Adsorption Isotherms Of Carbon Dioxide Research Articles

Evaluation of methane adsorption isotherms at ambient temperature on carbon materials from NLDFT pore size analysis derived from standard N2 and CO2 adsorption isotherms

In this paper, we attempt to estimate CH4 adsorption on carbon materials based on the pore size distribution (PSD) characteristics evaluated from standard nitrogen and carbon dioxide adsorption isotherms using the nonlocal density functional theory (2D-NLDFT), or more precisely, its two-dimensional version (2D-NLDFT). The PSDs of the carbons were calculated by the simultaneous fit of the NLDFT models to the corresponding N2 and CO2 adsorption data. This method is referred to in the literature as the dual gas analysis method which is implemented in SAIEUS software. Essential features of carbon PSDs affecting the shapes of methane adsorption isotherms measured at ambient temperature were identified as related to micro and mesopores carbon structure. We discuss how different micro and mesopore size ranges contribute to methane adsorption isotherms in the low and higher-pressure ranges. The results of the present study may serve as guidance for selecting and designing suitable carbon materials for practical applications such as PSA recovery of CH4 from its mixtures or for methane storage.

Temperature Evolution of Sorbonorit-4 Methane-Induced Deformation through the Eyes of Classical Density Functional Theory.

Activated carbons are widely used industrial adsorbents due to their attractive sorption properties. Although extensive research on activated carbon has been carried out for several centuries, some aspects of the adsorption-induced deformation of activated carbon remain unclear. The puzzling temperature dependence of the methane-induced deformation of activated carbon is investigated in the present work. Several experimental studies have shown that an increase in temperature leads to a reversal of the sign of adsorption strain at low pressures, i.e., the contraction turns into an expansion. Here we suggest a possible explanation for this effect by applying classical density functional theory to the adsorption isotherms of nitrogen, carbon dioxide, and methane as well as to methane-induced deformation isotherms. Our calculations show that the adsorption stress generated in the smallest pores predominates at higher temperatures and leads to material swelling. Lowering the temperature, on the other hand, leads to a predominance of larger pores and compression of the activated carbon material. We also investigated the possibility of determining the pore size distribution from methane-induced deformation and adsorption data and the predictive capabilities of our theoretical approach.

Modeling carbon dioxide and methane adsorption on illite and calcite: enhancing the simplified local density model through crystal structure modifications.

The simplified local density (SLD) model has been frequently utilized to describe gas adsorption in porous media. The common assumptions associated with the SLD model are the graphene slit and uniform distribution of atoms. However, these fail to depict the heterogeneous surface of minerals. In this study, the original SLD model was modified by substituting mineral crystal structures for the homogeneous carbon layer when building the slit. The modified model may capture the heterogeneity-induced variation of the fluid-pore interaction potential and adsorbed phase density near the mineral surface. The calculated adsorption isotherms of methane and carbon dioxide on illite and calcite surfaces at 330.15 K were compared with literature experiment data to validate the modified SLD model. For the simulation of gas adsorption isotherms, the modified model predictions agree reasonably well with the previously reported experiment results using the gravimetric method. The calculated density profile in the slit indicates the monolayer adsorption behavior of CH4 and CO2. Based on more precise interaction potentials, the number of regression parameters was reduced to two, and the physical meaning of the model parameters was clarified. Therefore, for estimating hydrocarbon storage in reservoirs, the modified SLD model could be used as an efficient alternative to time-consuming molecular simulation methods.

Adsorption Equilibrium of CO2 on Microporous Activated Carbon Produced from Avocado Stone Using H2SO4 as an Activating Agent

In this study, we conducted a comprehensive investigation into activated carbons derived from avocado stones produced through chemical activation using sulfuric acid. The analysis encompassed X-ray diffraction (XRD) spectra, FTIR, SEM and essential textural parameters, namely specific surface area, total pore volume, and micropore volume. Moreover, we scrutinized carbon dioxide adsorption isotherms and subjected the experimental data to fit with both two-parameter and four-parameter equilibrium isotherm models. To achieve the most accurate parameter estimation, five error functions were employed. Furthermore, we calculated the isosteric heat of adsorption for the most promising CO2 sorbent, providing valuable insights into the thermodynamic aspects of the adsorption process.

Nitrogen-Doped Starbons®: Methodology Development and Carbon Dioxide Capture Capability.

Five nitrogen sources (glycine, β-alanine, urea, melamine and nicotinamide) and three heating methods (thermal, monomodal microwave and multimodal microwave) are used to prepare nitrogen-doped Starbons® derived from starch. The materials are initially produced at 250-300 °C (SNx 300y ), then heated in vacuo to 800 °C to produce nitrogen-doped SNx 800y 's. Melamine gives the highest nitrogen incorporation without destroying the Starbon® pore structure and the microwave heating methods give higher nitrogen incorporations than thermal heating. The carbon dioxide adsorption capacities of the nitrogen-doped Starbons® determined gravimetrically, in many cases exceed those of S300 and S800. The carbon dioxide, nitrogen and methane adsorption isotherms of the most promising materials are measured volumetrically. Most of the nitrogen-doped materials show higher carbon dioxide adsorption capacities than S800, but lower methane and nitrogen adsorption capacities. As a result, the nitrogen-doped Starbons® exhibit significantly enhanced carbon dioxide versus nitrogen and methane versus nitrogen selectivities compared to S800.

A Comparative Investigation of the Adsorption Characteristics of CO2, O2 and N2 in Different Ranks of Coal

The adsorption mechanism of carbon dioxide, oxygen and nitrogen in coal is important for preventing and controlling coal spontaneous combustion and for understanding the technology of CO2 storage in goaf. Adsorption amount and adsorption heat are key adsorption parameters that are required to understand the material and energy conversions during adsorption in coal. In this study, we studied the factors that influence the adsorption amounts and adsorption heat values of carbon dioxide, oxygen and nitrogen in coal by testing four different coal samples using conventional coal quality analysis, low-pressure nitrogen and carbon dioxide adsorption, Fourier transform infrared spectroscopy and three gas adsorption experiments at different temperatures. Then, we analyzed the relationships between the structural parameters of the coal samples and the adsorption amounts and the adsorption heat values of carbon dioxide, oxygen and nitrogen. The results show that the adsorption isotherms of carbon dioxide conform to the Langmuir equation, and the adsorption isotherms of oxygen and nitrogen conform to Henry’s law between 0 and 110 kPa. The adsorption amounts of carbon dioxide, oxygen and nitrogen decreased with an increase in temperature, and the change in the rate of the adsorption amount with temperature was determined by the adsorption heat. The results of the pore structure show that the pores of the coal samples are composed of mesopores and micropores; the micropores contribute to the main specific surface area. The micropore and mesopore structures are the main determinants of the adsorption amounts of carbon dioxide, oxygen and nitrogen in coal. The gas adsorption heat is affected by the pore structure and the chemical composition of coal. The adsorption heat of nitrogen correlates positively with the pore structure of the coal. The adsorption heat of oxygen correlates positively with the ash, elemental nitrogen, elemental sulfur and mineral contents of the coal. The adsorption heat of carbon dioxide correlates positively with the elemental sulfur content of the coal.

Computing chemical potentials of adsorbed or confined fluids.

The chemical potential of adsorbed or confined fluids provides insight into their unique thermodynamic properties and determines adsorption isotherms. However, it is often difficult to compute this quantity from atomistic simulations using existing statistical mechanical methods. We introduce a computational framework that utilizes static structure factors, thermodynamic integration, and free energy perturbation for calculating the absolute chemical potential of fluids. For demonstration, we apply the method to compute the adsorption isotherms of carbon dioxide in a metal-organic framework and water in carbon nanotubes.

Ammonia capture by adsorption on doped and undoped activated carbon: Isotherm and breakthrough curve measurements

Doped and undoped activated carbons were characterized by scanning electron microscopy, energy dispersive spectrometry, helium pycnometry, mercury intrusion porosimetry, and adsorption isotherms of nitrogen and carbon dioxide. The adsorption isotherms of ammonia were measured at 278, 293, 303, and 318 K and pressures up to 105 kPa using a manometric system on both activated carbons. These measurements showed that the doped activated carbon had the highest ammonia adsorption capacity, especially at low ammonia partial pressures. The Toth isotherm model was used to correlate the adsorption isotherms and estimate the isosteric heats of adsorption at 278 K and at zero fractional loading that were 25.6 and 41.9 kJ.mol−1 for undoped and doped activated carbon, respectively. Ammonia breakthrough curves were measured with both activated carbons in a pilot column. The behavior of doped and undoped activated carbon during adsorption/desorption cycles shows that despite the possibility of regeneration and enhancement of undoped activated carbon, the doped activated carbon provides better single use performance. A study of the operating parameters of doped activated carbon was conducted to evaluate the effects of ammonia concentration, gas flow rate, operating temperature, and relative humidity. The occurrence of two independent ammonia adsorption mechanisms (chemical and physical) on the doped activated was demonstrated.

Analysis of the Influence of Activated Carbons' Production Conditions on the Porous Structure Formation on the Basis of Carbon Dioxide Adsorption Isotherms.

The results of a study of the impact of activation temperature and the mass ratio of the activator to the carbonised precursor on the porous structure of nitrogen-doped activated carbons obtained from lotus leaves by carbonisation and chemical activation with sodium amide (NaNH2) are presented. The analyses were carried out via the new numerical clustering-based adsorption analysis, the Brunauer-Emmett-Teller, the Dubinin-Raduskevich, and the density functional theory methods applied to carbon dioxide adsorption isotherms. Carbon dioxide adsorption isotherms' analysis provided much more detailed and reliable information about the pore structure analysed. The analyses showed that the surface area of the analysed activated carbons is strongly heterogeneous, but the analysed activated carbons are characterised by a bimodal pore structure, i.e., peaks are clearly visible, first in the range of pore size from about 0.6 to 2.0 nm and second in the range from about 2.0 to 4.0 nm. This pore structure provides optimal adsorption performance of carbon dioxide molecules in the pore structure both for adsorption at atmospheric pressure, which requires the presence of narrow pores for the highest packing density, as well as for adsorption at higher pressures, which requires the presence of large micropores and small mesopores. However, there are no micropores smaller than 0.5 nm in the analysed activated carbons, which precludes their use for carbon dioxide adsorption for processes conducted at pressures less than 0.01 MPa.

Mathematical analysis of the effect of process conditions on the porous structure development of activated carbons derived from Pine cones

This paper presents the results of a study on the influence of the degree of impregnation and activation temperature on the formation of the porous structure of activated carbons (ACs) obtained from Pine cones by the chemical activation process using potassium hydroxide as an activator. The advanced new numerical clustering based adsorption analysis (LBET) method, together with the implemented unique numerical procedure for the fast multivariant identification were applied to nitrogen and carbon dioxide adsorption isotherms determined for porous structure characterization of the ACs. Moreover, the Quenched Solid Density Functional Theory (QSDFT) method was chosen to determine pore size distributions. The results showed a significant influence of the primary structure of Pine cones on the formation of the porous structure of the developed ACs. Among others, it was evidenced by a very high degree of surface heterogeneity of all the obtained ACs, irrespective of the degree of impregnation with potassium hydroxide and the activation temperature. Moreover, the analysis of carbon dioxide adsorption isotherms showed, that the porous structure of the studied ACs samples contains micropores accessible only to carbon dioxide molecules. The results also showed a significant advantage of the LBET method over those conventionally used for porous structure analysis based on Brunauer–Emmett–Teller (BET) and Dubinin–Raduskevich (DR) equations, because it takes into account surface heterogeneities. The novel analyses methods were more fully validated as a reliable characterization tool, by extending their application to the isotherms for ACs developed from the same precursor by phosphoric acid activation, and for samples arising from these ACs, further subjected to additional post-treatments. The effect of the raw material used as precursor was moreover analysed by comparison with previous reported results for other ACs. The complementarity of the results obtained with the LBET and QSDFT methods is also noteworthy, resulting in a more complete and reliable picture of the analyzed porous structures.

Influence of layer slipping on adsorption of light gases in covalent organic frameworks: A combined experimental and computational study

Sorption of gases in micro- and mesoporous materials is typically interpreted on the basis of idealized structural models where real structure effects such as defects and disorder are absent. For covalent organic frameworks (COFs) significant discrepancies between measured and simulated adsorption isotherms are often reported but rarely traced back to their origins. This is because little is known about the real structure of COFs and its effect on the sorption properties of these materials. In the present work molecular simulations are used to obtain adsorption isotherms of argon, nitrogen, and carbon dioxide in the COF-LZU1 at various temperatures. The (perfect) model COF has a BET surface that is higher than the experimental BET surface by a factor of approximately 1.33, suggesting defects or inclusions are present in the real structure. We find that the saturation adsorption loading of small gaseous species in COF-LZU1, as determined from grand canonical Monte Carlo simulations, is also higher by approximately the same factor compared to the experimental saturation loading. The influence of interlayer slipping on the shape of the adsorption isotherm and the adsorption capacity is studied. Comparison between simulation and experiment at lower loadings suggests the layers to be shifted instead of perfectly eclipsed. The sensitivity of the adsorption isotherms in this regime towards the underlying framework topology shows that real structure effects have significant influence on the gas uptake. Accounting for layer slipping is important to applications such as catalysis, gas storage and separation.

Acid Gas Removal by Superhigh Silica ZSM-5: Adsorption Isotherms of Hydrogen Sulfide, Carbon Dioxide, Methane, and Nitrogen

Acid Gas Removal by Superhigh Silica ZSM-5: Adsorption Isotherms of Hydrogen Sulfide, Carbon Dioxide, Methane, and Nitrogen

Numerical analysis of the micropore structure of activated carbons focusing on optimum CO2 adsorption

In this work, the porous structure of activated carbons prepared from Moso bamboo were mathematically analysed. At first, the raw material was subjected to two-stage activation process i.e. in the first stage, phosphoric acid or zinc chloride was used followed by second stage physical activation or chemical activation with potassium hydroxide. Then, nitrogen and carbon dioxide adsorption isotherms were determined. Subsequently, a novel, clustering-based adsorption analysis method was applied, combined with a numerical procedure for the fast multivariant identification of adsorption systems. The mentioned method takes into consideration the heterogeneity of the adsorbent surface and allows the determination of the adsorption energy as well as the shape and size of the clusters of adsorbate molecules formed in the pores of the analysed material. Additionally, the Quenched Solid Density Functional Theory was selected to determine the cumulative pore volume, pore size distributions and other micropore parameters. The analyses revealed a considerable degree of complexity of the carbons’ porous structure, including differences in the adsorption of CO2 and N2. The complementarity of the applied methods leads to the reliable determination of the optimum activated carbon for CO2 adsorption and assists reverse engineering approaches in the production and activation stage.

Significance of extra-framework monovalent and divalent cation motion upon CO2 and N2 sorption in zeolite X

Experimental observations and the GCMC (Grand Canonical Monte Carlo) simulations with fixed and mobile cations in their cavities have been used to study nitrogen and carbon dioxide sorption in divalent cation (Ca, Sr, and Ba) exchanged Zeolite X. Simulations of carbon dioxide and nitrogen adsorption isotherms and the heat of adsorption in divalent cation exchanged zeolite X produced results that were similar to those found in experimental results. Both experimental and simulated isotherms showed that carbon dioxide adsorption capacity is saturated at lower pressure with high adsorption capacity than the nitrogen isotherm in all zeolite samples. In the order of electronegativity of the extra-framework cations, the isosteric heat of sorption results show that carbon dioxide as well as nitrogen molecules interact more with divalent metal ion exchanged zeolites. Simulations of carbon dioxide and the nitrogen sorption in zeolite -X revealed that the mobile extra-framework cations in the cages of zeolite X had a significant advantage over zeolite molecular sieves in the separation process. The simulation with mobile cations can be a good tool for developing selective and purposeful zeolite-based adsorbents by knowing the cation position and its migration upon the adsorption of various gases.

Digitization of Adsorption Isotherms from "The Thermodynamics and Hysteresis of Adsorption''

Sorption isotherms collected from tables in the seminal dissertation, “The Thermodynamics and Hysteresis of Adsorption” by A. J. Brown, have been digitized and made publicly available, along with supporting software scripts that facilitates usage of the data. The isotherms include laboratory measurements of xenon, krypton, and carbon dioxide adsorption (and, when possible, desorption) isotherms on a single sample of Vycor glass1, at various temperatures including subcritical conditions for xenon and krypton. The highlight of this dataset is the collection of “scanning” isotherms for xenon on Vycor at 131 K. The scanning isotherms examine numerous trajectories through the adsorption-desorption hysteresis region, such as primary adsorption and desorption scanning isotherms that terminate at the hysteresis boundary, secondary scanning isotherms made by selective reversals that return to the boundary, and closed scanning loops. This dataset was originally used to test the independent domain theory of adsorption and continues to support successor theories of adsorption/desorption scanning hysteresis including more recent theories based on percolation models. Through digital preservation and release of the tables from Brown’s dissertation, these data are now more easily accessible and can continue to find use in developing models of adsorption for fundamental and practical applications.

A novel Zn-based-MOF for efficient CO2 adsorption and conversion under mild conditions

A novel Zn-based-MOF material, called Zn-URJC-8, containing two different organic linkers, 2-aminoterephtallic acid and 4,4-bipyridyl, has been synthetized and used for catalytic purposes for the first time. The structure of Zn-URJC-8 has been determined by single-crystal X-ray diffraction (XRD) showing -NH2 groups inward-facing of narrow pores, providing the material with excellent properties as CO2 adsorbent. The good results obtained by means of carbon dioxide adsorption isotherms have demonstrated the high interaction between CO2 and -NH2 groups with a Qst value of 54 kJ/mol at low coverage. The Zn-URJC-8 material also display promising results as catalyst for CO2 transformation in added value products. Almost complete conversion of epichlorohydrin and CO2 in cycloaddition reaction has been achieved under mild conditions, and the influence of different radical groups coordinated to the epoxides has been evaluated on the reaction yield. The recyclability has been also tested and the structural integrity of the catalyst is maintained after several consecutive reaction cycles.

Novel Lanthanide(III) Porphyrin-Based Metal-Organic Frameworks: Structure, Gas Adsorption, and Magnetic Properties.

The present work focuses on the hydrothermal synthesis and properties of porous coordination polymers of metal–porphyrin framework (MPF) type, namely, {[Pr4(H2TPPS)3]·11H2O}n (UPJS-10), {[Eu/Sm(H2TPPS)]·H3O+·16H2O}n (UPJS-11), and {[Ce4(H2TPPS)3]·11H2O}n (UPJS-12) (H2TPPS = 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayl)tetrakisbenzenesulfonate(4-)). The compounds were characterized using several analytical techniques: infrared spectroscopy, thermogravimetric measurements, elemental analysis, gas adsorption measurements, and single-crystal structure analysis (SXRD). The results of SXRD revealed a three-dimensional open porous framework containing crossing cavities propagating along all crystallographic axes. Coordination of H2TPPS4– ligands with Ln(III) ions leads to the formation of 1D polymeric chains propagating along the c crystallographic axis. Argon sorption measurements at −186 °C show that the activated MPFs have apparent BET surface areas of 260 m2 g–1 (UPJS-10) and 230 m2 g–1 (UPJS-12). Carbon dioxide adsorption isotherms at 0 °C show adsorption capacities up to 1 bar of 9.8 wt % for UPJS-10 and 8.6 wt % for UPJS-12. At a temperature of 20 °C, the respective CO2 adsorption capacities decreased to 6.95 and 5.99 wt %, respectively. The magnetic properties of UPJS-10 are characterized by the presence of a close-lying nonmagnetic ground singlet and excited doublet states in the electronic spectrum of Pr(III) ions. A much larger energy difference was suggested between the two lowest Kramers doublets of Ce(III) ions in UPJS-12. Finally, the analysis of X-band EPR spectra revealed the presence of radical spins, which were tentatively assigned to be originating from the porphyrin ligands.

CARS‐measurement of adsorption isotherms of carbon dioxide in Vycor glass and CARS‐porosimetry

AbstractIt has been shown recently that coherent anti‐Stokes Raman scattering (CARS) allows probing the adsorption in optically transparent bulk nanoporous materials. The phases appearing in the pores at different conditions are identified by their resonant spectral contributions characterized by special values of the Raman shift and the linewidth. The present work demonstrates that the spectral amplitudes retrieved from the CARS spectra are the key for numerical description of the specific loadings of the phases. As a result, the adsorption isotherms can be obtained from the spectroscopic data. An essential point here is the presence of the nonresonant background caused by the material of the nanoporous matrix. It is used as the reference to overcome changes in collimated transparency of the sample in the pressure range at which the condensation occurs in the pores. Also, we show that the average pore radius can be estimated by analysis of a single CARS spectrum, allowing for the CARS‐porosimetry.

Gas transport parameters, density and free volume of nanocrystalline poly-2,6-dimethylphenylene oxide

Poly(2,6-dimethylphenylene oxide-1,4) (PPO) belongs to a fairly investigated group of polymers that, nevertheless, provokes permanent research interest. The current study is focused on a combination of various physicochemical methods of polymer testing (DSC; molecular weight distribution; surface area by low-temperature adsorption isotherms of nitrogen and carbon dioxide; X-Ray diffraction analysis; hydrostatic measurement of density; gas permeability and diffusion measurement) with variation of molecular weight and different states of polymer samples (amorphous, semi-crystalline, biaxial-oriented). The alteration of the density, gas permeability and diffusion parameters is evaluated through modeling of PPO as a polymer-polymer blend material with amorphous, nano-sized crystalline (≤7 nm), and so-called rigid amorphous fraction (RAF) phases. The estimation of the phase properties of PPO samples allows to conclude that the permeability and diffusion characteristics decline in a row crystalline > amorphous > RAF.

Insight on Coal Swelling Induced by Monolayer and Multilayer Adsorption

Summary Gas adsorption, desorption, and displacement occur throughout the coalbed methane (CBM) and enhanced coalbed methane (ECBM) recovery process, causing the coal pores to deform and affecting injectivity and productivity. The primary objectives of this study include determining the pressure at which the monolayer adsorption transitions to multilayer adsorption and linking the swelling strain to both classes of adsorption. In this study, the simplified local density (SLD) theory was first modified and applied to describe the characteristics of both types of adsorption and to determine the transition pressure. A strain model coupled with the SLD theory was then developed to describe adsorption-induced deformation. Next, the measured methane (CH4) and carbon dioxide (CO2) adsorption isotherms, and strain data on the same coals, were collected for model validation. Results suggest that gas adsorbed on coal surfaces at the very beginning (monolayer adsorption) and the adsorption on other gas molecules continues once the surface has been filled (multilayer adsorption). Results also suggest that swelling strain is proportional to both types of adsorption, with the multilayer case being larger than the monolayer case. This difference may be due to the additional repulsion between the adsorbate and multilayer liquid film.