Non-equilibrium molecular dynamics simulation of gas separation in a microporous carbon membrane

We have carried out non-equilibrium molecular dynamics simulations of gas separation in a “selective surface flow” membrane. The gas mixture studied is hydrogen/methane, which is relevant to hydrogen purification in refineries. The simulations give insight into the separation mechanism, which is based on the transport of the more strongly adsorbing species (methane) in a dense layer near the pore wall, with the less strongly adsorbed species (hydrogen) diffusing through a less dense region close to the centre of the pore. Good agreement is obtained with experimental selectivity data. This work is also relevant to the study of the combined effects of adsorption and diffusion in microporous carbon adsorbents.     

Molecular dynamics simulation of small gas molecule permeation through CAU-1 membrane

CAU-1 is one of aluminum-based amine-functionalized Metal–Organic Frameworks(MOFs). Gas permeation and separation behaviors through CAU-1 membrane were simulated by the dual-control plane nonequilibrium molecular dynamics(DCP-NEMD) method. The thickness of membrane was 3.55 nm.Gases CO_2, N_2, CH_4, H_2, He, Kr and Xe were chosen for the calculation in both single component and binary mixtures. The permeation process was calculated in grand canonical(l VT) ensemble with periodic boundary conditions(PBC) in x-and y-directions at different temperatures. The calculated permeance of H_2, CH_4, N_2, CO_2 and Kr decreased with increasing temperature in both single and binary system, while that of Xe with kinetic molecule of 0.41 nm increased with increasing temperature. It shows Xe permeation is governed by activated diffusion. The simulated separation factors of CO_2/N_2 and CO_2/CH_4 of 4.2 and 1.3 respectively were lower than the experimental ones when only considering van der Waals interaction. Further consideration of electrostatic potential leads to improved calculation CO_2/N_2 and CO_2/CH_4 separation factor of 23.0 and 12.9 respectively that were consistent with the experimental ones of 26.2 and 14.8. It suggests the necessity of considering the Coulomb interactions between CO_2 and NH_2-on the pore wall of CAU-1 for permeation of CO_2. For H_2/N_2 and H_2/CH_4 the ideal selectivities also keep consistent with our experimental results. Interestingly, the simulated separation factor for noble Kr/Xe reaches infinite, predicting that CAU-1 membrane possesses potential separation properties for radioactive Kr/Xe.     

Diffusion in a mesoporous silica membrane: Validity of the Knudsen diffusion model

Experimental permeance data for several light gases in a mesoporous silica membrane are analyzed in detail and shown to conform closely to the Knudsen diffusion model. The results of this study do not support the conclusions drawn from recent molecular simulations concerning the inadequacy of the Knudsen model.     

Adsorption of propane, propylene and isobutane on a metal-organic framework: Molecular simulation and experiment

The separation of propane/propylene mixtures is the most energy-intensive operation practiced in the petrochemical industry. Adsorptive processes are currently viewed as a promising alternative to cryogenic distillation for the separation of these mixtures. In this paper, we explore the possibility of using a new metal-organic framework material, CuBTC, in adsorptive separation processes, particularly in a simulated moving bed (SMB) context using isobutane as a potential desorbent. A gravimetric method has been used to measure the adsorption equilibrium isotherms of propylene, propane and isobutane onto a commercial CuBTC powder over a temperature range from 323 to 423 K and pressures up to 100 kPa. These were complemented by a detailed experimental characterization of the structure of CuBTC using XRD and SEM techniques. Comparison of experimental isotherms with grand canonical Monte Carlo simulations in CuBTC showed that propane adsorption occurs preferentially in small octahedral pockets, while isobutane is excluded from these pockets due to its bulky structure. Propylene was seen to interact strongly with unsaturated metal sites, due to specific π‐Cu bonds. These interactions significantly enhance the affinity of this MOF for unsaturated hydrocarbons. Furthermore, in a range of temperatures and pressures, the affinity of CuBTC for isobutane is intermediate to that of propane and propylene. Our results suggest that CuBTC-isobutane is a very promising adsorbent-desorbent pair for use in SMB processes for propane/propylene separations.     

An integrated model for adsorption-induced strain in microporous solids

Deformation of porous materials during adsorption of gases, driven by physico- or chemo-mechanical couplings, is an experimentally observed phenomenon of importance to adsorption science and engineering. Experiments show that microporous adsorbents exhibit compression and dilation at different stages of the adsorption process. A new integrated model based on the thermodynamics of porous continua (assumed to be linear, isotropic and poroelastic) and statistical thermodynamics is developed to calculate the adsorption-induced strain in a microporous adsorbent. A relationship between the strain induced in the adsorbent and the equilibrium thermodynamic properties of the adsorbed gas is established. Experimental data of CO₂ adsorption-induced strain in microporous activated carbon adsorbents (Yakovlev, V.Y., Fomkin, A.A., Tvardovskii, A.V., Sinitsyn, V.A., 2005. Carbon dioxide adsorption on the microporous ACC carbon adsorbent. Russian Chemical Bulletin, International Edition 54, 1373-1377) is used to fit the model parameters and to validate the model. Assuming that the initial contraction in a microporous adsorbent is caused due to an attractive interaction between the adsorbed gas and the adsorbent, we demonstrate that there also exists a repulsive interaction amongst the adsorbed gas molecules and that this repulsive interaction can be correlated to the adsorption-induced strain. The proposed correlation can be extended to take into account the adsorbate-adsorbent attractive interaction in order to offer an undisputed and complete explanation of the adsorption-induced strain in microporous adsorbents.     

Influence of oxidation temperature on the gas permeation and separation properties in a microporous carbon membrane

Of thermosetting polymers, polyphenylene oxide (PPO) is considered as one of the promising alternative polymeric precursors for carbon membrane preparation. In this study, the PPO derived carbon membranes were prepared by carbonization and followed by air-oxidation as post-treatment method to modify the membrane pore structures. The characterization of the pore properties showed that air-oxidation enlarged the pore structure for the postoxidized carbon materials. The permeation results for the post-oxidized carbon membranes showed that the extent of the permeation modification was strongly dependent on the oxidation temperature. In the binary mixture gas systems, the permeation performance of the adsorbing gas species increased due to the surface diffusion mechanism. It is considered in the oxidation effect on the permeation modification that the post-oxidation of the carbon membranes increased gas permeation and separation properties.     

Dimethyl silane-modified silica in polydimethylsiloxane as gas permeation mixed matrix membrane

The gas transport behaviors of O₂, N₂, CO₂ and CH₄ were investigated in mixed matrix membranes (MMMs) prepared from polydimethylsiloxane (PDMS) filled with surface functionalized silica (SiO₂) nanoparticles. SiO₂ surface modification was performed through silanization using chlorodimethyl silane. FTIR confirmed the presence of dimethyl silane on SiO₂ (Si-DMS) whereas elemental analysis showed 94.2% successful modification. Thermal gravimetric analysis revealed the improved thermal stabilities of PDMS MMMs. Field emission scanning electron microscopy revealed the uniform distribution of Si-DMS within the membrane. The effect of Si-DMS in gas permeabilities (P) was in contrast to the Maxwell model prediction. Enhanced P values of all gases in PDMS MMMs (as compared to pure PDMS) were associated to the improvement in diffusion coefficients (D_m) despite the reduction in gas solubility coefficients. The increase in D_m values was attributed to the higher free volumes in PDMS MMMs. However, slight declines (<8% of pure PDMS) in selectivities were observed. Overall, PDMS MMMs have improved performances due to enhanced gas permeabilities.     

多孔石墨烯气体分离膜分子渗透机理

通过分子动力学方法模拟了4种不同气体分子（He,H₂,N₂和CH₄）在多孔石墨烯气体分离膜中的穿透过程,揭示了气体分子穿透石墨烯纳米孔的渗透机理,指出分子的渗透不仅与其动力学参数有关,如分子直径和质量,还与分子在石墨烯表面的吸附有关。石墨烯表面的吸附层给气体分子的渗透提供了一个额外的路径,因此分子在石墨烯表面的吸附越强,分子的渗透通量越大。同时,不同大小的纳米孔下H₂分子的渗透通量都随着压力的增加而线性增加。     

Molecular dynamics simulation of diffusion and permeation of gases in polystyrene

Molecular dynamics simulations are performed to study the diffusion and permeation of gases, including argon, nitrogen, methane, carbon dioxide, and propane, in polystyrene over a wide range of temperatures. A jumping mechanism is observed for the diffusion of diffusants in polymer. The calculated diffusion coefficients agree well with the experimental data and with the results of former simulation studies. The relation between the diffusion coefficient and the molecular diameter is confirmed by the results. Our calculated results on the temperature-dependence of diffusion coefficients show that for some gases a break is seen, at the glass transition temperature, in the Arrhenius plot of ln (D) versus 1/T, while for some other light gases, argon and nitrogen, the plot is linear over the whole temperature range. We have also calculated the permeability coefficients, using the diffusion coefficients calculated in this work and our recently published solubility coefficients [Eslami and Müller-Plathe, Macromolecules 2007; 40:6413]. Our results show that the calculated permeability coefficients are higher than the experimental data by almost the same trend observed in the solubility calculations, but the ratios of calculated permeabilities are in a very good agreement with experiment.     

Molecular modeling and adsorption properties of porous carbons

In this work, we calculate the adsorption isotherms and isosteric heat of argon in molecular models of saccharose coke obtained via the Hybrid Reverse Monte Carlo method. In the first route (method A), the molecular models were built by considering only carbon atoms, and all other heteroatoms present were neglected. In the second route (method B), the molecular models were built by considering carbon and hydrogen atoms. We find that the models obtained via method B have smaller pores as compared to the models obtained via method A. This is reflected in the adsorption properties. The amount adsorbed is less in models obtained via method B as compared to method A. We also find that the isosteric heat calculated in the models obtained via method B match the experimental data more closely as compared to models obtained from method A.     

On the dynamics and control of through-plane water distributions in PEM fuel cells

We provide a semi-analytic solution to simplify an experimentally validated numeric realization of a two-phase, reaction-diffusion, distributed parameter model of the through-plane water distributions as they evolve inside polymer electrolyte membrane (PEM) fuel cell gas diffusion layers. The semi-analytic solution is then analyzed for stability and to gain insight into the dynamics of the equilibrium (steady-state) water distributions. Candidate distributions for vapor and liquid water are then identified which allow maximum membrane hydration while simultaneously avoiding voltage degradation that results from anode liquid water accumulation (flooding). The desired anode water distributions could be maintained via control of the anode channel conditions (boundary value control) with the ultimate goal to maximize the hydrogen utilization and prolong fuel cell life.     

A new method to quantify parameters of membrane morphology from electron microscopy micrographs by texture recognition

A new method has been developed in order to automatically quantify parameters of membrane morphology from micrographs obtained through microscopy techniques. The parameters estimated by this algorithm are: pore size distribution, porosity, pore symmetry, regularity and tortuosity, as well as various statistical measures. These properties determine the performance of a membrane.The proposed method is based on texture recognition. It first identifies the pores present in the membrane from a cross-section micrograph of it, then labels them and finally makes the corresponding measurements. The main difference and advantage of this technique with respect to previous proposals is that the algorithm does not perform generic particle recognition, but direct scanning of typical pore structures and no user decisions are needed in all the steps of the process. Additionally, the proposed technique does not only determine typical parameters, such as pore size, but also particular characteristics of membrane topology, such as symmetry.The source information consists of cross-section membrane micrographs that can be typically obtained from electron microscopy (scanning or transmission), as well as from other types of microscopy, which are the most common acquisition techniques used by membranologists. The system provides quantitative, systematic and fast results, which represents a significant advance in the field of membrane analysis.     

MOF-74 building unit has a direct impact on toxic gas adsorption

Metal organic framework (MOF-74) analogs have been synthesized using cobalt, magnesium, nickel, and zinc metal centers. The capability of these materials to remove ammonia, cyanogen chloride, and sulfur dioxide from air has been evaluated via fixed-bed breakthrough testing in both dry and humid conditions. Octane breakthrough tests were performed to determine the physisorption capacities of the materials. All materials were stored in air prior to use. Dynamic breakthrough capacities of the analogs were compared to 13X zeolite and BPL activated carbon. The impact of the metal center on the adsorption behavior is illustrated with each analog providing different ammonia and cyanogen chloride adsorption capacities. The results provide an important step in the assessment of the potential of MOFs to function as porous adsorbent materials.     

Parametric investigations of premixed methane-air combustion in two-section porous media by numerical simulation

Motivated by detailed designs of industrial porous burners published in patents, the combustion of methane-air mixtures in a two-section porous burner has been studied numerically. The software FLUENT is used to solve a two-dimensional transient mathematical model of the combustion. In order to reveal the reality of the combustion in porous media, the user defined function (UDF) is used to extend the ability of FLUENT and enable two-dimensional distributions of temperature and velocity to be obtained. Some operating or property parameters, which mainly affect the functions and quality of the industrial burner design, such as the inlet velocity of the reactants, the equivalence ratio, the extinction coefficient and the thermal conductivity of porous media, have been investigated. The results show that the contours of temperature and velocity change considerably at the interface of the porous media and near the wall, the gas temperature at the low inlet velocity limit is higher than that for the high velocity limit, the thermal conductivity in the upstream section has more influence on the temperature than that in the downstream section and finally, the temperature profiles of both the gas and the porous skeleton vary considerably with changes of the radiative extinction coefficient of the large-pore porous media.     

Aerodynamic behavior of a gas mask canister containing two porous media

This paper discusses the aerodynamic behaviors of a gas mask canister with a complex inner structure and two porous materials in the filter layer and the activated carbon layer. The effects of the distribution and area of holes in the main sieve diaphragm and the thickness of the activated carbon layer on the pressure drop and the flow structure were determined using computational fluid dynamic (CFD) tools. The momentum loss of porous flow calculated by Forchheimer's equation was added to the source term in the momentum equation. Streakline flow visualization was employed to observe gas flow structures within the empty canister and to identify the shortcomings of the prototype canister. Simulation results for the estimated inertial and viscosity parameters in Forchheimer's equation agree closely with experimental values. The porosity of the canister for intake flows of 15-135 L/min causes the flow behavior to transition gradually from linear (viscous effect) to slight non-linear behavior (slight inertia effect). This study uses air age as an index of the time that air resides within the canister to displace the adsorption time of toxic gas. This approach conveniently elucidates overall filter capacity and the positions of dead zones in the activated carbon layer. The simulation results reveal that the channel design of the main sieve diaphragm dominates the aerodynamic behavior of the fluid within the activated carbon layer. Better hole distribution and a larger hole area correspond to a lower pressure drop, a smaller dead zone, and a higher adsorption time. The results in this study provide a valuable reference for designing channels in the main sieve diaphragm, and will be helpful in designing gas mask canisters.     

Effects of non-ideal adsorption equilibria of gas mixtures on column dynamics

A theoretical study has been made for simulating the dynamic behavior of non-ideal gas mixtures in an isothermal fixed-bed adsorber. A mathematical model was developed which takes into account the non-ideality of adsorbable species on the adsorbed phase under equilibrium. The model is based on both the real adsorbed solution theory (RAST), which incorporates the activity coefficients in the multicomponent isotherm equations to account for the deviations from ideality, and the linear driving force (LDF) model for representing diffusion resistance inside the adsorbent particles. To describe the effect of non-ideal adsorption equilibrium of gas mixtures on the breakthrough curves, we considered several model mixtures of binary and ternary components which exhibit non-ideal behavior with azeotropic crossovers in the composition domains at equilibrium. Sample calculations of a fixed-bed adsorption were done with various inlet gas compositions of binary and ternary mixtures, respectively, at a fixed total concentration. From the calculation results, it was shown that the order of breakthrough curves could be changed at a certain value of inlet gas composition ratio. This result implies that the dynamic behaviors of fixed-bed adsorption are greatly influenced by multicomponent equilibrium models. Furthermore, the reversal phenomenon of breakthrough curves could not be simulated by the ideal adsorbed solution theory (IAST).     

Time evolution of dynamic heterogeneity in a polymeric glass: a molecular dynamics simulation study

Dynamic heterogeneity, where it is noticed in molecular dynamics (MD) simulations that, for example, conformational transition rates vary greatly from bond to bond, is characteristic of polymeric glasses. The phenomenon can be attributed to the fact that certain local bond sequences are more capable of conformational rearrangement than others. These local sequences become fixed sites when the overall chain trajectory is frozen-in in the glass. Although this is no doubt the case, because of the relatively short times of MD trajectories and the relatively small numbers of transitions it is important to establish that the heterogeneity does evolve in time in the manner expected from the local site picture and is not an artifact of short simulations or small numbers. This is undertaken here using a polyethylene system that has been much studied previously. Long trajectories are generated where the time evolution of heterogeneity can be studied. It is found that both the standard deviation and the mean value of the transitions over the bonds evolve linearly in time. This is consistent with the local fixed site picture and not with a random process involving relatively small numbers of transitions.     

Multi-component lattice gas diffusion

In this paper, diffusional transport of multi-component mixtures within the framework of a three-dimensional lattice gas is studied using dynamic Monte Carlo simulations. The mobile species, instantaneously hopping from one site to another, are assumed to have no mutual interactions, other than the usual ‘hard core’ interactions. Most strikingly, percolation phenomena occur for multi-component mixtures with significant differences in mobility. These greatly reduce the flux of the mobile component and cause failure of the standard macroscopic theories, including, e.g., the Maxwell-Stefan theory. Furthermore, we demonstrate that the well-known correlation effect disappears for systems in which gradients in the vacancy concentration are present. For systems in which co-operative displacements of two or more molecules are allowed to occur the effect of correlation between successive jumps vanishes, while the plot of the mobility versus occupancy shows a maximum. This intricate relation between mobility and occupancy again complicates the use of standard theories for describing mass transport.     

A comparative simulation analysis of propane dehydrogenation in composite and microporous membrane reactors

Propane dehydrogenation has been simulated for a composite membrane reactor and a microporous membrane reactor using plug‐flow reactor models, in which both were packed with Pt/Al₂O₃ catalyst in the tube‐side. The reaction kinetics employed in the analysis were obtained from experimental data produced in an integral fixed bed reactor with the same catalyst. Comparative studies were carried out to analyse the performances of reactors containing the different membranes in terms of contact time, flow pattern and flow rate of sweep gas, and pressure. In general, the composite membrane reactors gave the better performance for all cases investigated. © 2002 Society of Chemical Industry