Predicting Mixture Adsorption Research Articles

Computing Mixture Adsorption in Porous Materials through Flat Histogram Monte Carlo Methods.

Mixture adsorption properties of porous materials are critical to determine their potential as adsorbents in separation applications. Toward the discovery of optimal adsorbents, in silico screening studies typically employ the grand canonical Monte Carlo (GCMC) technique to compute adsorption properties of gas mixtures in materials of interest at a given condition (i.e., composition, total pressure, and temperature) or to compute their adsorption properties for each component, followed by utilizing methods to predict mixture adsorption isotherms. However, the former approach results in the need for repeated calculations when different conditions such as compositions are considered. For the latter, the predictions may involve uncertainties, sometimes originating from the fitting quality to the pure component isotherms, and repeated simulations may also be needed for different temperatures. To this end, this study demonstrates the potential of flat histogram Monte Carlo methods in addressing the abovementioned shortfalls. Specifically, the so-called NVT + W method, first reported by Smit and co-workers, is extended herein to determine the macrostate probability distribution (MPD) of binary mixtures in porous materials. The obtained MPD can be reweighted to any conditions, yielding accurate adsorption isotherms of any desired compositions and temperatures. This approach, denoted as 2D NVT + W, is also compared with the widely adopted ideal adsorbed solution theory (IAST) method, and the former is found to offer more reliable predictions. Overall, the 2D NVT + W approach represents an efficient and effective alternative to compute mixture adsorption isotherms for porous materials, and the obtained MPD can be conveniently reused by peer researchers. A user-friendly Python code is also provided along with this article to employ this method.

Surprising Use of the Business Innovation Bass Diffusion Model To Accurately Describe Adsorption Isotherm Types I, III, and V

Using adsorption isotherm data to determine heats of adsorption or predict mixture adsorption using the ideal adsorbed solution theory (IAST) relies on accurate fits of the data with continuous, mathematical models. Here, we derive an empirical two-parameter model to fit isotherm data of IUPAC types I, III, and V in a descriptive way based on the Bass model for innovation diffusion. We report 31 isotherm fits to existing literature data covering all six types of isotherms, various adsorbents, such as carbons, zeolites, and metal-organic frameworks (MOFs), as well as different adsorbing gases (water, carbon dioxide, methane, and nitrogen). We find several cases, especially for flexible MOFs, where previously reported isotherm models reached their limits and either failed to fit the data or could not sufficiently be fitted due to stepped type V isotherms. Moreover, in two instances, models specifically developed for distinct systems are fitted with a higher R2 value compared to the models in the original reports. Using these fits, it is demonstrated how the new Bingel-Walton isotherm can be used to qualitatively assess the hydrophilic or hydrophobic behavior of porous materials from the relative magnitude of the two fitting parameters. The model can also be employed to find matching heats of adsorption values for systems with isotherm steps using one, continuous fit instead of partial, stepwise fits or interpolation. Additionally, using our single, continuous fit to model stepped isotherms in IAST mixture adsorption predictions leads to good agreement with the results from the osmotic framework adsorbed solution theory that was specifically developed for these systems using a stepwise, approximate fitting, which is yet far more complex. Our new isotherm equation accomplishes all of these tasks with only two fitted parameters, providing a simple, accurate method for modeling a variety of adsorption behavior.

Adsorption-Based Separation of Near-Azeotropic Mixtures-A Challenging Example for High-Throughput Development of Adsorbents.

Adsorption of gas mixtures is central to adsorption-based gas separations, and the number of adsorbate mixture/adsorbent systems that exist is staggering. Because examples of machine learning (ML) models predicting single-component adsorption of arbitrary molecules in large libraries of crystalline adsorbents have been developed, it is interesting to determine whether these models can accurately predict mixture adsorption. Here, we use molecular simulations to generate mixture adsorption data with a set of 12 near-azeotropic molecules in a diverse set of MOFs. These data provide a challenging example for any method to rapidly predict mixture adsorption in MOFs. We combine a previous ML single-component isotherm model with ideal adsorbed solution theory (IAST) to make predictions that can be compared directly with molecular simulation data for these adsorbed mixtures. This combination of ML and IAST illustrates the scope that is available with these methods, but the accuracy of the resulting predictions is disappointing. By examining the same examples with IAST based on minimal molecular simulation data for single-component isotherms, we show that having an accurate description of adsorption in the dilute loading limit is critical to being able to accurately predict mixture adsorption. This observation points to a useful direction for future work developing robust ML models of adsorption isotherms for diverse collections of molecules and adsorbents.

PyGAPS: a Python-based framework for adsorption isotherm processing and material characterisation

Material characterisation through adsorption is a widely-used laboratory technique. The isotherms obtained through volumetric or gravimetric experiments impart insight through their features but can also be analysed to determine material characteristics such as specific surface area, pore size distribution, surface energetics, or used for predicting mixture adsorption. The pyGAPS (Python General Adsorption Processing Suite) framework was developed to address the need for high-throughput processing of such adsorption data, independent of the data origin, while also being capable of presenting individual results in a user-friendly manner. It contains many common characterisation methods such as: Brunauer–Emmett–Teller and Langmuir surface area, t and αs plots, pore size distribution calculations (Barrett–Joyner–Halenda, Dollimore–Heal, Horvath–Kawazoe, DFT/NLDFT kernel fitting), isosteric enthalpy calculations, ideal adsorbed solution theory calculations, isotherm modelling and more, as well as the ability to import and store data from Excel, CSV, JSON and SQLite databases. In this work, a description of the capabilities of pyGAPS is presented. The code is then be used in two case studies: a routine characterisation of a UiO-66(Zr) sample and in the processing of an adsorption dataset of a commercial carbon (Takeda 5A) for applications in gas separation.

Enrichment of ventilation air methane by adsorption with displacement chromatography technology: Experiment and numerical simulation

Using the principles of displacement chromatography, a cost-effective adsorption separation method for the recovery of ventilation air methane (VAM) is developed. A fixed bed with activated carbon beads (ACBs) is used to adsorb low-concentration methane from VAM gas. The stronger adsorption component CO2 passes through the column to displace the adsorbed CH4. This displacement step generates a product with highly pure CH4 gas. Adsorption equilibrium isotherms of CH4, N2 and CO2 have been measured gravimetrically at different temperatures up to 10bar. These isotherms are fitted to the Sips model. Diluted breakthrough results are analyzed using a bi-pore diffusion model to obtain the micropore diffusivities of CH4, N2 and CO2 in the ACBs. Mixture breakthrough results have been employed to validate the applicability of the IAST-Sips model to predict mixture adsorption equilibria. A rigorous mathematical model is used to investigate the evolution curves of CH4, N2 and CO2 along the fixed bed during the CO2 displacement step, where it is found that the enrichment of the low concentration CH4 is improved significantly. Furthermore, the CO2 displacement experiments in the fixed bed for methane recovery from CH4/N2 mixtures with 1% and 10% CH4 content are performed and compared with the simulated results. It is found that 10% CH4 gas is concentrated to 89% CH4 purity and 1% CH4 gas can be concentrated to 53.5% CH4 purity, demonstrating that CO2 displacement is a promising technology for the enrichment of ventilation air methane.

Mixture adsorption on zeolites applying the [formula omitted] temperature-dependency approach

In this study, the feasibility of the Pisat temperature-dependency approach in predicting mixture adsorption loadings on zeolites is examined. The presented case examples show that IAST, RAST or extended Langmuir together with the pure component saturated vapour pressure Pisat to describe the temperature dependency of adsorption, can be used to predict mixture adsorption. The approach makes it possible to predict mixture adsorption in various temperature, pressure and composition conditions by utilizing pure component adsorption data at only one temperature. In addition to vapour phase adsorption, the Pisat temperature-dependency approach is also found to be applicable in modelling liquid mixture adsorption. The approach is a valuable engineering tool especially in cases where there is a lack of adsorption data. The approach can be used e.g., in zeolite membrane permeation modelling, where the adsorption phenomenon has a considerable significance.

Efficient Methods for Screening of Metal Organic Framework Membranes for Gas Separations Using Atomically Detailed Models

Metal organic frameworks (MOFs) define a diverse class of nanoporous materials having potential applications in adsorption-based and membrane-based gas separations. We have previously used atomically detailed models to predict the performance of MOFs for membrane-based separations of gases, but these calculations require considerable computational resources and time. Here, we introduce an efficient approximate method for screening MOFs based on atomistic models that will accelerate the modeling of membrane applications. The validity of this approximate method is examined by comparison with detailed calculations for CH4/H2, CO2/CH4, and CO2/H2 mixtures at room temperature permeating through IRMOF-1 and CuBTC membranes. These results allow us to hypothesize a connection between two computationally efficient correlations predicting mixture adsorption and mixture self-diffusion properties and the validity of our approximate screening method. We then apply our model to six additional MOFs, IRMOF-8, -9, -10, and -14, Zn(bdc)(ted)0.5, and COF-102, to examine the effect of chemical diversity and interpenetration on the performance of metal organic framework membranes for light gas separations.

Shape versus inverse-shape selective adsorption of alkane isomers in carbon nanotubes

Simulation results are reported for the adsorption of pure pentane (C5) isomers and their ternary mixture in a series of open-ended armchair-type (m,m) single-walled carbon nanotubes (SWNTs). Inverse-shape selective adsorption occurs in the order of nC5<iC5<neoC5 only in the (7,7) SWNT as a result of the length entropy effect. In the larger (20,20) and (10,10) SWNTs, shape selective adsorption occurs in the order of nC5>or=iC5>neoC5 as a result of the configurational entropy effect. In smaller SWNTs, depending on the diameter, only nC5 adsorbs, or no adsorption at all occurs. The entropy effects are found to lead to a large adsorptive separation among the C5 isomers from their mixture. Using the ideal-adsorbed-solution theory with data on the adsorption of only the pure isomers, we predict mixture adsorption. The agreement between predictions and simulations deteriorates with decreasing diameter of the SWNT.

Adsorption of N 2, Ar, acetone, chloroform and acetone–chloroform mixture on carbon black in the framework of molecular layer structure theory (MLST)

Adsorption of pure nitrogen, argon, acetone, chloroform and acetone–chloroform mixture on graphitized thermal carbon black is considered at sub-critical conditions by means of molecular layer structure theory (MLST). In the present version of the MLST an adsorbed fluid is considered as a sequence of 2D molecular layers, whose Helmholtz free energies are obtained directly from the analysis of experimental adsorption isotherm of pure components. The interaction of the nearest layers is accounted for in the framework of mean field approximation. This approach allows quantitative correlating of experimental nitrogen and argon adsorption isotherm both in the monolayer region and in the range of multi-layer coverage up to 10 molecular layers. In the case of acetone and chloroform the approach also leads to excellent quantitative correlation of adsorption isotherms, while molecular approaches such as the non-local density functional theory (NLDFT) fail to describe those isotherms. We extend our new method to calculate the Helmholtz free energy of an adsorbed mixture using a simple mixing rule, and this allows us to predict mixture adsorption isotherms from pure component adsorption isotherms. The approach, which accounts for the difference in composition in different molecular layers, is tested against the experimental data of acetone–chloroform mixture (non-ideal mixture) adsorption on graphitized thermal carbon black at 50 °C.

Mixed Gas Equilibrium Adsorption on Zeolites and Energetic Heterogeneity of Adsorption Volume

A model for binary mixture adsorption accounting for energetic heterogeneity and intermolecular interactions is proposed in this paper. The model is based on statistical thermodynamics, and it is able to describe molecular rearrangement of a mixture in a nonuniform adsorption field inside a cavity. The Helmholtz free energy obtained in the framework of this approach has upper and lower limits, which define a permissible range in which all possible solutions will be found. One limit corresponds to a completely chaotic distribution of molecules within a cavity, while the other corresponds to a maximum ordered molecular structure. Comparison of the nearly ideal O2−N2−zeolite NaX system at ambient temperature with the system of O2−N2−zeolite CaX at 144 K has shown that a decrease of temperature leads to a molecular rearrangement in the cavity volume, which results from the difference in the fluid−solid interactions. The model is able to describe this behavior and therefore allows predicting mixture adsorption more accurately compared to those assuming energetic uniformity of the adsorption volume. Another feature of the model is its ability to correctly describe the negative deviations from Raoult's law exhibited by the O2−N2−CaX system at 144 K. Analysis of the highly nonideal CO2−C2H6−zeolite NaX system has shown that the spatial molecular rearrangement in separate cavities is induced by not only the ion−quadrupole interaction of the CO2 molecule but also the significant difference in molecular size and the difference between the intermolecular interactions of molecules of the same species and those of molecules of different species. This leads to the highly ordered structure of this system.

Untersuchungen zur Einzel‐ und Gemischadsorption von Phenolen an Aktivkohlen. Teil 2: Gemischadsorptionsgleichgewichte des Systems p‐Nitrophenol/p‐Chlorphenol/Aktivkohle

AbstractOn the thermodynamic basis of the theory of the Ideal Adsorbed Solution (IAS) a calculation method was used to predict mixture adsorption equilibria from the individual isotherms. The results of the prediction were compared with the results of practical measurements by the example of the adsorption of p‐nitro‐ and p‐chlorophenol mixture on the activated carbon DO 4. According to the explanations concerning the graphically represented results, the mean percent differences between calculated and experimental data by the exact solution of the IAS‐theory and by a described simplified method were 11 % and 13 %, respectively. It is thus confirmed that the IAS‐theory is very well suited for predicting adsorption equilibria for, e.g., phenol mixtures.