Diffusion Coefficients Of CO2 Research Articles

Determination of the Diffusion Coefficient in Electrodeposition Reactions by Electrochemical Impedance Spectroscopy: A Case Study of Cobalt in Molten LiCl-KCl Salt

Compared to direct current (DC) techniques, electrochemical impedance spectroscopy (EIS) allows for a more accurate determination of the diffusion coefficient of metal ions in electrodeposition reactions. However, its actual application has been less attempted due to the difficulty in determining complex parameters, such as the concentration of deposited species in the electrode matrix. Here, we introduce a simplified approach to facilitate the EIS application to electrodeposition reactions, using the Co(II)/Co(0) reaction in molten LiCl-KCl salt as a case study. The working electrode surface area was determined by the photography of the electrochemical cell taken in situ. The diffusion coefficients of Co(II) in the LiCl-KCl salt, determined by EIS, were found to be (3.56 ± 0.49) × 10−5 cm2/s and (1.61 ± 0.12) × 10−5 cm2/s for the tungsten and liquid bismuth electrodes, respectively. The possible reasons for the observed discrepancy in the diffusion coefficients of Co(II) obtained from the two different electrodes were discussed.

Application of group method of data handling and gene expression programming to modeling molecular diffusivity of CO2 in heavy crudes

Successful enhancement of heavy oil and bitumen production using CO2-based enhanced oil recovery (EOR) techniques requires extensive knowledge about the diffusivity of CO2 in heavy crudes. In this work, two advanced correlative approaches, namely group method of data handling (GMDH) and gene expression programming (GEP), were utilized to establish simple-to-use mathematical correlations by applying a comprehensive dataset including 260 laboratory data of CO2 diffusion coefficient (DC) in heavy crudes and taking into account all the parameters affecting the accuracy of the models. Moreover, the response surface and contour plots were analyzed to obtain the desired response values and operating conditions. The GMDH correlation represented more reliable results with better statistical criteria including average absolute percentage error (AAPRE) values of 7.47%, 7.83%, and 7.54% for training, testing, and the total sets, respectively. Also, the results showed that the increase in pressure and/or temperature caused an increment in the amount of diffusivity of CO2 in heavy crudes; and the maximum amount of CO2 DC was obtained at the upper limit of these operational parameters. At a given temperature and pressure, it appears that the highest CO2 DC in heavy crudes was obtained when the CO2 mass fraction was less than 0.02. Furthermore, the Pearson and Spearman correlation coefficients were used to investigate linear and non-linear relationships between input variables and the responses of GMDH and GEP correlations. The mass fraction of CO2, temperature, pressure, and temperature_PVT had a direct relationship, and on the other hand, the viscosity and density of crudes had a reverse relationship with CO2 DC. Finally, the reliability of the data bank of CO2 DC in heavy crudes along with the high validity of GMDH and GEP correlations was verified by the leverage technique. Notably, no out-of-leverage data were identified, with only seven and five data points considered as suspected for GMDH and GEP models, respectively.

Enhanced oil recovery via dissolution of low molecular weight PDMS in CO2 during immiscible gas injection in matrix-fracture system

Oil recovery in natural fracture reservoirs can be improved by reducing the capillary force during the gravity drainage process in matrix-fracture system. In the current study, a modified gas was generated via dissolution of low molecular weight poly(dimethyl siloxane) (PDMS, average Mw 3780 g/mol, 10000 – 50000 ppm) in CO2 to enhance oil recovery at 50 °C or 70 °C and 3000 psi. Cloud point measurements indicated that PDMS dissolved in CO2 at pressures less than 3000 psi, which was below the minimum miscibility pressure (MMP) of ∼3600 psi at 70 °C determined with the vanishing interfacial technique. The solution density increased from 669.6 kg/m3 for pure CO2 to 780.3 kg/m3 for CO2/PDMS (50000 ppm) at 70 °C and 3000 psi, thereby reducing the density difference between the CO2-rich fluid and crude oil (ρo=865.2 kg/m3) in matrix-fracture system. Also, CO2-oil interfacial tension (IFT) was reduced from 65 to 15 dyn/cm via the dissolution of 50000 ppm PDMS in CO2. Therefore, it led to the CO2 diffusion coefficient increased in both reservoir-fluid saturated porous media and bulk oil scenarios 3–4 fold and 4–7 fold respectively in comparison to pure CO2 injection. These PDMS-induced changes reduced the capillary effects in gas-invaded zone, which consequently led to an increase in oil recovery of 25% points (from 31% to 56%) compared to pure CO2 injection in the case of capillary continuity during gravity drainage tests. For the field-scale, because the PDMS can dissolve in CO2 at pressures and temperatures which are commensurate with CO2 EOR, it is a promising CO2-philic chemical for increasing CO2 density and improving CO2 diffusion coefficient in gas invaded zone compared to conventional CO2 injection.

Calculating diffusion coefficients from molecular dynamics simulations for modelling foam processes of polypropylene: Investigating different process conditions and blowing agents

The choice of blowing agent is very important in foaming processes. In an earlier work the use of molecular dynamics simulations for the estimation of the diffusion coefficients of different blowing agents was discussed at elevated temperatures above the melting point. Therein it was shown that these simulations can give valuable information on blowing agent diffusion in polypropylene. The aim of the recent work is to expand this discussion to the simulation of different influences like pressure, blowing agent mixtures and blowing agents with higher molecular weight at temperatures above the melting point of PP. First a pressure range applied on the combined system of polymer and blowing agent, reasonable for the foam processing is discussed and their influence on the diffusion coefficients for CO2 in polypropylene is evaluated via MD simulations. The next step is the investigation of the influence of mixing a blowing agent with a co-blowing agent. The last part is the presentation of diffusion coefficients for different organic solvents, namely 2-propanol, acetone, ethyl acetate and butyl acetate which could be used as potential co-blowing agents. For both, the change in pressure and the mixing of blowing agents for the systems in question only small influences on the diffusion coefficients was discovered. The results of the diffusion coefficients for the different organic solvents are compared to each other and with former results, considered different molecular structure, size and polarities and are found to be reasonable.

Simulation study on the coupled heat and mass transfer of CO2 in a heavy oil-water liquid system based on an improved lattice Boltzmann (LB) method

This study investigates the heat and mass transfer when low-temperature CO2 diffuses in a heavy oil–water liquid system based on an improved Lattice Boltzmann (LB) method. First, we determine the CO2 diffusion coefficients in heavy oil and water and the heat transfer coefficients of heavy oil and water using the pressure drop (DP) method and the laser flash (LF) method, respectively. Then, a numerical model that couples the heat and mass transfer in the system is established based on the improved LB method. The effect of low-temperature CO2 on the temperature field of the system and the effect of changes in the temperature field on CO2 diffusion are investigated. Finally, we develop a micro-model reproducing the heat and mass transfer of CO2 in water and heavy oil-saturated porous media to validate the accuracy of the numerical model. The results demonstrate that the CO2 diffusion coefficients in heavy oil and water linearly increase with the temperature increases. The heat transfer coefficients of heavy oil and water are insensitive to the changes in temperature. The heat transfer process has a great impact on the mass transfer of CO2 in the liquid system. The CO2 diffusion velocity slows down as the system temperature decreases because of the heat transfer (from 400 K to 300 K), leading to a reduction percentage of 300 % in the CO2 front movement velocity. Compared to the scenarios neglecting heat transfer, CO2 diffusion distance and amount decrease by 38 % and 50 %, respectively because of the changes in the temperature field of the system.

Optimization of Flow-By CO2 Electrolyzers: Impact of Differential Pressure and Gas Diffusion Layer Composition

The electrochemical reduction of CO2 (eCO2R) into valuable chemicals offers a great ecological solution to lower anthropogenic CO2 in the atmosphere, since it can close the carbon cycle by utilizing renewable energy, resulting in a sustainable carbon recycling system. Consequently, it has gathered significant scientific interest over the past decade [1,2]. However, to make significant progress towards making the process industrially feasible, it would be beneficial to replace the typical anodic oxygen evolution reaction at the counter electrode with an economically more interesting one, like alkane dehydrogenation, while at the same time lowering cell potential and increasing energy efficiency. However, this requires the CO2 reduction to operate efficiently at elevated temperatures (up to 100°C) [3]. Unfortunately, little is known on the impact of elevated temperatures on the overall performance of CO2 electrolyzers and its components.In this research, we studied the effect of increasing the temperature on CO2 electrolyzers to ultimately enable selective and stable eCO2R to formic acid not only at room temperature. Heating the system leads to many changes (e.g. decreased electrolyte surface tension, decreased hydrophobicity of the gas diffusion layer (GDL), lower dissolved CO2 content and, increased CO2 diffusion coefficient), all affecting the performance of a conventional CO2 electrolyzer, consequently raising the need for re-evaluating many of its components and their configuration, considering they have been optimized for operation at ambient conditions. Specifically, we focused on the three-phase boundary, where the eCO2R reaction actually takes place. Logically, it is important that this boundary is at the exact location of the catalyst layer (CL), as the catalyst is the active species towards the desired reaction. To this end, GDLs are specifically designed to align this boundary to the right location through variations in hydrophobic additives, thickness, porosity, etc. However, we have found that all these efforts to perfect the GDL's properties can be forfeited if the differential pressure across it were to change as it shifts the three-phase boundary. A shift inwards the GDL will result in a flooded CL, lengthening the diffusion path of the gaseous CO2 in the electrolyte to the active sites of the CL resulting in increased hydrogen evolution. A shift outward the GDL will result in a CL that is not fully used, as such lowering the activity. Since the CL is a thin layer, it can be easily understood that the margin within which the boundary can shift without becoming catastrophic for the overall performance is very small, making it extremely critical to have precise control over its position. Changing the temperature of the system will affect the location of the boundary layer and by optimizing the differential pressure we can shift its location back to its optimal position and increase the performance of the CO2 electrolyzer.We investigated the influence of deliberately altering the differential pressure across a GDE in a flow-by electrolyzer with Bi2O3 nanoparticles for the eCO2R towards formate, at different temperatures. At higher temperatures (i.e. 85°C), flooding was a pronounced problem, which resulted in a rapid decrease of performance, and after 24 hours of electrolysis only a 40% faradaic efficiency towards formate (FEHCOOH) was maintained from the initial 70%. We discovered that by increasing the differential pressure, by elevating the backpressure at the gas side, we could limit flooding of the GDE. By mitigating the flooding, the system was able to maintain a better performance, i.e. FEHCOOH of 65% after 24 hours of electrolysis was maintained, which is a 1.6 factor increase (Figure). The present findings confirm that, without altering any of the more significant electrochemical aspects of the electrolyzer, it is possible to increase performance by solely varying the differential pressure over the GDE, showing the importance of also optimizing the operational conditions.Once the optimal differential pressure of the system was established, it was still necessary to investigate the GDE structure itself. Indeed, the GDE should be designed to appropriately mediate all transport processes necessary to achieve high eCO2R performance and further reduce flooding phenomena, by favourably affecting CO2 transport, local pH and water transport [4]. Therefore, the next step was to investigate and compare other commercially available GDLs. For this research we selected commercially available GDLs that are primarily used in high-temperature proton exchange fuel cells, since their required characteristics (hydrophobicity, thickness and pore structure) are similar to the needs of our system.By re-evaluating and optimizing these (operational) conditions, we are getting closer to making the electrochemical CO2 reduction efficient, also at elevated temperatures.[1] https://doi.org/10.1016/j.petlm.2016.11.003[2] https://doi.org/10.1016/j.joule.2017.09.003[3] https://doi.org/10.1002.celc.201900872[4] https://doi.org/10.1038/s41578-021-00356-2 Figure 1

Effect of metal ion intercalation on the gas diffusion confined in two-dimensional MXene nanosheets

Designing and regulating the metal ion adsorption sites is an effective strategy to improve the gas separation performance of porous materials. The diffusion behavior of gas molecules (H2, H2O, CO2, N2, CH4, SO2 and COS) confined in ion intercalated (Li+, Na+, K+, Rb+, Cs+, Mg2+ and Al3+) MXene nanoslits was studied by molecular dynamics method. The results showed that, due to the increase of steric hindrance after ion intercalation, the diffusion of gas molecules in confined nanoslits is subject to varying degrees of restriction. The diffusion coefficients of CO2, SO2 and COS, which interact strongly with metal ions, are significantly reduced, thus significantly improving the diffusion selectivity between these molecules and weakly interacting molecules (H2, N2 and CH4). In particular, Al3+, which has a high charge number and a small ionic radius, has a significant effect on improving the diffusion selectivity of mixed gases. The effect of metal ion intercalated MXene on the selectivity of the gas mixture is the result of the synergistic effect of adsorption and steric hindrance.

Insights into adsorption and diffusion of CO2, CH4 and their mixture in MIL-101(Cr) via molecular simulation

An in-depth comprehension of the adsorption and diffusion properties of CH4, CO2, and their mixture in MIL-101(Cr) is crucial for its application in the highly selective separation of CO2 and CH4 mixtures in biogas. Existing studies often overlook the influence of gas molecular radius and MIL-101 topological structure on adsorption and lack quantitative analysis of the primary and secondary adsorption sites of MIL-101. Additionally, there is a significant gap in research on the adsorption mechanism of gas mixtures. To address these gaps and to provide new knowledge, this study employs Monte Carlo and molecular dynamics simulations to evaluate various factors such as CH4 and CO2 adsorption isotherms, density distribution profiles, self-diffusion coefficients, radial distribution functions (RDF), and CO2/CH4 selectivity within MIL-101 metal-organic framework (MOF). The insightful and comprehensive atomic-level study reveals several unique and new findings, include 1) the RDF analysis shows that the C = C double bond of the benzene ring within MIL-101 primarily governs the adsorption of CH4, while the open metal center (Cr) exhibits significant adsorption effects on CO2; 2) the density distribution profile analysis indicates that CH4 molecules tend to localize in the larger and medium-sized cages, whereas CO2 molecules exhibit relatively uniform distribution. 3) evaluation of self-diffusivity coefficients and diffusion activation energies demonstrated that CH4 diffuses more easily than CO2, and in the CO2 and CH4 two-component gas, the existence of CH4 can further reduce the diffusion coefficient of CO2. This investigation provides a microscopic understanding of adsorption and diffusion phenomena within MIL-101, contributing to the overall comprehension of its behavior in gas separation applications.

Amino acid ionic liquids as efficient catalysts for CO2 capture: A combined static and dynamic approach

Amino acid ionic liquids (AAILs) have gained significant attention as green solvents that are biocompatible, biodegradable, and useful in various applications, including catalysts, absorbents, and solvents. This study investigates the detailed interactions of three amino acid anions (glycine [Gly]-, histidine [His]-, and arginine [Arg]-) with the cation 1-methoxylbutyl-3-methylimidazolium [MOBMIM]+ and their role in CO2 absorption using quantum mechanical calculations and molecular dynamics (MD) simulations. The Density Functional Theory (DFT) calculations elucidate the reaction mechanisms underlying CO2 absorption and cycloaddition, and facilitate a comparative analysis of the impact of different amino acids on these reactions, and the synergies between them. Notably, arginine displays superior CO2 absorption capacity in comparison to glycine and histidine. Additionally, the cycloaddition reaction with CO2 exhibits a lower energy barrier when arginine is involved. Insights from the MD simulations highlight the higher level of electrostatic interaction between [MOBMIM]+[Arg]- and CO2, relative to the other studied molecules. Moreover, the Lennard Jones interaction emerges as the dominant type of interaction in these systems. The diffusion coefficient for CO2 was highest when interacting with [MOBMIM]+[Gly]-, followed by [MOBMIM]+[Arg]-. Consequently, both MD and DFT investigations converge to suggest that [MOBMIM]+[Arg]- followed by [MOBMIM]+[Gly]- may serve as advantageous choices for CO2 fixation and cycloaddition. The findings from this study underscore the considerable potential of the investigated AAILs as materials conducive to CO2 capture and utilization, thus paving the way for the integration of CO2 capture into valuable chemical products.

Effect of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes on Structure-Property Relationships of Thermostable Hybrid Cyanate Ester Resin Based Nanocomposites.

Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of the CER matrix by 12-15 °C, depending on the type of amino-POSS. A significant increase of the glass transition temperature, Tg (DSC data), and the temperature of α relaxation, Tα (DMTA data), by 45-55 °C of the CER matrix with loading of nanofillers was evidenced. CER/POSS films exhibited a higher storage modulus than that of neat CER in the temperature range investigated. It was evidenced that CER/aminopropylisobutyl (APIB)-POSS, CER/N-phenylaminopropyl (NPAP)-POSS, and CER/aminoethyl aminopropylisobutyl (AEAPIB)-POSS nanocomposites induced a more homogenous α relaxation phenomenon with higher Tα values and an enhanced nanocomposite elastic behavior. The value of the storage modulus, E', at 25 °C increased from 2.72 GPa for the pure CER matrix to 2.99-3.24 GPa for the nanocomposites with amino-functionalized POSS nanoparticles. Furthermore, CER/amino-POSS nanocomposites possessed a higher specific surface area, gas permeability (CO2, He), and diffusion coefficients (CO2) values than those for neat CER, due to an increasing free volume of the nanocomposites studied that is very important for their gas transport properties. Permeability grew by about 2 (He) and 3.5-4 times (CO2), respectively, and the diffusion coefficient of CO2 increased approximately twice for CER/amino-POSS nanocomposites in comparison with the neat CER network. The efficiency of amino-functionalized POSS in improving the thermal and transport properties of the CER/amino-POSS nanocomposites increased in a raw of reactive POSS containing one primary (APIB-POSS) < eight secondary (NPAP-POSS) < one secondary and one primary (AEAPIB-POSS) amino groups. APIB-POSS had the least strongly pronounced effect, since it could form covalent bonds with the CER network only by a reaction of one -NH2 group, while AEAPIB-POSS displayed the most highly marked effect, since it could easily be incorporated into the CER network via a reaction of -NH2 and -NH- groups with -O-C≡N groups from CER.

Controlling Microstructure-Transport Interplay in Poly(ether-block-amide) Multiblock Copolymer Gas Separation Membranes.

In this study, we investigated the effect of morphology on the gas-transport properties of a poly(ether-block-amide) (PEBA) multiblock copolymer. We annealed the copolymer samples and varied the annealing temperature to evaluate the influence of changes in the microstructure on the gas transport properties of PEBA. In addition, we used time-resolved attenuated total reflection Fourier transform infrared spectroscopy to evaluate the diffusion coefficient of CO2 in PEBA based on the Fickian model. The effect of the annealing temperature on the microphase-separated structure of the multiblock copolymer is discussed in detail. Furthermore, the gas diffusivity was significantly affected by the purity of the soft domains. The annealed sample demonstrated a 38% increase in CO2 permeability while maintaining a high CO2/N2 permselectivity of approximately 53. The findings of this study provide valuable insight into the design and optimization of PEBA membranes for gas separation applications.

Carbonation of a Synthetic CAF Compound by CO2 Absorption and Its Effect on Cement Matrix

In the field of construction materials, the development of fundamental technologies to reduce energy consumption and CO2 emissions, such as manufacturing process improvement and the expanded use of alternative materials, is required. Technologies for effectively reducing energy consumption and improving CO2 absorption and reduction that can meet domestic greenhouse gas reduction targets are also required. In this study, calcium–aluminate–ferrite (CAF), a ternary system of CaO·Al2O3·Fe2O3, was sintered at a low temperature (1100 °C) to examine the possibility of CO2 adsorption, and excellent CO2 absorption performance was confirmed, as the calcite content was found to be 11.01% after 3 h of the reaction between synthetic CAF (SCAF) and CO2. In addition, the physical and carbonation characteristics were investigated with respect to the SCAF substitution rate for cement (10%, 30%, 50%, 70%, and 100%). It was found that SCAF 10% developed a compressive strength similar to that of ordinary Portland cement (OPC 100%), but the compressive strength tended to decrease as the SCAF substitution rate increased. An increase in the SCAF substitution rate led to the rapid penetration of CO2, and carbonation was observed in all the specimens after 7 days. As carbonation time increased, the CO2 diffusion coefficient tended to decrease. This is because the diffusion of CO2 in the cement matrix follows the semi-infinite model of Fick’s second law. SCAF can contribute to reduced energy consumption and CO2 emissions because of the low-temperature sintering and can absorb and fix CO2 when a certain amount is substituted.

Engineering design of direct‐air‐capture contactors composed of sorbent particles using numerical simulations

AbstractWe study the transport of CO2 molecules inside direct‐air‐capture (DAC) contactors made of packed beds of solid‐sorbent‐particles separated by airgaps using numerical solution of the convection‐diffusion and first‐order adsorption kinetics equations. We quantify an apparent slowdown in the CO2 uptake in such contactors relative to the CO2 uptake of a high‐capacity sorbent particle making the bed. We derive two naturally occurring length‐scales associated with the adsorption process: (1) thickness of the sorbent related to the sorbent chemistry (capacity and adsorption rate constants), packing density, and diffusion coefficient of CO2 inside bed; and (2) extent of the bed in the air‐flow direction related to convective air‐flow velocity, sorbent chemistry, packed bed thickness, and packing density. DAC designs that have a bed thickness of O() and streamwise extent O() are shown to have faster CO2 uptake and more economical capture costs ($/ton‐CO2) compared with designs further away from this design set‐point. Our work should provide guidance to engineering design of DAC contactors with packed bed sorbents and related porous materials.

CO2 diffusion in shale oil based on molecular simulation and pore network model

Field practices show that CO2 huff and puff can effectively promote the exploitation of shale resources, and CO2 diffusion is noteworthy as a crucial mechanism of enhanced oil recovery (EOR). Understanding the confinement effect on CO2 diffusion is imperative to accurately characterize the fluid transport in shale nanopores and further upscaling. We integrate molecular simulation and pore network model (PNM) to study CO2 diffusion behavior at the nanoscale and pore scale. We first explored CO2 diffusion into heptane in kerogen and calcite pores using molecular dynamics, and analyzed the impacts of pore size, molar fraction, temperature, and pore pressure on the confined Fick diffusion. Based on the molecular simulation results, a model characterizing the ratio of the confined diffusion coefficient to that of the bulk phase is constructed for further upscaling. Based on the PNM containing organic and inorganic pores, we established a model to simulate the CO2 diffusion at the pore scale by introducing the characterization model at the nanoscale into the convective diffusion equation. Considering the microscale effects and the influence of CO2 concentration on diffusion is beneficial to improve the simulation accuracy at the pore scale. The estimated CO2 diffusion coefficients are in good agreement with the experimental results. This work provides better insight into CO2 diffusion behavior in shale oil, which can afford effective support for industrial exploitation and the breakthrough of the technical bottleneck of shale oil production.

Effect of Graphene Oxide-Modified CaAl-Layered Double Hydroxides on the Carbon Dioxide Permeation Properties of Fluoroelastomers.

This work aimed to investigate the CO2 gas barrier and mechanical properties of fluorine rubber nanocomposites filled with Ca/Al layered hydroxide (graphene oxide [GO]/LDH-Ca2Al) modified by GO. GO/LDH-Ca2Al nanocomposite fillers were prepared by depositing Ca/Al layered hydroxide (LDH-Ca2Al) into the surface of alkalized GO (Al-GO). The prepared GO/LDH-Ca2Al nanocomposite fillers and complexes were characterized by Fourier infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) for structural and micromorphological characterization. The results showed that GO/LDH-Ca2Al was successfully prepared with strong interactions between Al-GO and LDH, and the compatibility of GO/LDH-Ca2Al nanocomposite fillers with the polymer was significantly improved compared with that of LDH-Ca2Al. Consequently, both the fracture strength (σb) and strain (εb) of GO/LDH-Ca2Al nanocomplexes remarkably increased, and they exhibited excellent mechanical properties. Differential scanning calorimetry and thermogravimetric analysis were used to characterize the thermal stability of GO/LDH-Ca2Al nanocomposite fillers, and GO/LDH-Ca2Al nanocomposite fillers have better thermal stability than LDH-Ca2Al. The reaction products (S-LDH-Ca2Al and S-GO-Ca2Al) of LDH-Ca2Al and GO/LDH-Ca2Al with CO2 were characterized using XRD and TGA, respectively, and the results show that LDH-Ca2Al reacts readily and chemically with CO2, resulting in a lower diffusion coefficient of CO2 in the LDH-Ca2Al nanocomplexes than that of the GO/LDH-Ca2Al nanocomplexes and leading to the destruction of the laminar structure of LDH-Ca2Al, while GO/LDH-Ca2Al has better CO2 resistance stability. GO/LDH-Ca2Al nanocomplexes exhibited a reduced content of hydroxyl groups with pro-CO2 nature exposed on the surface of LDH-Ca2Al, improving the interfacial interaction between the nanofillers and the rubber matrix and enhancing the dispersion of GO/LDH-Ca2Al in the polymers. Moreover, CO2 in the soluble GO/LDH-Ca2Al nanocomposites was significantly reduced, while the diffusion properties demonstrated weak temperature dependence on solubility. The mechanism of the CO2 gas barrier of polymers filled with GO/LDH-Ca2Al was proposed on the basis of the Arrhenius equation.

Copolyimide Brushes as a Component of a Hybrid Poly(phenylene Oxide) Membrane for Controlling Gas Separation: Effect of Water, Methanol, and Hexane Vapors.

The effect of water, methanol, and hexane vapors on gas permeability was studied in a hybrid membrane containing 5 wt% copolyimide brushes with poly(methyl methacrylate) side chains (PI-g-PMMA) in a poly(phenylene oxide) (PPO) matrix, and in a pristine PPO membrane. These membranes in the form of dense nonporous films were further examined by atomic force microscopy (AFM) and scanning electron microscopy (SEM), as well as by measuring their mechanical and gas transport properties. A gas separation study of the membranes in a dry state and the membranes saturated with water, methanol, and hexane vapors was performed to estimate the effect of each vapor on the H2, CO2, N2 permeability and selectivity in the separation of H2/N2 and CO2/N2 pairs. In general, saturation with water, methanol, and hexane vapors caused a decrease in the gas permeability of both membranes. The hybrid membrane containing copolyimide brushes demonstrated enhanced selectivity in the separation of H2/N2 and CO2/N2 pairs. It was found that a special effect of the vapors used for membrane saturation is associated with their molar volume. The solubility and diffusion coefficients of N2 and CO2 were obtained by Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations.

PEI@MOFs thin film nanocomposite (TFN) membrane for efficient CO2 separation

Polyetherimide (PEI) membrane exhibits high CO2 selectivity while suffer from low permeance thus limiting the further application in CO2 separation. Thin film nanocomposite (TFN) membrane which contains a thin selective functional layer with nanomaterials porous fillers is a new class of high-performance membranes. In this work, a series of novel PEI@MOFs TFN membranes were prepared for efficient CO2 separation. The sub-micro scale PEI layers (about 400 nm) with four kinds of MOFs fillers including 3-dimensional MOFs nanoparticles (UiO-66 and MIL-101 (Cr)) and MOFs nanosheets (2-D CuBDC and Zn2(bim)4) were prepared by a simple spin-coating strategy. The properties and CO2 separation performance of the TFN membranes were further studied. The MOFs in PEI increased the diffusion coefficient and selectivity for CO2, at the same time, the ultra-thin functional layer maximized reducing the CO2 transport resistance. As a result, the PEI@MOFs TFN membranes exhibited high CO2 permeance as well as enhanced CO2 separation performance which close to the Robeson upper bound. The PEI@CuBDC TFN membrane exhibited CO2 permeance of 15.6 GPU (3.3 times higher than the neat PEI membrane), and the selectivity of CO2/CH4 reached 39.8 (2.2 times higher than the neat PEI membrane). In addition, the PEI@MOFs TFN membranes showed good thermal and operation stability.

Diffusion model of gas hydrate formation from ice considering the gas pressure drop

A kinetic model of the process of gas hydrate formation from ice that considers the gas pressure drop caused by this process is presented. This model is based on the diffusion equation. The issues during the formation of gas hydrate from ice powder and that from a flat ice layer are considered separately. For each of these problems, a solution in the framework of a quasi-stationary approximation is obtained, allowing for the calculation of the gas pressure drop in the gas phase. The calculated data are compared with available experimental data on the kinetics of CO2 hydrate formation from pure ice powder and ice powder with the addition of sodium dodecyl sulfate (SDS) at a mass concentration of 240 ppm: the calculated and experimental curves of CO2 pressure drop are compared with each other. From this comparison, the values of the diffusion coefficient of CO2 through a layer of CO2 hydrate formed from pure ice and ice with the addition of SDS at a mass concentration of 240 ppm were determined. Based on these values, it was found that SDS molecules present in the gas hydrate affect the rate of gas diffusion through the gas hydrate layer.

Molecular dynamics simulation of CO2 dissolution-diffusion in multi-component crude oil

In order to study the dissolution-diffusion process and mechanism of CO2 in multi-component crude oil, a model of multi-component crude oil system with octane as the main component and 16 other alkanes as a compound was constructed by using molecular dynamics simulation method. We estimated the CO2 density distribution in crude oil model and the shift in crude oil model volume change. We then investigated the microscopic influence mechanism of CO2 dissolution-diffusion on the volume expansion of crude oil by simulating the action of CO2 dissolution-diffusion in the multi-component crude oil model. Based on the variation law of mean square displacement between crude oil molecules, the dissolution and diffusion coefficients of CO2 were predicted, and the influence of CO2 dissolution-diffusion on crude oil mobility was analyzed. It is found that temperature intensifies the molecular thermal motion and increases the voids between alkane molecules, which promotes the dissolution of CO2 and encourages CO2 molecules to transmit, making the crude oil expand and viscosity decrease, and improving the flow ability of crude oil; with the enhancement of given pressure, the potential energy difference between the inside and outside of the crude oil model becomes larger, and the voids between alkane molecules become larger, which is favorable to the dissolution of CO2. Nevertheless, the action of CO2 molecules’ diffusing in the crude oil sample is significantly limited or even tends to zero, besides, the mobility of crude oil is affected due to the advance of external pressure. The mechanism of CO2 dissolution and diffusion in multi-component crude oil is revealed at the microscopic level, and provides theoretical guidance for the development of CO2 flooding.

CO2 diffusive characteristics and influencing factors in the porous medium with saturated polyacrylamide solutions

Polyacrylamide has been widely utilized to store CO2 in reservoirs in order to alleviate the greenhouse impact. However, no studies have been conducted on the motion of CO2 in a polyacrylamide solution within porous media. This study illustrates the effect of polyacrylamide molecular weight, concentration, pressure, temperature, and pore size on the dynamic diffusion of CO2 in the core with saturated polyacrylamide solutions. The diffusion motion characteristics of CO2 were obtained by diffusion experiments. The microscopic analysis of core slices following testing showed the presence of polyacrylamide on rock particles. The pressure and CO2 mass fraction distribution inside the core were calculated by constructing a mathematical model. The results show that the increase in molecular weight and concentration of polyacrylamide decreased the diffusion ability of CO2, while temperature and pressure accelerated the diffusion of CO2. The polyacrylamide moved into the core to form an effective inhibiting effect, which was affected by CO2 and pressure. While the increase in pore size accelerates the flow rate of the polyacrylamide, it also enhances the sealing capacity of the polyacrylamide solution. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) showed that the core had a high content of polyacrylamide solution inside it, and these molecules were attached to the surface of the core particles in an irregular lamellar pattern. The calculation model was consistent with the diffusion experimental results, where the CO2 diffusion coefficient in the polyacrylamide solution was in the order of 10-12 m2/s under the conditions of 5–30 MPa, 323–343 K, and a core permeability of 60 × 10-3 μm2. The results of this paper provide a new calculation for evaluating the performance of polymer plugging.