a diverse range of pore types with relatively large pore sizes. The dominant pore types are organic and intragranular pores, with pore morphologies predominantly appearing as slit and parallel plate structures. According to the experimental data on gas adsorption, the total SSA values range from 11.126 to 47.220 m2/g. The total PV values range from 0.014 to 0.056 cm3/g. Micropores make up a greater proportion of the total SSA, whereas mesoporous pores make up a greater proportion of the total PV. The distribution of shale pore fractal dimensions D1 and D2 (D1 is 2.470 to 2.557; D2 is 2.531 to 2.755), obtained through LT-N2A data, is relatively concentrated. D1 and D2 have a positive correlation with the TOC content, clay mineral content, and BET-SSA, and D1 and D2 have a negative correlation with the quartz content. D2 is positively correlated with the Langmuir volume, showing that D2 can be used to evaluate the methane adsorption capacity.

Polyacrylonitrile-Based Composite Carbon Nanofibers with Tailored Microporosity

Carbon nanofibers are currently used in many applications including electrochemical power sources, particularly, fuel cells. Their properties are highly dependent on the micro- and mesoporous structure. Here we provide a porosimetric analysis of the polyacrylonitrile-based electrospun composite Zr- and Ni-containing carbon nanofiber mats by N2 and CO2 adsorption methods for the first time. It was found that pyrolysis temperature affects specific surface area and volume: the values increase for the sample pyrolyzed at 900 °C compared with the initial stabilized nanofibers (300 °C, air) according to the Dubinin --- Radushkevich, non-local density functional theory (NLDFT) and grand canonical Monte-Carlo methods (GCMC). For higher pyrolysis temperatures (1000 and 1200 °C), the porosimetric parameters decrease compared with the one pyrolyzed at 900 °C. According to the NLDFT and GCMC pore size distribution, the difference for pyrolyzed samples is mostly related to a sharp decrease in the specific surface area for pores with a size of ~ 0.5 nm and an increase for pores at 0.55--0.8 nm compared with the initial stabilized sample. The study demonstrates a way to adjust porosimetric parameters depending on the pyrolysis conditions of the nanofiber mats, since it can improve characteristics of such type of carbon materials in electrochemical devices

Nanopore Characteristics of the Cambrian Niutitang Formation Organic-Rich Shales in the Middle Yangtze Region and Its Formation Controlling Factors

The shale of Cambrian Niutitang Formation is one of the most important shale gas reservoirs in the Middle Yangtze region, South China. Nanopores are important reservoir spaces for shale gas. The study of pore characteristics and its formation controlling factors is of great significance for the exploration and development of shale gas in the Niutitang Formation. In this study, two drilling core samples and two profile samples were investigated. The laser Raman, X-ray diffraction analysis, FE-SEM, and low-pressure N2 and CO2 adsorption methods are used to study the geochemical and mineral compositions of the shales, and the nanopore characteristics and its formation controlling factors of the shales are discussed. Results show that the shales have the following features: (1) rich in organic matter (OM) and the total organic carbon (TOC) contents ranging from 2.65 to 11.33%, with an average value of 6.81%. (2) The main mineral components of these shales are quartz, feldspar, clay minerals, calcite, and a small amount of pyrite. (3) The samples from the center of the Middle Yangtze region (EY1 well and BGP profile) have a higher maturity value ( Rmc R 0 % = 4.0 %) relatively to the samples from the south of the Middle Yangtze region (XD1 well and JF profile), where the Rmc R 0 % is 2.8%. (4) The maximum N2 adsorption capacity of the four groups of shale samples ranges from 5.090 to 27.333 cm3/g, with an average value of 15.571 cm3/g, while the maximum CO2 adsorption capacity ranges from 2.686 to 5.567 cm3/g, with an average value of 3.776 cm3/g. The higher maturity leads to the EY1 well having the lowest average maximum N2 adsorption capacity, while most of the OM pores in the EY1 well and BGP profile samples are smaller than 10 nm in diameter. The tectonic uplift leads to the profile samples having more meso-macropores than the core samples. The dissolution pores and granular mineral support are the key factors for the better pore structure of the high-evolution stage Niutitang Formation shale.

Ammonia Removal in Activated Carbons Prepared from Olive Oil Industry Waste

Activated carbons (ACs) from olive stone were prepared using CO2, steam, KOH, and H3PO4 as activating agents. The resultant activated carbons were characterized by proximate and ultimate analysis, N2 adsorption (Brunauer-Emmett-Teller (BET) method), iodine number, Boehm titration, temperature-programmed desorption (TPD), and Fourier transform infrared spectroscopy (FTIR). Ammonia (NH3) was used as a test molecule to be adsorbed. The BET surface areas of the ACs obtained ranged from 1000 to 1986 m2 g-1. Type I isotherms were obtained for all the samples, although steam and H3PO4 ACs showed a significant mesopore contribution. KOH activation resulted in carbon with a high microporosity (98%) and high iodine adsorption (1030 mg g-1). KOH AC prepared with a KOH/pyrolyzed char weight ratio of 2 and at 900 °C showed the highest NH3 adsorption (252 mg g-1), favored by the high microporosity and adequate acidity. Chemical activation (KOH and H3PO4) promotes higher NH3 adsorption than the physical ACs prepared (CO2 and steam). Langmuir and Freundlich adsorption equilibrium models were used to correlate the NH3 adsorption isotherms, obtaining the best fit for the Freundlich equation. The results indicated that olive stone-based activated carbon could be used for commercial AC to remove NH3 from gaseous streams.

Effects of CO2 intrusion on pore structure characteristics of mineral-bearing coal: Implication for CO2 injection pressure

CO2 intrusion has a crucial effect on the pore structure of mineral-bearing coal. In this study, we selected long flame coal, lean coal, and anthracite after CO2 adsorption at different pressures and tested the coal samples using X-ray diffraction, mercury intrusion porosimetry, and N2 (77 K) adsorption methods. The tests were conducted to determine the variations in mineral content, pore structure, and fractal characteristics. The results showed that supercritical CO2 had a greater ability to dissolve minerals in coal than that of subcritical CO2. Although the total pore volume and BET specific surface area gradually increased with the increase in CO2 intrusion pressure in coal, the transformation of different pores and partial new pores caused by the dissolution of minerals and the adsorption swelling of coal matrix caused the micro-macropores in the three coal samples to exhibit different trends. The pore surface roughness and pore structure complexity of seepage pore in the long-flame coal after CO2 adsorption increased while those of the lean coal and anthracite decreased. Meanwhile, CO2 intrusion caused the surface of the adsorption pore in coal to become smooth, and the pore structure was more regular, except for the lean coal. A conceptual model of the mineral-bearing coal was developed to describe the relationship between the mineral composition and pore structure induced by CO2 intrusion. These findings help to understand the transformation effect of CO2 on coal seams. Thus, a higher CO2 injection pressure should be used to obtain a larger injection volume and shorter injection time during CO2 storage implementation.

The Multitype Pore Structure Evolution Characteristics of Ziliujing Formation Shale from the Northeastern Sichuan Basin in China: Experimental Study Using Small Angle Neutron Scattering Technology

The high complexity and heterogeneity of shale pore compositions and abundant nanopores complicate the multiscale characterization of a shale reservoir pore structure. As the degree of geological evolution changes, the pore structure and connectivity also undergo complex changes and the thermal simulation experiment is a practical method to reveal the evolution characteristics of shale within a relatively short time period using the time–temperature compensation principle. In this study, thermal simulation experiments were used to obtain shale samples of the Ziliujing Formation in Northeastern Sichuan Basin with different evolution degrees. The pore structure of the samples was quantitatively characterized by SANS combined with N2 adsorption and mercury injection capillary pressure (MICP) methods. The pore morphology was qualitatively characterized by the field emission scanning electron microscopy (FE-SEM) experiment. Finally, the influence of thermal evolution on the pore structure of shale samples was investigated. The results show that the pore size distribution of SANS is similar to that of MICP and N2 adsorption methods, and the pore volume is mainly concentrated in 5–100 nm. The porosity and pore specific surface area obtained by the three characterization methods showed the trend of SANS > MICP > N2 adsorption, and the difference in pore structure was mainly affected by fluid accessibility. With the increase in thermally simulated temperature, the total pore volume and pore specific surface area of shale samples show a trend of an increase first and then a decrease. The proportion of >10 nm pores increases gradually, and the fraction of closed pores shows a downward trend as a whole. Basically, with the increase in thermally simulated temperature, the pore connectivity is enhanced, and the sample heterogeneity is weakened, all of which are conducive to the migration of shale reservoir fluid. Overall, clarifying the evolution of closed pores in shale reservoirs is of great significance for estimating original oil and gas reserves more accurately and improving oil and gas recovery.