A molecular simulation study on amine-functionalized silica/polysulfone mixed matrix membrane for mixed gas separation.

Polysulfone (PSF) based mixed matrix membranes (MMMs) are one of the most broadly studied polymeric materials used for CO2/CH4 separation. The performance of existing PSF membranes encounters a bottleneck for widespread expansion in industrial applications due to the trade-off amongst permeability and selectivity. Membrane performance has been postulated to be enhanced via functionalization of filler at different weight percentages. Nonetheless, the preparation of functionalized MMMs without defects and its empirical study that exhibits improved CO2/CH4 separation performance is challenging at an experimental scale that needs prior knowledge of the compatibility between the filler and polymer. Molecular simulation approaches can be used to explore the effect of functionalization on MMM's gas transport properties at an atomic level without the challenges in the experimental study, however, they have received less scrutiny to date. In addition, most of the research has focused on pure gas studies while mixed gas transport properties that reflect real separation in functionalized silica/PSF MMMs are scarcely available. In this work, a molecular simulation computational framework has been developed to investigate the structural, physical properties and gas transport behavior of amine-functionalized silica/PSF-based MMMs. The effect of varying weight percentages (i.e., 15-30 wt.%) of amine-functionalized silica and gas concentrations (i.e., 30% CH4/CO2, 50% CH4/CO2, and 70% CH4/CO2) on physical and gas transport characteristics in amine-functionalized silica/PSF MMMs at 308.15 K and 1 atm has been investigated. Functionalization of silica nanoparticles was found to increase the diffusion and solubility coefficients, leading to an increase in the percentage enhancement of permeability and selectivity for amine-functionalized silica/PSF MMM by 566% and 56%, respectively, compared to silica/PSF-based MMMs at optimal weight percentage of 20 wt.%. The model's permeability differed by 7.1% under mixed gas conditions. The findings of this study could help to improve real CO2/CH4 separation in the future design and concept of functionalized MMMs using molecular simulation and empirical modeling strategies.

Investigation of transport properties of 6FDA-durene polymeric membrane for landfill gas application using molecular simulation approach.

Gas separation of carbon dioxide (CO2) and methane (CH4) from landfill gas (LFG) is very crucial to be undertaken to treat significant greenhouse gases (GHG) emitted to the atmosphere. Among the well-developed conventional technologies, membrane has drawn a huge attraction from many researchers to leverage on its application, which favors an efficient and environmentally safe process. In membrane technology, inorganic membrane type requires a complex and pricey fabrication process which is contradictory from the polymeric membrane features. The impressive gas permeability and acceptable value of selectivity possessed by polymeric membranes has contributed to its main attractiveness over the other types of membranes available. Besides, the frequent approach used which is through experimental methods requires complicated procedures and possess high difficulty to obtain a defect-free membrane sample. In this work, 6FDA-durene has been investigated by employing a molecular simulation approach to further examine its fractional free volume within the membrane matrix and transport properties. The structure creation of complete framework and the analysis of project deliverables has been adopted through a molecular dynamic simulation in Materials Studio software. FFV value obtained based on the simulated framework is 0.1743 which establishes about 3.15% deviation to the published experimental works. Upon the increment of operating temperature, most of the gasses would be in their activation condition and possess higher gas diffusivities and permeabilities. However, with increasing operating pressure simulation, the membrane framework was compressed and reached its asymptotic limit at 7 atm which acts as a maximum point when the membrane system becomes saturated. In both cases, the selectivity of CO2/CH4 gas pairs are validated with low percentage deviation (less than 10%) towards the reported experimental works hence affirms the reliability of results and methodology conducted.

A systematic review of the molecular simulation of hybrid membranes for performance enhancements and contaminant removals.

Number of research on molecular simulation and design has emerged recently but there is currently a lack of review to present these studies in an organized manner to highlight the advances and feasibility. This paper aims to review the development, structural, physical properties and separation performance of hybrid membranes using molecular simulation approach. The hybrid membranes under review include ionic liquid membrane, mixed matrix membrane, and functionalized hybrid membrane for understanding of the transport mechanism of molecules through the different structures. The understanding of molecular interactions, and alteration of pore sizes and transport channels at atomistic level post incorporation of different components in hybrid membranes posing impact to the selective transport of desired molecules are also covered. Incorporation of molecular simulation of hybrid membrane in related fields such as carbon dioxide (CO2) removal, wastewater treatment, and desalination are also reviewed. Despite the limitations of current molecular simulation methodologies, i.e., not being able to simulate the membrane operation at the actual macroscale in processing plants, it is still able to demonstrate promising results in capturing molecule behaviours of penetrants and membranes at full atomic details with acceptable separation performance accuracy. From the review, it was found that the best performing ionic liquid membrane, mixed matrix membrane and functionalized hybrid membrane can enhance the performance of pristine membrane by 4 folds, 2.9 folds and 3.3 folds, respectively. The future prospects of molecular simulation in hybrid membranes are also presented. This review could provide understanding to the current advancement of molecular simulation approach in hybrid membranes separation. This could also provide a guideline to apply molecular simulation in the related sectors.

Enrichment of biogas through composite membrane of PEBA-1657/ hierarchical T-type zeolite.

Presently, composite membranes emerged as a promising approach to overcome the limitations of polymeric and inorganic membranes particularly in acid gas separation. In the present work, composites membranes were fabricated by combining hierarchical T-Type (h-zeolite T) zeolite and PEBA-1657 at different filler composition that ranging from 5 wt% - 30 wt% for the CO2/CH4 separation. The physicochemical properties of the resultant inorganic filler and membranes were investigated by using Brunauer-Emmett- Teller (BET), field emission scanning electron microscopy (FESEM), Fourier Transform infra-red (FTIR), x-ray diffraction (XRD), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). FESEM and EDX analysis revealed that the formation of voids and agglomeration of particles is pronounced as the fillers loading was increased up to 30 wt%. The single gas permeation test demonstrated that amalgamation of h-zeolite T particles into PEBA-1657 has resulted in the improvement of CO2 permeability up to 122% and CO2/CH4 selectivity up to 31%. Hybrid membrane encapsulated with 25 wt% of h-zeolite T displayed a maximum separation efficiency with the highest CO2 permeability of 164.83 Barrer and CO2/CH4 selectivity of 19.37. However, further increment of fillers composition up to 30 wt% resulted in a sharp reduction of CO2/CH4 selectivity to 15.80 due to the particles sedimentation and agglomeration. Overall, the favorable gas transport behavior of PEBA-1657/h-zeolite T composite membrane indicates its promising prospect for CO2/CH4 separation especially in biogas and natural gas purification application. Future research efforts are directed on the optimization of the fabrication parameters and performance investigation at different operating condition to further enhance the CO2 separation and extend its operability under various environment.

RSM Modeling and Optimization of CO2 Separation from High CO2 Feed Concentration over Functionalized Membrane.

The challenges in developing high CO2 gas fields are governed by several factors such as reservoir condition, feed gas composition, operational pressure and temperature, and selection of appropriate technologies for bulk CO2 separation. Thus, in this work, we report an optimization study on the separation of CO2 from CH4 at high CO2 feed concentration over a functionalized mixed matrix membrane using a statistical tool, response surface methodology (RSM) statistical coupled with central composite design (CCD). The functionalized mixed matrix membrane containing NH2-MIL-125 (Ti) and 6FDA-durene, fabricated in our previous study, was used to perform the separation performance under three operational parameters, namely, feed pressure, temperature, and CO2 feed concentration, ranging from 3.5-12.5 bar, 30.0-50.0 °C and 15-70 mol%, respectively. The CO2 permeability and CO2/CH4 separation factor obtained from the experimental work were varied from 293.2-794.4 Barrer and 5.3-13.0, respectively. In addition, the optimum operational parameters were found at a feed pressure of 12.5 bar, a temperature of 34.7 °C, and a CO2 feed concentration of 70 mol%, which yielded the highest CO2 permeability of 609.3 Barrer and a CO2/CH4 separation factor of 11.6. The average errors between the experimental data and data predicted by the model for CO2 permeability and CO2/CH4 separation factor were 5.1% and 3.3%, respectively, confirming the validity of the proposed model. Overall, the findings of this work provide insights into the future utilization of NH2-MIL-125 (Ti)/6FDA-based mixed matrix membranes in real natural gas purification applications.

Performance of Multilayer Composite Hollow Membrane in Separation of CO2 from CH4 in Mixed Gas Conditions.

Composite membranes comprising NH2-MIL-125(Ti)/PEBAX coated on PDMS/PSf were prepared in this work, and their gas separation performance for high CO2 feed gas was investigated under various operating circumstances, such as pressure and CO2 concentration, in mixed gas conditions. The functional groups and morphology of the prepared membranes were characterized by Fourier transform infrared spectroscopy (FTIR) and field emission scanning electron microscopy (FESEM). CO2 concentration and feed gas pressure were demonstrated to have a considerable impact on the CO2 and CH4 permeance, as well as the CO2/CH4 mixed gas selectivity of the resultant membrane. As CO2 concentration was raised from 14.5 vol % to 70 vol %, a trade-off between permeance and selectivity was found, as CO2 permeance increased by 136% and CO2/CH4 selectivity reduced by 42.17%. The membrane produced in this work exhibited pressure durability up to 9 bar and adequate gas separation performance at feed gas conditions consisting of high CO2 content.

A Molecular Simulation Study of Silica/Polysulfone Mixed Matrix Membrane for Mixed Gas Separation.

Polysulfone-based mixed matrix membranes (MMMs) incorporated with silica nanoparticles are a new generation material under ongoing research and development for gas separation. However, the attributes of a better-performing MMM cannot be precisely studied under experimental conditions. Thus, it requires an atomistic scale study to elucidate the separation performance of silica/polysulfone MMMs. As most of the research work and empirical models for gas transport properties have been limited to pure gas, a computational framework for molecular simulation is required to study the mixed gas transport properties in silica/polysulfone MMMs to reflect real membrane separation. In this work, Monte Carlo (MC) and molecular dynamics (MD) simulations were employed to study the solubility and diffusivity of CO2/CH4 with varying gas concentrations (i.e., 30% CO2/CH4, 50% CO2/CH4, and 70% CO2/CH4) and silica content (i.e., 15-30 wt.%). The accuracy of the simulated structures was validated with published literature, followed by the study of the gas transport properties at 308.15 K and 1 atm. Simulation results concluded an increase in the free volume with an increasing weight percentage of silica. It was also found that pure gas consistently exhibited higher gas transport properties when compared to mixed gas conditions. The results also showed a competitive gas transport performance for mixed gases, which is more apparent when CO2 increases. In this context, an increment in the permeation was observed for mixed gas with increasing gas concentrations (i.e., 70% CO2/CH4 > 50% CO2/CH4 > 30% CO2/CH4). The diffusivity, solubility, and permeability of the mixed gases were consistently increasing until 25 wt.%, followed by a decrease for 30 wt.% of silica. An empirical model based on a parallel resistance approach was developed by incorporating mathematical formulations for solubility and permeability. The model results were compared with simulation results to quantify the effect of mixed gas transport, which showed an 18% and 15% percentage error for the permeability and solubility, respectively, in comparison to the simulation data. This study provides a basis for future understanding of MMMs using molecular simulations and modeling techniques for mixed gas conditions that demonstrate real membrane separation.

Cellulose acetate-based membranes by interfacial engineering and integration of ZIF-62 glass nanoparticles for CO2 separation.

Composite membranes typically used for gas separation are susceptible to interfacial voids and CO2 plasticization which adversely affects the gas permeation performance. This paper evaluates routes towards the enhancement of CO2 permeation performance and CO2 plasticization resistance of composite membranes using non-stoichiometric ZIF-62 MOF glass and cellulose acetate (CA). Single and mixed gas permeation results, obtained with CO2 and CH4, demonstrate that the presence of ZIF-62 glass in CA polymer enhanced the CO2 permeability and CO2/CH4 ideal selectivity from 15.8 to 84.8 Barrer and 12.2-35.3, respectively. The composite membrane loaded with 8 wt% of ZIF-62 glass showed the highest CO2 permeability and CO2/CH4 ideal selectivity of 84.8 Barrer and 35.3, which were 436.7% and 189.3% higher compared to the pristine CA membrane, respectively. A CO2 plasticization pressure of 26 bar was achieved for the composite membranes, which is 160% higher compared to the pristine CA membranes, at about 10 bar. The mechanisms for the materials stabilization and greater separation performance were attributed to higher pore size (7.3 Å) and significant CO2 adsorption on the unsaturated metal nodes followed by metal cites electrostatic interaction with CO2. These findings confirm the potential of ZIF-62 glass materials as promising materials solutions towards the design of composite membranes for CO2 separation at industrial scale.

WITHDRAWN: Sustainable liquid membrane separation using interfacial engineering of deep eutectic solvent and cellulose acetate.

This article has been withdrawn at the request of the editor. The Publisher apologizes for any inconvenience this may cause. The full Elsevier Policy on Article Withdrawal can be found at https://www.elsevier.com/about/our-business/policies/article-withdrawal.

Biomethane generation from biogas upgrading by means of thin-film composite membrane comprising Linde T and fluorinated polyimide: optimization of fabrication parameters.

Generation of biogas from organic substances is an attractive evolution of energy generation from fossil-based energy supply to renewable resources. In order to exhibit viability in terms of technical execution while being economically feasible, successful purification strategies for biomethane formation must be applicable to industrial gas streams at realistic pressures and temperatures. Membrane-based upgrading technologies have great potential to promote biogas processes because they involve less energy and low maintenance. However, the development of membranes with good polymer-filler contact and minimum defects remains a great challenge. Hitherto, researchers have been making many attempts at developing an established route to fabricate thin-film composite membranes. In the present work, an innovative coupling between Linde T and fluorinated polyimide was employed for biogas upgrading. A facile technique for membrane fabrication was proposed via optimization of the fabrication parameters. The results indicated that composite membrane fabricated with 2 hours of total dispersion duration demonstrated a homogeneous distribution of Linde T particles in the fluorinated polyimide matrix and improved the separation characteristics by up to 172% in upgrading biomethane quality. Thus, the fabricated membrane is feasible to be employed for large-scale and lucrative production with enhanced performance in biogas purification via the feasible fabrication method employed in this work.

Physical property and gas transport studies of ultrathin polysulfone membrane from 298.15 to 328.15 K and 2 to 50 bar: atomistic molecular simulation and empirical modelling.

Elucidation of ultrathin polymeric membrane at the laboratory scale is complicated at different operating conditions due to limitation of instruments to obtain in situ measurement data of membrane physical properties. This is essential since their effects are reversible. In addition, tedious experimental work is required to collect gas transport data at varying operating conditions. Recently, we have proposed a validated Soft Confining Methodology for Ultrathin Films that can be used to simulate ultrathin polysulfone (PSF) membranes upon confinement limited to 308.15 K and 2 bars. In industry application, these ultrathin membranes are operated within 298.15-328.15 K and up to 50 bars. Therefore, our proposed methodology using computational chemistry has been adapted to circumvent limitation in experimental study by simulating ultrathin PSF membranes upon confinement at different operating temperatures (298.15 to 328.15 K) and pressures (2 to 50 bar). The effect of operating parameters towards non-bonded and potential energy, free volume, specific volume and gas transport data (e.g. solubility and diffusivity) for oxygen and nitrogen of the ultrathin films has been simulated and collected using molecular simulation. Our previous empirical equations that have been confined to thickness dependent gas transport properties have been modified to accommodate the effect of operating parameters. The empirical equations are able to provide a good quantitative characterization with R 2 ≥ 0.99 consistently, and are able to be interpolated to predict gas transport properties within the range of operating conditions. The modified empirical model can be utilized in process optimization studies to determine optimal membrane design for typical membrane specifications and operating parameters used in industrial applications.

Tailoring CO2/CH4 Separation Performance of Mixed Matrix Membranes by Using ZIF-8 Particles Functionalized with Different Amine Groups.

CO2 separation from CH4 by using mixed matrix membranes has received great attention due to its higher separation performance compared to neat polymeric membrane. However, Robeson's trade-off between permeability and selectivity still remains a major challenge for mixed matrix membrane in CO2/CH4 separation. In this work, we report the preparation, characterization and CO2/CH4 gas separation properties of mixed matrix membranes containing 6FDA-durene polyimide and ZIF-8 particles functionalized with different types of amine groups. The purpose of introducing amino-functional groups into the filler is to improve the interaction between the filler and polymer, thus enhancing the CO2 /CH4 separation properties. ZIF-8 were functionalized with three differents amino-functional group including 3-(Trimethoxysilyl)propylamine (APTMS), N-[3-(Dimethoxymethylsilyl)propyl ethylenediamine (AAPTMS) and N1-(3-Trimethoxysilylpropyl) diethylenetriamine (AEPTMS). The structural and morphology properties of the resultant membranes were characterized by using different analytical tools. Subsequently, the permeability of CO2 and CH4 gases over the resultant membranes were measured. The results showed that the membrane containing 0.5 wt% AAPTMS-functionalized ZIF-8 in 6FDA- durene polymer matrix displayed highest CO2 permeability of 825 Barrer and CO2/CH4 ideal selectivity of 26.2, which successfully lies on Robeson upper bound limit.

Effect of a Different Number of Amine-Functional Groups on the Gas Sorption and Permeation Behavior of a Hybrid Membrane Comprising of Impregnated Linde T and 4,4'- (Hexafluoroisopropylidene) Diphthalic Anhydride-Derived Polyimide.

The bottleneck of conventional polymeric membranes applied in industry has a tradeoff between permeability and selectivity that deters its widespread expansion. This can be circumvented through a hybrid membrane that utilizes the advantages of inorganic and polymer materials to improve the gas separation performance. The approach can be further enhanced through the incorporation of amine-impregnated fillers that has the potential to minimize defects while simultaneously enhancing gas affinity. An innovative combination between impregnated Linde T with different numbers of amine-functional groups (i.e., monoamine, diamine, and triamine) and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA)-derived polyimide has been elucidated to explore its potential in CO2/CH4 separation. Detailed physical properties (i.e., free volume and glass transition temperature) and gas transport behavior (i.e., solubility, permeability, and diffusivity) of the fabricated membranes have been examined to unveil the effect of different numbers of amine-functional groups in Linde T fillers. It was found that a hybrid membrane impregnated with Linde T using a diamine functional group demonstrated the highest improvement compared to a pristine polyimide with 3.75- and 1.75-fold enhancements in CO2/CH4 selectivities and CO2 permeability, respectively, which successfully lies on the 2008 Robeson's upper bound. The novel coupling of diamine-impregnated Linde T and 6FDA-derived polyimide is a promising candidate for application in large-scale CO2 removal processes.

Finned spacer for efficient membrane fouling control in produced water filtration.

Membrane based technologies are highly reliable for water and wastewater treatment, including for removal of total oil and grease from produced water. However, performances of the pressure driven processes are highly restricted by membrane fouling and the application of traditional air bubbling system is limited by their low shear stress due to poor contacts with the membrane surface. This study develops and assesses a novel finned spacer, placed in between vertical panel, for membrane fouling control in submerged plate-and-frame module system for real produced water filtration. Results show that permeability of the panel is enhanced by 87% from 201 to 381 L/(m2 h bar). The spacer system can be operated in switching mode to accommodate two-sided panel aeration. This leads to panel permeability increment by 22% higher than the conventional vertical system. The mechanisms of finned spacer in encouraging the flow trajectory was proven by visual observation and flow simulation. The fins alter the air bubbles flow trajectory toward the membrane surface to effectively scour-off the foulant. Overall results demonstrate the efficacy of the developed spacer in projecting the air bubble trajectory toward the membrane surface and thus significantly enhances membrane panel productivity.

Rapid-synthesis of zeolite T via sonochemical-assisted hydrothermal growth method.

Sonochemical-assisted method has been identified as one of the potential pre-treatment methods which could reduce the formation duration of zeolite as well as other microporous and mesoporous materials. In the present work, zeolite T was synthesized via sonochemical-assisted pre-treatment prior to hydrothermal growth. The durations for sonochemical-assisted pre-treatment were varied from 30min to 90min. Meanwhile, the hydrothermal growth durations were ranged from 0.5 to 3days. The physicochemical properties of the resulting samples were characterized using XRD, FESEM, FTIR and BET. As verified by XRD, the samples synthesized via hydrothermal growth durations of 1, 2 and 3days and sonochemical-assisted pre-treatment durations of 60min and 90min demonstrated zeolite T structure. The samples which underwent sonochemical-assisted pre-treatment duration of 60min yielded higher crystallinity with negligible change of zeolite T morphology. Overall, the lengthy synthesis duration of zeolite T has been successfully reduced from 7days to 1day by applying sonochemical-assisted pre-treatment of 60min, while synthesis duration of 0.5days via sonochemical-assisted pre-treatment of 60min was not sufficient to produce zeolite T structure.