Adsorption Isotherms Of Carbon Dioxide Research Articles

Modeling of Organically Functionalized Mesoporous Silicas for the Design of Adsorbents

In order to obtain atomic-level models for hybrid inorganic-organic adsorbents that are based on ordered mesoporous silicas, molecular simulation methods have been developed which follow the reaction path of the synthesis of the silica material in a kinetic Monte Carlo Simulation. Organic surface groups such as phenyl or aminopropyl are introduced by replacing surface hydroxyl groups. The adsorption in these models is simulated by Grand Canonical Monte Carlo simulation. The experimental and simulated adsorption isotherms of ethane and carbon dioxide on MCM-41-based hybrid adsorbents agree well. In combination, these methods enable the computer-aided design of hybrid inorganic-organic adsorbents.

Carbon dioxide adsorption on the microporous ACC carbon adsorbent

Adsorption isotherms of carbon dioxide on the microporous ACC carbon adsorbent and the adsorption deformation of the adsorbent were measured. The heats of adsorption at temperatures raising from 243 to 393 K and pressures from 1 to 5⋅106 Pa were measured. In the low-temperature region (243 K), an increase in the amount adsorbed is accompanied by adsorbent contraction, and at high micropore fillings (a > 10 mmol g−1) the ACC carbon adsorbent expands. At high temperatures, adsorbent expansion is observed in the whole region of micropore filling. At 243 K in the low filling region (a < 1 mmol g−1), the heat of adsorption decreases smoothly from 27 to 24 kJ mol−1. The heat of adsorption remains virtually unchanged in the interval 2 mmol g−1 < a < 11 mmol g−1 and then decreases to 8 kJ mol−1 at a = 12 mmol g−1. Taking into account the nonideal character of the gas phase and adsorbent deformation the heats of adsorption are strongly temperature-dependent in a region of high pressures.

Gas Adsorption in Active Carbons and the Slit-Pore Model 1: Pure Gas Adsorption

We describe procedures based on the polydisperse independent ideal slit-pore model, Monte Carlo simulation and density functional theory (a 'slab-DFT') for predicting gas adsorption and adsorption heats in active carbons. A novel feature of this work is the calibration of gas-surface interactions to a high surface area carbon, rather than to a low surface area carbon as in all previous work. Our models are used to predict the adsorption of carbon dioxide, methane, nitrogen, and hydrogen up to 50 bar in several active carbons at a range of near-ambient temperatures based on an analysis of a single 293 K carbon dioxide adsorption isotherm. The results demonstrate that these models are useful for relatively simple gases at near-critical or supercritical temperatures.

Gas Adsorption in Active Carbons and the Slit-Pore Model 2: Mixture Adsorption Prediction with DFT and IAST

We use a fast density functional theory (a "slab-DFT") and the polydisperse independent ideal slit-pore model to predict gas mixture adsorption in active carbons. The DFT is parametrized by fitting to pure gas isotherms generated by Monte Carlo simulation of adsorption in model graphitic slit-pores. Accurate gas molecular models are used in our Monte Carlo simulations with gas-surface interactions calibrated to a high surface area carbon, rather than a low surface area carbon as in all previous work of this type, as described in part 1 of this work. We predict the adsorption of binary mixtures of carbon dioxide, methane, and nitrogen on two active carbons up to about 30 bar at near-ambient temperatures. We compare two sets of results; one set obtained using only the pure carbon dioxide adsorption isotherm as input to our pore characterization process, and the other obtained using both pure gas isotherms as input. We also compare these results with ideal adsorbed solution theory (IAST). We find that our methods are at least as accurate as IAST for these relatively simple gas mixtures and have the advantage of much greater versatility. We expect similar results for other active carbons and further performance gains for less ideal mixtures.

An investigation of the effects of pyrolysis parameters on gas separation properties of carbon materials

A significant extension of an earlier analysis of molecular sieving carbons formed from polymeric precursors is reported for separation of important gas pairs including O 2/N 2, CO 2/CH 4 and C 3H 6/C 3H 8. Previously, it was shown that changing the time or temperature of the pyrolysis protocol for a commercially available polyimide (Matrimid ®) altered the final properties of the carbons produced. Changing the precursor material was shown in this study to also affect the final carbon material obtained for a given final pyrolysis temperature. Analysis of low temperature carbon dioxide adsorption isotherms using density functional theory was employed to characterize the microporosity of the materials. Results are given here for a totally different packing-inhibited polyimide precursor (6FDA/BPDA-DAM). Sorption, permeation and diffusion data are compared with those obtained using the more densely packed commercial polyimide precursor Matrimid ® studied earlier. Thermal soak was also investigated and the effect on permeation properties determined for carbons using both precursors. The results indicate that carbons from both precursors have size-selective ultramicropores as well as larger nonselective micropores that provide high capacity sorption sites for penetrants. High permselectivities, combined with high permeabilities are found for some of the samples when compared with conventional polymer materials. A hypothetical ultramicropore size distribution is shown to be useful to relate transport data to results from more commonly used characterization techniques such as pore size distribution analysis.

Influence of micropore structure on Li-storage capacity in hard carbon spherules

Hard carbon spherules (HCS) were synthesized by a normal hydrothermal method (HCS1) and a microemulsion-mediated (reverse micelles) hydrothermal method (HCS2). The results from nitrogen adsorption isotherm at 77 K and carbon dioxide adsorption isotherm at 273 K showed that the micropores of HCS2 are smaller than that of HCS1. HCS2 with smaller micropores shows higher emf value and larger Li-storage capacity around 0 V while HCS1 with larger micropores exhibits better kinetic performance at high current density. It is found that micropore structure plays a key role in the thermodynamic and kinetic behaviors of Li-ion insertion and extraction process.

Porous materials from clays by the gallery template approach: synthesis, characterization and adsorption properties

Porous materials were obtained from clays by gallery templated synthesis. The equivalent surface areas of the samples were in the range 600–700 m 2 g −1 and the corresponding microporous volumes were near 0.3 cm 3 g −1. HRTEM confirmed the lack of long-range order of the prepared samples. Low temperature nitrogen adsorption showed textural differences in the samples, namely those arising from the neutral amines of different chain length used in synthesis. The possibility of using such materials as adsorbents of volatile organic compounds, due to their textural and hydrophobic characteristics, was studied by the adsorption of ethanol and methyl ethyl ketone and water for comparison. Their potential use as adsorbents for the purification of methane, e.g., for upgrading natural or landfill gas, was also studied by the determination of the room temperature adsorption isotherms of carbon dioxide, ethane, methane and nitrogen, where high initial selectivity values were obtained for the methane/carbon dioxide separation.

Nature of Adsorption and Desorption Branches in Cylindrical Pores

To examine the nature of the adsorption and desorption branches in hysteretic adsorption isotherms of gases on mesoporous materials, we measured the temperature dependence of the adsorption and desorption isotherms of argon, oxygen, and carbon dioxide onto MCM-41 with a pore diameter of 4.4 nm. The results clearly show that in the open-ended cylindrical pores of MCM-41, capillary condensation rather than evaporation takes place near a thermodynamical equilibrium transition, as opposed to the general statement that capillary evaporation can occur via a meniscus formed at the pore mouth, and, thus, takes place at equilibrium.

Importance of Volume Effects to Adsorption Isotherms of Carbon Dioxide on Coals

Attempts to describe high-pressure carbon dioxide (CO2) adsorption isotherm data using conventional adsorption equations to model the coal behavior have been only partially successful. Because swelling of the coal organic matrix in the presence of adsorbing gases is a well-known phenomenon and because traditional isotherm models assume a rigid structure, an adsorption isotherm equation was derived to account for the volume effects which may occur when an adsorbate alters the structure of an adsorbent. The equation, which accounts for volume change in general, was applied to the particular example of CO2 adsorption on coal. In some cases, significantly better fits were obtained when the adsorption data were fit to the swelling-modified model. The modified model partitions the experimentally determined adsorption into a surface adsorption term, which is important at lower pressure, and a rectilinear term, related to volume effects, which is important at higher pressures. This is particularly significant to ...

Investigation of porosity of carbon materials and related effects on gas separation properties

Carbon molecular sieving membranes are chemically robust materials with tailorable gas transport properties for O 2/N 2, CO 2/CH 4 and C 3H 6/C 3H 8 separations. Such carbon materials were formed in this study by the pyrolysis of polyimide precursors. The final pyrolysis temperature was varied to alter the carbon structure, which changed the average pore size. Characterization of the porosity of these materials and how this feature changes when pyrolysis conditions are varied could guide the systematic control of these materials. However, the carbon is an amorphous, microporous material, which makes it difficult to characterize compared to crystalline materials. From separation studies of penetrants on these materials it appears that these materials have both ultramicropores (<7 Å) and larger micropores. The ultramicropores are believed to be mainly responsible for molecular sieving while the micropores provide negligible resistance to diffusion but provide high capacity sorption sites for penetrants. Techniques such as wide angle X-ray diffraction and the analysis of carbon dioxide adsorption isotherms using density functional theory were employed to characterize the microporosity of the material. The small dimensions of the key ultramicropores make accurate determination of their pore size distribution difficult. Therefore, to effectively discuss the differences in transport properties when different pyrolysis temperatures are used as well as penetrants with different dimensions, a hypothetical ultramicropore size distribution was used as a tool to discuss and interpret a combination of parameter effects and trends of separation properties.

Characterization of synthetic carbons activated with phosphoric acid

The structural heterogeneity of synthetic phosphoric acid activated carbons has been analyzed using pore-size distributions (PSDs) obtained from nitrogen at −196 °C and carbon dioxide at 0 °C isotherms. PSDs where obtained by the BET–Kelvin method. It is shown that the BET–Kelvin method is in good agreement with DFT and provides a fast means for assessment of the porous structure of adsorbents. PSDs obtained by the BET–Kelvin method using different adsorbates give results consistent with each other. Due to the restricted pressure range for carbon dioxide adsorption isotherm the PSD gives information only about pores in the micropore range. The agreement between different methods is better for small micropores.

Micropore Size Distributions of Activated Carbons and Carbon Molecular Sieves Assessed by High-Pressure Methane and Carbon Dioxide Adsorption Isotherms

Experimental N 2 adsorption isotherms and high-pressure CO 2 and CH 4 adsorption isotherms have been obtained for a series of microporous carbon materials prepared for being used in gas separation and methane storage. Theshape of the isotherms is very different, which is due in part to differences in the overall micropore volume but, additionally and importantly, to the significant differences in the micropore size distribution of those samples. Micropore size distributions (MPSDs) have been deduced from those N 2 , CO 2 , and CH 4 isotherms by application of the General Adsorption Isotherm (GAI), according to two different approaches proposed in previous independent works. The comparison of the results has shown that, despite the different characteristics of CH 4 and CO 2 , and the different experimental temperatures and adsorption conditions (298 K, supercritical conditions, and 273 K, subcritical conditions, respectively), a quite good consistency between the MPSDs from these two gases has been obtained for all the samples studied. That suggests that both methods are suitable to analyze more sensibly the changes in the MPSDs of microporous samples. The fact that these MPSDs analysis are based on high-pressure adsorption isotherms and that CO 2 is especially useful for characterizing the narrow microporosity not accessible to N 2 makes both techniques very useful for the characterization of microporous samples.

Characterization of Porous Materials by Gas Adsorption: Comparison of Nitrogen at 77 K and Carbon Dioxide at 298 K for Activated Carbon

Amorphous materials are usually characterized using nitrogen adsorption isotherms at 77 K taken at pressures up to 1 bar to obtain pore size distributions. Activated carbons are amorphous microporous graphitic materials containing pores which can range from nanometers to microns in width and which can, in principle, be tailored to adsorb specific molecules or classes of molecule by changing the method of preparation (the activation process). For the physical chemist, they pose the challenge of understanding how gases adsorb in graphitic nanopores, that is, in restricted geometries, and of using that understanding to improve their characterization. In this paper, we compare pore size distributions of an ultrahigh surface area activated carbon (AX21) determined from nitrogen adsorption measurements up to 0.6 bar at 77 K with those determined from carbon dioxide adsorption measurements up to 20 bar at 298 K. Our analysis employs grand canonical and Gibbs ensemble Monte Carlo simulations together with accurate site−site interaction models of the adsorbates. We find that the calculated pore size distributions for each adsorbate are quite different, and the adsorption of one gas can be estimated from the adsorption of the other gas to within an error of 25% at the highest pressures only. At lower pressures, we speculate that large errors are due to the behavior of nitrogen in carbon micropores in which diffusion is severely limited. To substantiate this speculation, we have calculated the self-diffusion coefficient for nitrogen at 77 K and carbon dioxide at 298 K in carbon slit pores using equilibrium molecular dynamics. The results suggest that nitrogen is diffusionally limited, and possibly frozen, in such pores whereas carbon dioxide remains mobile. We conclude that room-temperature carbon dioxide adsorption isotherms up to the saturation pressure could provide a more accurate characterization of carbon microstructure than nitrogen isotherms at 77 K up to 1 bar.

Adsorption of Supercritical Carbon Dioxide on Silica

In this work, the adsorption isotherms of carbon dioxide on silica have been measured with a gravimetric method at nine different temperature values (from 312 up to 466 K) and at pressure levels up to 366 bar. The adopted technique allows for a direct evaluation of the density that is measured simultaneously to the adsorption load, thus avoiding possible systematic errors arising from the use of an equation of state to calculate density from pressure and temperature data. The enthalpy changes related to the adsorption process have been obtained from a thermodynamic analysis based only on excess properties.

High‐resolution adsorption isotherms of supercritical carbon dioxide on activated carbon

AbstractSupercritical fluids are attractive solvents for heterogeneous processes, including catalysis and adsorptive separation. However, adsorption processes in the near‐critical region are poorly understood and exhibit unique behavior where the adsorption of the supercritical solvent plays an important role in the solute adsorption. The behavior of supercritical fluids in confined pores has been studied theoretically, but there are few experimental data on their behavior in industrially important microporous materials. The adsorption of carbon dioxide on Calgon F400 activated carbon over a wide range of pressures (0–20 MPa) at temperatures near the critical point of carbon dioxide (30 to 45°C) was studied. Near‐continuous adsorption and desorption isotherms were measured with a new flow gravimetric apparatus with precise control over pressure and temperature. As pressure is increased, the excess adsorption increases sharply at low pressures; then a broad maximum is observed. At temperatures greater than the critical temperature, there is a sharp drop in excess adsorption near the critical region where the density of the bulk fluid increases sharply. A crossover is observed near the critical region where, below a certain pressure, the excess adsorption decreases with temperature, while above the crossover point the trend is reversed. When analyzed as a function of solvent density, the crossover disappears, revealing an anomalous maximum in total adsorption near the critical point similar to the enhanced local density or “charisma” observed in binary solute–supercritical fluid systems. A 2‐D EOS model using the 2‐D Peng‐Robinson EOS was able to qualitatively describe the adsorption behavior over the entire pressure range, but the quantitative agreement was poor in the near‐critical region.

Adsorption of Carbon Dioxide on Basic Alumina at High Temperatures

Adsorption isotherms of carbon dioxide at temperatures ranging from 293 K to 573 K and pressures up to 1 bar on two types of commercial basic alumina are presented.

Single and Mixed Gas Adsorption Equilibria of Carbon Dioxide/Methane on Activated Carbon

Single gas adsorption isotherms of methane and carbon dioxide on micro-porous Norit RB1 activated carbon were determined in a gravimetric analyser in the temperature range of 292 to 349 K and pressures to 0.8 Mpa. Furthermore binary isotherms of carbon dioxide and methane mixtures were determined at 292 K and pressures up to 0.65 MPa. Adsorbed phase compositions were determined from the gravimetric data by the rigorous thermodynamic method of Van Ness. These experimental binary equilibrium data were compared with equilibrium data calculated by the Ideal Adsorbed Solution (IAS) model. Only moderate agreement could be obtained. Finally, activity coefficients, accounting for the non-ideality of the adsorbate mixture, were calculated from the experimental data. The Wilson equation, derived for bulk solutions, was fitted on these activity data and the Wilson interaction parameters were determined. The Wilson equation proved to correlate the experimental data reasonably. However, the Wilson interaction parameters are not only completely different from those found for bulk solutions, but also the physical interpretation of these parameter values is completely lacking. It is concluded that new solution models should be developed encompassing both non-ideal solution behaviour and surface heterogeneity.

Geological controls on coalbed methane reservoir capacity and gas content

The influence of coal composition and rank on coalbed methane reservoir capacity, gas content and gas saturation have been investigated for a series of Australian, Canadian and United States coals. Globally there is no or little correlation between coal rank and methane adsorption capacity (as commonly assumed), although in particular basins there are general trends with rank and composition. Micropore 1 Micropores are less than 2 nm in diameter, mesopores 2 to 50 nm in diameter and macropores greater than 50 nm in diameter following current IUPAC classification [International Union of Pure and Applied Chemistry (IUPAC), 1994. Pure Applied Chemistry, 66, 1739]. 1 capacity and surface area, determined from low-pressure carbon dioxide adsorption isotherms (0°C) decrease and then increase with rank, passing through a minimum in the high volatile bituminous coal rank. There is no consistent variation in modal micropore size or size distribution with rank. For suites of isorank coals there is a poor (Permian Bulli and Wongawilli seams, Australia) to good positive correlation (Gates Formation coal seams, Lower Cretaceous, Canada) between vitrinite content and methane adsorption capacity (dry ash free and as received bases). For each isorank coal suite there is a good correlation between micropore capacity and abundance of vitrinite and high-pressure methane adsorption capacity. Comparison of coals of similar composition, but from different isorank suites, indicates however that the coals with the highest methane adsorption capacity do not necessarily have the highest micropore capacity. Such results are counterintuitive: most pore volume available for methane adsorption is generally assumed to be microporosity. It is suspected that moisture prevents methane from accessing (some?) microporosity or competes with methane for adsorption space. Carbon dioxide micropore capacity (which is performed on a dry basis) may thus not reflect the microporosity available for gas adsorption in moisture equilibrated coals. Alternatively because of differing physical and chemical properties of carbon dioxide and methane, apparent microporosity available to carbon dioxide (due to greater energy of adsorption) may not be available to methane. Total desorbed gas from canister analyses of Sydney Basin Australian coals suggests that most coals are under-saturated. For a small data set the degree of saturation is negatively correlated with permeability ( r=−0.78) suggesting preferential gas leakage from the higher permeability coals which are vitrite rich. Some degree of under-saturation is probably the result of increased reservoir capacity as a consequence of uplift of the coal seams and thus lower temperatures following gas generation. Rates of desorption are correlated with total gas content ( r=0.79) but do not correlate with rank or any compositional parameter.

Pure and Multicomponent Adsorption Equilibrium of Carbon Dioxide, Ethylene, and Propane on ZSM-5 Zeolites with Different Si/Al Ratios

Experimental adsorption isotherms of pure carbon dioxide, ethylene, and propane as well as their mixtures have been obtained on three samples of ZSM-5 zeolite of different atomic Si/Al ratios (15, 29, and 60) over the pressure range 0−100 kPa. The data are given at temperatures of 281, 293, and 308 K (pure data) and 293 K (binary and ternary data). Changes in the zeolite selectivity with its Si/Al ratio were observed for the pure components, with an increase in the loading of polar molecules, like carbon dioxide and ethylene, as the atomic Si/Al ratio decreases. The selectivity, however, was nearly constant for propane. The characteristic equilibrium curve was obtained for each adsorbent, and a good fit of the equilibrium data was obtained for all adsorbates at the three temperatures. Some equilibrium overadsorption and displacement effects with large deviations from the ideal behaviorincluding binary azeotropeswere found for the mixtures of polar and nonpolar compounds. Thus, ethylene and carbon dioxide ...

Adsorption Equilibria of C1to C4Alkanes, CO2, and SF6on Silicalite

Adsorption isotherms of methane, ethane, propane, n-butane, isobutane, carbon dioxide, and sulfur hexafluoride were measured gravimetrically on silicalite crystals at temperatures ranging from 3 to 81 °C and at pressures up to 2000 kPa. A virial equation was used to correlate the experimental data and to calculate the isosteric heats of adsorption and the limiting heats of adsorption at zero loading. The adsorption isotherms of isobutane exhibit inflection points at loadings of 4−6 molecules/unit cell in a certain temperature range. This unusual adsorption behavior is attributed to adsorption of isobutane in different locations of the channel system.