CH4 Adsorption Research Articles

Microscopic Characterization of Deformation Behavior during Kerogen Evolution: Effects of Maturity and Skeleton Moisture Content.

The CH4 storage and seepage capacity of shale kerogen are the main controlling factors of the natural gas production rate, and the porosity and permeability of kerogen are greatly affected by kerogen deformation. Therefore, the study of the deformation rule and CH4 adsorption characteristics of kerogen at different maturities and skeleton moisture contents has an important impact on the proper understanding of the development potential of shale gas reservoirs. In this paper, kerogen maturity (II-A, II-B, II-C, and II-D) and skeleton moisture content (0.0, 0.6, 1.2, 1.8, and 2.4 wt %) were considered. The deformation of kerogen, the adsorption of CH4 after deformation, and the quadratic deformation induced by CH4 were studied by using Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD). The results show that the kerogen volume strain increases with increasing skeleton moisture content, following the order II-A < II-B < II-C < II-D for the same moisture content. The density of the kerogen matrix decreases, and porosity increases with rising moisture content. The void fraction of immature kerogen decreases with increasing water content, while the opposite is true for postmature kerogen. The presence of skeleton moisture decreases the CH4 adsorption capacity of immature kerogen and increases the CH4 adsorption capacity of postmature kerogen. The chemical structure of immature kerogen is relatively soft, making its volume more affected by CH4 adsorption compared with postmature kerogen. In the same water environment, postmature kerogen has greater CH4 storage, diffusion, and seepage capacity compared to those of immature kerogen, suggesting that reservoirs with high organic matter maturity should be prioritized for development.

Molecular simulation of the effect of water content on CO2, CH4, and N2 adsorption characteristics of coal

The objective of this work was to investigate the sorption behavior of gases, namely CO2, CH4, and N2, by molecules of coal sampled from Linglu mine under different water inclusion rates. To this end, the adsorption, diffusion, adsorption heat, and potential energy distribution characteristics of the gases in the coal pores at different water inclusion rates were analyzed using molecular dynamics and grand canonical ensemble Monte Carlo methods. The results showed that the adsorption relationship of the coal molecules on CO2, CH4, and N2 exhibited a downtrend followed by an uptrend when the water content was increased from 0 to 3.6%. The adsorption amount of CO2 was approximately twice as much as those of CH4 and N2, indicating that the competitive adsorption advantage of CO2 compared with those of CH4 and N2 was unaffected by the water content. The trend in the average heat of adsorption was generally consistent with the trend in the density of coal molecules under different moisture contents. Under the same conditions, the diffusion coefficient within a coal molecule was negatively related to the water content in the system. The layer spacing of the water molecules (2.875 Å) was greater than the liquid–water layer spacing, indicating the formation of a water molecule layer at this point, which inhibited gas adsorption. This study lays a theoretical foundation for further investigating the microscopic mechanism of coal–water interaction.

Zeolite-templated carbon synthesized with ion-exchanged FAU-zeolite using alkaline earth metal ions for the selective adsorption of C2 hydrocarbons over C1 hydrocarbon

In this study, zeolite-templated carbon (ZTC) was synthesized using ion-exchanged faujasite-Y (FAU, NaY) zeolites with different alkali earth metals (Mg2+, Ca2+, Sr2+, and Ba2+) to investigate the effects of these metals on the synthesis, characteristics, and C2/C1 hydrocarbon separation performance of ZTC. Thermogravimetric and temperature-programmed desorption of NH3 (TPD-NH3) analyses showed that carbon deposition tends to occur outside the pores because of the increasing number of moderate acid sites as the atomic number increases. In particular, in the case of FAU-ZTC(Ca) synthesized using CaY as the ZTC template, carbon accumulated inside the pores owing to the distribution of the appropriate acid strength, resulting in the highest specific surface area of 2,835 m2/g among the synthesized ZTCs. The combined X-ray photoelectron and Raman spectroscopy results confirm that these defect sites of ZTC act as adsorption sites for large molecules such as C2H4 and C2H6. The isothermal adsorption of CH4, C2H4, and C2H6 showed that FAU-ZTC(Ca) exhibited the highest adsorption capacity ratios of C2H4 and C2H6 to CH4, with a C2H6/CH4 ratio of 5.897 and C2H4/CH4 ratio of 5.288, respectively. The effective pore size ranges affecting the adsorption of CH4, C2H4, and C2H6 determined using linear regression analysis are 0.4 to 0.6 nm for CH4 and 0.6 to 1.1 nm for C2H4 and C2H6. Molecular simulations confirmed that the adsorption energy was maximized by the interaction between the hydrogen atoms of the hydrocarbons and the carbon atoms of ZTC. Furthermore, C2H4 and C2H6 require larger pores than CH4 adsorption because C2H4 and C2H6 prefer to lie horizontally rather than vertically in the pores of the ZTC.

High-vacuum-calcined multi-MOF mixed-matrix membrane for CH4/N2 separation

Methane/nitrogen (CH4/N2) separation remains a persistent challenge owing to the similar polarities, kinetic diameters, and boiling points of CH4 and N2. Herein, a novel method is proposed for enhancing the separation performance of CH4/N2 via vacuum resistance calcination, which uses surface-carbonized and hardened ZIF-8 (SCH-Z), MOF-74-Ni (SCH-M), and UiO-66-NH2 (SCH–U). The nanoparticles treated by vacuum resistance calcination remain the microporous characteristics of MOF, while introducing additional mesoporous structure and unsaturated metal sites. Such multistage pore structure and rich metal sites display a significant improvement in the CH4 adsorption over N2. In addition, the separation performance of multiple metal–organic frameworks (MOFs) mixed matrix membranes (MMMs) fabricated by homogeneously mixing the alkaline polymer polyvinylamine (PVAm) with SCH-M/SCH-Z and SCH-M/SCH–U was investigated, respectively. When the measured pressure was 0.1 MPa and the binary filler loading was 48 %, the PVAm/(SCH-M)0.7(SCH-Z)0.3/MPSf MMM exhibited outstanding CH4/N2 separation performance (CH4 permeance of 2888.48 GPU and selectivity of 4.38). Furthermore, when the loading of the binary filler was 45 %, the ideal CH4/N2 selectivity and CH4 permeance of PVAm/(SCH-M)0.67(SCH–U)0.33/MPSf MMM are 5.57 and 2263.94 GPU, respectively. This study provides a novel idea that introducing multi-MOF nanoparticles into MMMs for optimizing gas separation performance.

Adsorption of methane by modified-biochar aiming to improve the gaseous fuels storage/transport capacity: process evaluation and modeling.

The CH4 storage by adsorption on activated carbons for natural gas handling has gained interest due to the appearance of lightweight materials with large surface areas and pore volumes. Consequently, kinetic parameters estimation of the adsorptive process can play a crucial role in understanding and scaling up the system. Concerning its versatility, banana peel (BP) is a biomass with potential for obtaining different products, such as biochar, a solid residue from the biomass' thermal decomposition of difficult disposal, where through an activation process, the material porous features are taken advantage to application as adsorbent of gaseous substances. This research reported data for the CH4 adsorption kinetic modeling by biochar from BP pyrolysis. The activated biochar textural characterization showed particles with fine mesoporous structure (pore diameter ranging between 29.39 and 55.62Å). Adsorption kinetic analysis indicated that a modified pseudo-first-order model was the most suitable to represent the experimental data, with equilibrium adsorption of 28mgg-1 for the samples activated with 20.0% vol wt.-1 of H3PO4 and pyrolysis at 500°C. The equilibrium constant was consistent with the Freundlich isotherm model, suggesting a physisorption mechanism, and led to a non-ideal, reversible, and not limited to monolayer CH4 adsorption.

Adsorption Modeling Based on Classical Density Functional Theory and PC-SAFT: Temperature Extrapolation and Fluid Transfer.

Adsorption is at the heart of many processes from gas separation to cooling. The design of adsorption-based processes requires equilibrium adsorption properties. However, data for adsorption equilibria are limited, and therefore, a model is desirable that uses as little data as possible for its parametrization, while allowing for data interpolation or even extrapolation. This work presents a physics-based model for adsorption isotherms and other equilibrium adsorption properties. The model is based on one-dimensional classical density functional theory (1D-DFT) and the perturbed-chain statistical associating fluid theory (PC-SAFT). The physical processes inside the pores are considered in a thermodynamically consistent approach that is computationally efficient. Once parametrized with a single isotherm, the model is able to extrapolate to other temperatures and outperforms the extrapolation capabilities of state-of-the-art models, such as the empirical isotherm models from Langmuir or Toth. Furthermore, standard combining rules can be used to transfer parameters adjusted to an adsorbent/fluid pair to other fluids. These features are demonstrated for the adsorption of N2, CH4, and CO2 in metal-organic frameworks. Thereby, the presented model can calculate temperature-dependent isotherms for various fluids by using data limited to a single isotherm as input.

Adsorption and sensing performances of greenhouse gases (CO2，CH4，SF6, N2O) on Ni modified GeSe surface

The greenhouse effect has drawn significant recent attention due to its serious impact on Earth's climate and ecosystems. Therefore, this study investigates the adsorption and sensing properties of four greenhouse gases (CH4, CO2, SF6, and N2O) on the Ni-GeSe monolayer using first principles of DFT. The doping behavior of Ni on intrinsic GeSe monolayer is initially studied and the most stable doping structure is selected. Then the adsorption energies, adsorption distances, charge transfers, energy band structures, molecular frontier orbitals and recovery times of the selected Ni-GeSe structure with the four greenhouse gases are analyzed and compared. The results show that Ni modification can improve the surface activity of the intrinsic GeSe monolayers, thereby improving their adsorption and sensing properties. Ni-GeSe has weak adsorption of CH4 and CO2, while strong chemisorption of SF6 and N2O, making it suitable as an adsorbent for these two gases. Analysis of the recycling performance of Ni-GeSe monolayers shows that Ni-GeSe has a good recovery time for N2O at a temperature of 398 K, suggesting its potential as an efficient low-power resistive N2O gas sensor. And gas sensors based on GeSe and its modified materials can be theoretically guided by these calculations.

Efficient separation of carbon dioxide and methane in high-pressure and wet gas mixtures using Zr-MOF-808

The capture and separation of carbon dioxide (CO2) has been the focus of a plethora of research in order to mitigate its emissions and contribute to global development. Given that CO2 is commonly found in natural gas streams, there have been efforts to seek more efficient materials to separate gaseous mixtures such as CO2/CH4. However, there are only a few reports regarding adsorption processes within pressurized systems. In the offshore scenario, natural gas streams still exhibit high moisture content, necessitating a greater understanding of processes in moist systems. In this article, a metal-organic framework synthesis based on zirconium (MOF-808) was carried out through a conventional solvothermal method and autoclave for the adsorption of CO2 and CH4 under different temperatures (45–65 °C) and pressures up to 100 bar. Furthermore, the adsorption of humid CO2 was evaluated using thermal analyses. The MOF-808 synthesized in autoclave showed a high surface area (1502 m2/g), a high capacity for CO2 adsorption at 50 bar and 45 °C and had a low selectivity to capture CH4 molecules. It also exhibited a fine stability after five cycles of CO2 adsorption and desorption at 50 bar and 45 °C − as confirmed by structural post-adsorption analyses while maintaining its adsorption capacity and crystallinity. Furthermore, it can be observed that the adsorption capacity increased in a humid environment, and that the adsorbent remained stable after adsorption cycles in the presence of moisture. Finally, it was possible to confirm the occurrence of physisorption processes through nuclear magnetic resonance (NMR) analyses, thus validating the choice of mild temperatures for regeneration and contributing to the reduction of energy consumption in processing plants.

Effect of Tectonic Deformation on the Pore System and Methane Adsorption of Anthracite Coal.

Tectonic deformation significantly alters the physical structure of coals, holding great importance to the coal mining industry and coalbed methane. In this study, eight anthracite coal samples with varying degrees of deformation were collected to investigate the effects of tectonic deformation on the pore system and CH4 adsorption of anthracite coals. In addition, low-temperature gas adsorption (N2 and CO2), Raman spectroscopy, and CH4 isothermal experiments were performed. The results revealed that coal samples with higher degrees of deformation exhibited larger ratios of D-band intensity to G-band intensity (I D/I G), indicating increased molecular defects induced by tectonic deformation. As the deformation degree of the coal samples increased, the mesopore volume increased from 0.00044 cm3/g (primary coal) to 0.0019 cm3/g (scaly coal). Conversely, the micropore volume tended to decrease with the increasing deformation degree of the coal samples. Moreover, the impact of deformation degree on the CH4 adsorption capacity of anthracite coals was complex. With the deformation degree increasing, the Langmuir volume initially decreased from 32.0 to 24.55 cm3/g and then rose to 30.14 cm3/g. This complexity arose from the differential effects of tectonic deformation on various pore types, where micropores and mesopores collectively determined the CH4 adsorption capacity of anthracite coals. This study analyzed the influence of tectonic deformation on the pore structure and CH4 adsorption capacity at the molecular level, providing valuable insights for evaluating the in situ CH4 content in anthracite coal seams.

Green and Scalable Preparation of an Isomeric CALF-20 Adsorbent with Tailored Pore Size for Molecular Sieving of Propylene from Propane.

Molecular sieving of propylene (C3H6) from propane (C3H8) is highly demanded for C3H6 purification. However, delicate control over aperture size to achieve both high C3H6 uptake and C3H6/C3H8 selectivity with low cost remains a significant challenge. Herein, a green and scalable approach is reported for preparing an isomeric CALF-20 adsorbent, termed as NCU-20, using water as the only solvent with a cost of $10 per kilogram. NCU-20 features a contracted pore size (4.2×4.7Å2) compared to CALF-20 (5.2×5.7Å2), which enables molecular sieving of C3H6 (4.16×4.65Å2) from C3H8 (4.20×4.80Å2). Notably, NCU-20 exhibits record-high C3H6 adsorption capacity (94.41 cm3cm-3) at 298K and 1.0bar, outperforming all C3H6/C3H8 molecular sieving adsorbents. The sieving performances of C3H6/C3H8 are well maintained at elevated temperatures. Therefore, a delicate balance between C3H6 adsorption capacity (91.62 cm3cm-3) and C3H6/C3H8 selectivity (uptake ratio of 22.2) is obtained on NCU-20 at 298K and 0.5bar. Furthermore, dynamic breakthrough experiments demonstrate a high productivity of 65.39 cm3cm-3 for high-purity C3H6 (>99.5%) from an equimolar C3H6/C3H8 gas-mixture.

Reservoir Characteristics of Marine–Continental Transitional Taiyuan Formation Shale and Its Influence on Methane Adsorption Capacity: A Case Study in Southern North China Basin

To further study the reservoir characteristics and adsorption capacity of the Taiyuan Formation shale in the South North China Basin (SNCB), the pore structure and adsorption capacity of shale are discussed using various analysis tests, including elemental geochemistry, organic geochemistry, mineral composition, low-temperature nitrogen adsorption (LTNA), and methane adsorption experiments. The results indicate that the Taiyuan Formation shale formed in a poor oxygen and anaerobic sedimentary environment in still water. The average value of total organic carbon (TOC) content is 2.37%. The organic matter type mainly consists of type III kerogen. The vitinite reflectance (Ro) ranges from 3.11% to 3.50%. The clay mineral content varies greatly, averaging at 40.7%, while the quartz content averages at 37.7%. The Taiyuan Formation shale mainly develops interparticle (InterP) pores, followed by organic pores, intraparticle (IntraP) pores, solution pores, and microfractures. BET specific surface area (SSA) is between 9.47 m2/g and 22.14 m2/g, while pore volume (PV) ranges from 0.0098 cm3/g to 0.022 cm3/g, indicating favorable conditions for shale gas storage. According to the results of the CH4 adsorption experiment, Langmuir volume from Taiyuan Formation shales exhibits 1.35~4.30 cm3/g, indicating excellent adsorption capacity. TOC content shows a positive correlation with both Langmuir volume and BET SSA from Taiyuan Formation shales, suggesting that TOC plays a crucial role in controlling microscopic pores and gas adsorption capacity. Organic matter enhances the shale adsorption capacity by providing abundant pore SSA. Due to formation compaction, the pore size of clay minerals decreases, leading to an increase in pore SSA, while kaolinite exhibits weak hydrophilic ability. Consequently, with the increase in clay minerals and kaolinite content, the shale adsorption capacity is enhanced to a certain extent. However, an increase in the carbonate mineral content may result in a decrease in the proportion of clay minerals, therefore reducing the CH4 adsorption capacity of shale.

Numerical simulation of CO2-ECBM for deep coal reservoir with strong stress sensitivity

CH4 production rate of coalbed methane (CBM) well decreases rapidly during primary recovery in the deeply buried coal seam, resulting in a lot of CH4 residues. CO2 pour into deep coal seam with high stress sensitivity is available for enhancing CH4 recovery by improving permeability for reservoir fracture and displacing CH4 adsorbed in matrix. A coupled adsorp-hydro-thermo-mechanical (AHTM) model for deep methane development is established by considering the coupling relationships of non-isothermal and non-constant pressure competitive adsorption between CO2 and CH4, multi-phase flow, unsteady diffusion, heat transmission and in-situ stress variety. The model is verified by historical production and then used for CO2 enhanced CBM (CO2-ECBM) of deep coal reservoir in a sedimentary basin in Northwest China. The simulation results show that: (1) For primary recovery, permeability in coal reservoir drops rapidly with the development of CBM, which seriously restricts the production of CH4. The permeability of the reservoir decreases from 7.89 × 10−16 m2 to less than 1.50 × 10−16 m2, CH4 production rate in CBM well reduces to below 2000 m3/d, and the average total CH4 content of coal reservoir is reduced by 5.49 m3/t with the decrease of only 1.12 m3/t of average adsorbed CH4 in a production duration of 2000 d (2) With 10 MPa CO2 continuous injection into coal seam after 700d of primary, the permeability for reservoir and CH4 production rate increase while the total CH4 content and adsorption CH4 content in reservoir decrease compared with the primary recovery. (3) CO2 pouring into coal reservoir increases the CH4 production time and rate, which improves CH4 recovery of coal reservoir. And it increases by 23.36 %, 23.07 % and 22.46 % with shut-in thresholds of CH4 production rate of 1000 m3/d, 800 m3/d and 600 m3/d, respectively. The investigation is of great significance for the development of deep coalbed methane.

High‐Pressure Molecular Sieving of High‐Humidity C2H4/C2H6 Mixture by a Hydrophobic Flexible Metal–Organic Framework

AbstractMolecular sieving is an ideal separation mechanism, but controlling pore size, restricting framework flexibility, and avoiding strong adsorption are all very challenging. Here, we report a flexible adsorbent showing molecular sieving at ambient temperature and high pressure, even under high humidity. While typical guest‐induced transformations are observed, a high transition pressure of 16.6 atm is observed for C2H4 at 298 K because of very weak C2H4 adsorption (~16 kJ mol−1). Also, C2H6 is completely excluded below the pore‐opening pressure of 7.7 atm, giving single‐component selectivity of ca. 300. Quantitative high‐pressure column breakthrough experiments using 1 : 1 C2H4/C2H6 mixtures at 10 atm as input confirm molecular sieving with C2H4 adsorption of 0.73 mmol g−1 or 32 cm3(STP) cm−3 and negligible C2H6 adsorption of 0.001(2) mmol g−1, and the adsorbent can be completely regenerated by inert gas purging. Furthermore, it is highly hydrophobic with negligible water adsorption, and the C2H4/C2H6 separation performance is unaffected at high humidity.

High-Pressure Molecular Sieving of High-Humidity C2H4/C2H6 Mixture by a Hydrophobic Flexible Metal-Organic Framework.

Molecular sieving is an ideal separation mechanism, but controlling pore size, restricting framework flexibility, and avoiding strong adsorption are all very challenging. Here, we report a flexible adsorbent showing molecular sieving at ambient temperature and high pressure, even under high humidity. While typical guest-induced transformations are observed, a high transition pressure of 16.6 atm is observed for C2H4 at 298 K because of very weak C2H4 adsorption (~16 kJ mol-1). Also, C2H6 is completely excluded below the pore-opening pressure of 7.7 atm, giving single-component selectivity of ca. 300. Quantitative high-pressure column breakthrough experiments using 1 : 1 C2H4/C2H6 mixtures at 10 atm as input confirm molecular sieving with C2H4 adsorption of 0.73 mmol g-1 or 32 cm3(STP) cm-3 and negligible C2H6 adsorption of 0.001(2) mmol g-1, and the adsorbent can be completely regenerated by inert gas purging. Furthermore, it is highly hydrophobic with negligible water adsorption, and the C2H4/C2H6 separation performance is unaffected at high humidity.

Reversible oxidation of ethylene on ferroelectric BaTiO3(001): An X-ray photoelectron spectroscopy study

Adsorption and desorption of ethylene on BaO-terminated (001) barium titanate are investigated by X-ray photoelectron spectroscopy. Carbon is found in an oxidized state, at a binding energy similar to that resulting from CO adsorption on BaTiO3(001). The amount of carbon adsorbed on the surface is also similar to the case of CO/BaTiO3(001). Upon heating the substrate up to the loss of its ferroelectric polarization, the C 1s signal from the oxidized spectral region vanishes. At the same time, there was no noticeable oxygen depletion of the surface after repeated C2H4 adsorption and desorption. The substrate remains stable after repeated oxidative adsorption and desorption of ethylene. Desorption occurs at different temperatures, depending on the adsorption temperature, which suggests different adsorption geometries: non-dissociated adsorption at high temperature with ethylene bond on two surface oxygen atoms, and locally dissociated adsorption at lower temperatures, in “formaldehyde-like” local configurations.

Effective heat transfer associated with CO2 and CH4 adsorption on HKUST-1 metal-organic framework deposited in situ on heat exchanger

The aim of this study was to analyze the heat transfer properties a copper heat exchanger with the in situ synthesized HKUST-1 metal-organic framework (MOF). For this purpose, a dedicated reactor was constructed to enable the direct measurements of heat of adsorption of CO2 and CH4, that accompanies the dynamic course of these processes. In parallel, CO2 and CH4 adsorption isotherms were determined at various temperatures and the heat of adsorption was calculated by an indirect method. Temperature changes on the heat exchanger as a result of cyclic adsorption/desorption processes of CO2 and CH4 on the HKUST-1 layer were registered, and the results of adsorption heat by direct and indirect methods were compared. Comparing the results of indirect and direct measurements of temperature changes accompanying CO2 adsorption, a difference of 19 % was obtained. In the case of CH4 adsorption, the results obtained by the two methods differed by 22 %. Based on the experimental results, it was proven that HKUST-1 synthesized in situ on a copper heat exchanger has improved heat transfer properties. The proposed concept of MOF layer on heat exchanger allows for efficient thermal stimulation of sorption processes and simultaneous MOF regeneration while minimizing the thermal energy supplied to the system.

CH4 Adsorption in Wet Metal-Organic Frameworks under Gas Hydrate Formation Conditions Using A Large Reactor

Nanoporous materials, such as metal-organic frameworks (MOFs), are renowned for their high selectivity as gas adsorbents due to their specific surface area, nanoporosity, and active surface chemistry. A significant challenge for their widespread application is reduced gas uptake in wet conditions, attributed to competitive adsorption between gas and water. Recent studies of gas adsorption in wet materials have typically used small amounts of powdered porous materials (in the milligram range) within very small reactors (1–5 mL). This leaves a gap in knowledge about gas adsorption behaviors in larger reactors and with increased MOF sample sizes (to the gram scale). Additionally, there has been a notable absence of experimental research on MOFs heavily saturated with water. In this study, we aimed to fill the gaps in our understanding of gas adsorption in wet conditions by measuring CH4 adsorption in MOFs. To do this, we used larger MOF samples (in grams) and a large-volume reactor. Our selection of commercially available MOFs, including HKUST-1, ZIF-8, MOF-303, and activated carbon, was based on their widespread application, available previous research, and differences in hydrophobicity. Using a volumetric approach, we measured high-pressure isotherms (at T = 274.15 K) to compare the moles of gas adsorbed under both dry and wet conditions across different MOFs and weights. The experimental results indicate that water decreases total CH4 adsorption in MOFs, with a more pronounced decrease in hydrophilic MOFs compared to hydrophobic ones at lower pressures. However, hydrophilic MOFs exhibited stepped isotherms at higher pressures, suggesting water converts to hydrate, positively impacting total gas uptake. In contrast, the hydrophobic ZIF-8 did not promote hydrate formation due to particle aggregation in the presence of water, leading to a loss of surface area and surface charge. This study highlights the additional challenges associated with hydrate-MOF synergy when experiments are scaled up and larger sample sizes are used. Future studies should consider using monolith or pellet forms of MOFs to address the limitations of powdered MOFs in scale-up studies.

Transforming a mixture of real post-consumer plastic waste into activated carbon for biogas upgrading

Plastic waste management is a current environmental issue that demands potential solutions since complete mechanical recycling is limited to the complexity and feasibility regarding the quality and purity of plastic waste. Pyrolysis has emerged as a reasonable solution for the recycling of those fractions that are not further suitable for recycling. Although the implementation of this technology is mature, the generated solid fraction or char has not been completely inserted in the closed loop of plastic recycling. This work explores the possibility of using the carbonaceous char as a precursor for the preparation of porous activated carbons for environmental application as CO2 adsorbent and biogas upgrading. The effect of the pyrolysis temperature (450 or 500 ºC) on the obtained chars has been assessed for the benefits in the second stage of chemical activation, exploring the possibility of the use of diverse chemical agents. The composition, textural, and surface properties of the porous materials were characterized. N2 isotherms showed that the char prepared at 500 ºC provided the best textural properties with a performance of K2CO3 ∼ KOH > Na2CO3 > NaOH > ZnCl2 > FeCl3. Isotherms of CO2 adsorption showed that the activation with K2CO3 displayed the best uptake (130.2 mg g−1 at 273 K), closely followed by KOH (125.0 mg g−1 at 273 K), also confirmed by dynamic tests in a fixed bed column configuration. The uptake was well correlated with the ultramicropore volume and the oxygenated functional groups. The CO2 and CH4 adsorption were studied either in static or dynamic assays. The behavior of the sample activated with K2CO3 was studied in detail in column tests, suggesting that the activated material exhibits promising behavior for biogas upgrading.

Adsorption and Diffusion Properties of Gas in Nanopores of Kerogen: Insights from Grand Canonical Monte Carlo and Molecular Dynamics Simulations

Investigating the adsorption and diffusion processes of shale gas within the nanopores of kerogen is essential for comprehending the presence of shale gas in organic matter of shale. In this study, an organic nanoporous structure was constructed based on the unit structure of Longmaxi shale kerogen. Grand canonical Monte Carlo and molecular dynamics simulation methods were employed to explore the adsorption and diffusion mechanisms of pure CH4, CO2, and N2, as well as their binary mixtures with varying mole fractions. The results revealed that the physical adsorption characteristics of CH4, CO2, and N2 gases on kerogen adhered to the Langmuir adsorption law. The quantity of adsorbed gas molecules increased with rising pressure but decreased with increasing temperature. The variation in the heat of adsorption was also analyzed. Under identical temperature and pressure conditions, the adsorption of CH4 increased with higher mole fractions of CH4, whereas it decreased with greater mole fractions of CO2 and N2. Notably, CO2 molecules exhibited a robust interaction with kerogen molecules compared to the adsorption properties of CH4 and N2. Furthermore, the self-diffusion coefficient of gas within kerogen nanopores gradually decreased with increasing pressure or decreasing temperature. The diffusion capacity of gas molecules followed the descending order N2 &gt; CH4 &gt; CO2 under the same pressure and temperature conditions.

Revealing La doping activation or inhibition of crystal facet effects in Co3O4 for catalytic combustion and water resistance improvement

It was challenging to enhance the catalytic activity and water resistance of transition metal oxides in the CH4 treatment process. Here, La with large atomic radii was doped onto Co3O4 on the (110), (111) and (100) crystal facets, respectively, and successfully doped into the (110) and (100) lattices, but accumulation occurs on the (111) crystal surface. Doping La into the Co3O4 lattice achieved a dual excitation effect for surface optimization and structural defects, causing lattice expansion, enhancing the electrophilicity of the O atoms in the vicinity of La, and significantly stimulating the Co-O bond. This significantly improved reactive oxygen species content, CH4 adsorption capacity, and gaseous oxygen activation and replenishment capability for higher catalytic activity. Conversely, the (111) facet with accumulated La showed an opposite trend. Meanwhile, La doping effectively improved the stability of Co3O4 and weakened its hydrophilicity, which effectively enhanced its water resistance. This research provided a viable strategy for designing high-performance and water-resistant Co3O4-based catalysts.