Two-Dimensional Nanoporous Cross-linked Polymer Networks as Emerging Candidates for Gas Adsorption.

This paper illustrates the gas adsorption properties of newly synthesized nanoporous cross-linked polymer networks (CPNs). All synthesized CPNs possess N-rich functional groups and are used for the utilization of carbon dioxide and methane. Good gas adsorption and selectivities are obtained for all of the samples. Among the materials, HEREON2 outperforms better selectivity for methane separation from nitrogen rather than zeolites, activated carbons, molecular sieves, covalent organic frameworks, and metal-organic frameworks (MOFs). The accessibility of the N-rich functionalities makes these materials potential candidates for the separation of hydrocarbons via increased polarizabilities. High-pressure adsorption experiments showed that the synthesized two-dimensional nanoporous materials also have a high affinity toward carbon dioxide. HEREON2 powders showed an increased experimental CO2/N2 selectivity of ∼25,000 at 50 bar due to the presence of nitrogen groups in the structure. Fourier-transform infrared spectroscopy (FTIR), solid-state NMR, X-ray diffraction, thermogravimetric analysis, energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) were applied for the characterization of the synthesized nanoporous CPNs. The results show a potential new pathway for future CPN membrane development.

Pioneering the preparation of porous PIM-1 membranes for enhanced water vapor flow.

In this study, porous polymers of intrinsic microporosity (PIM-1) membranes were prepared by non-solvent induced phase inversion (NIPS) and investigated for water vapor transport in view of their application in membrane distillation (MD). Due to the lack of high boiling point solvents for PIM-1 that are also water miscible, the mixture of tetrahydrofuran (THF) and N-methyl-2-pyrrolidone (NMP) was found to be optimal for the formation of a membrane with a developed porous system both on the membrane surface and in the bulk. PIM-1 was synthesized by using low and high temperature methods to observe how molecular weight effects the membrane structure. Low molecular weight PIM-1 was produced at low temperatures, while high molecular weight PIM-1 was obtained at high temperatures. Several membranes were prepared, including PM-6, PM-9, and PM-11 from low molecular weight PIM-1, and PM-13 from high molecular weight PIM-1. Scanning electron microscopy (SEM) was used to image the surface and cross-section of different porous PIM-1 membranes. Among all the PIM-1 membranes (PM) obtained, PM-6, PM-9, PM-11 and PM-13 showed the most developed porous structure, while PM-13 showed large voids in the bulk of the membrane. Contact angle measurements showed that all PIM-1 porous membranes are highly hydrophobic. Liquid water flux measurements showed that PM-6, PM-9 and PM-11 showed minimal water fluxes due to small surface pore size, while PM-13 showed a high water flux due to a large surface pore size. Water vapor transport measurements showed high permeance values for all membranes, demonstrating the applicability of the developed membranes for MD. In addition, a thin film composite (TFC) membrane with PIM-1 selective layer was prepared and investigated for water vapor transport to compare with porous PIM-1 membranes. The TFC membrane showed an approximately 4-fold lower vapor permeance than porous membranes. Based on these results, we postulated that the use of porous PIM-1 membranes could be promising for MD due to their hydrophobic nature and the fact that the porous membranes allow vapor permeability through the membrane but not liquid water. The TFC membrane can be used in cases where the transfer of water-soluble contaminants must be absolutely avoided.

Permeance of Condensable Gases in Rubbery Polymer Membranes at High Pressure.

The gas transport properties of thin film composite membranes (TFCMs) with selective layers of PolyActive™, polydimethylsiloxane (PDMS), and polyoctylmethylsiloxane (POMS) were investigated over a range of temperatures (10-34 °C; temperature increments of 2 °C) and pressures (1-65 bar abs; 38 pressure increments). The variation in the feed pressure of condensable gases CO2 and C2H6 enabled the observation of peaks of permeance in dependence on the feed pressure and temperature. For PDMS and POMS, the permeance peak was reproduced at the same feed gas activity as when the feed temperature was changed. PolyActive™ TFCM showed a more complex behaviour, most probably due to a higher CO2 affinity towards the poly(ethylene glycol) domains of this block copolymer. A significant decrease in the permeate temperature associated with the Joule-Thomson effect was observed for all TFCMs. The stepwise permeance drop was observed at a feed gas activity of p/po ≥ 1, clearly indicating that a penetrant transfer through the selective layer occurs only according to the conditions on the feed side of the membrane. The permeate side gas temperature has no influence on the state of the selective layer or penetrant diffusing through it. The most likely cause of the observed TFCM behaviour is capillary condensation of the penetrant in the swollen selective layer material, which can be provoked by the clustering of penetrant molecules.

Effect of Immobilization of Phenolic Antioxidant on Thermo-Oxidative Stability and Aging of Poly(1-trimethylsilyl-1-propyne) in View of Membrane Application.

The effect of phenolic antioxidant Irganox 1076 on the structure and gas permeation behavior of poly(1-trimethylsilyl-1-propyne) (PTMSP) was investigated. Isotropic films as well as thin film composite membranes (TFCM) from pure PTMSP and with added antioxidant (0.02 wt%) were prepared. PTMSP with antioxidant has a significantly higher thermal degradation stability in comparison to pure polymer. The thermal annealing of isotropic films of PTMSP with antioxidant was carried out at 140 °C. It revealed the stability of gas permeation properties for a minimum of up to 500 h of total heating time after a modest permeation values decrease in the first 48 h. X-ray diffraction data indicate a decrease in interchain distances during the heat treatment of isotropic films and indicate an increase in the packing density of macromolecules during thermally activated relaxation. Isotropic films and TFCMs from pure PTMSP and with antioxidant stabilizer were tested under conditions of constant O2 and N2 flow. The physical aging of thick and composite PTMSP membranes point out the necessity of thermal annealing for obtaining PTMSP-based membranes with predictable properties.

Membrane-Assisted Methanol Synthesis Processes and the Required Permselectivity.

Water-selective membrane reactors are proposed in the literature to improve methanol yield for a standalone reactor. However, the methanol productivity is not a precise metric to show the system improvement since, with this approach, we do not consider the amount of energy loss through the undesirable co-permeation of H2, which could otherwise remain on the reaction side at high pressure. In other words, the effectiveness of this new technology should be evaluated at a process flowsheet level to assess its advantages and disadvantages on the overall system performance and, more importantly, to identify the minimum required properties of the membrane. Therefore, an equation-based model for a membrane reactor, developed in Aspen Custom Modeler, was incorporated within the process flowsheet of the methanol plant to develop an integrated process framework to conduct the investigation. We determined the upper limit of the power-saving at 32% by exploring the favorable conditions wherein a conceptual water selective membrane reactor proves more effective. Using these suboptimal conditions, we realized that the minimum required H2O/H2 selectivity is 190 and 970 based on the exergy analysis and overall power requirement, respectively. According to our results, the permselectivity of membranes synthesized for this application in the literature, showing improvements in the one-pass conversion, is well below the minimum requirement when the overall methanol synthesis process flowsheet comes into consideration.

Multicomponent Network Formation in Selective Layer of Composite Membrane for CO2 Separation.

As a promising material for CO2/N2 separation, PolyActiveTM can be used as a separation layer in thin-film composite membranes (TFCM). Prior studies focused on the modification of PolyActiveTM using low-molecular-weight additives. In this study, the effect of chemical crosslinking of reactive end-groups containing additives, forming networks within selective layers of the TFCM, has been studied. In order to understand the influence of a network embedded into a polymer matrix on the properties of the resulting materials, various characterization methods, including Fourier transform infrared spectroscopy (FTIR), gas transport measurements, differential scanning calorimetry (DSC) and atomic force microscopy (AFM), were used. The characterization of the resulting membrane regarding individual gas permeances by an in-house built "pressure increase" facility revealed a twofold increase in CO2 permeance, with insignificant losses in CO2/N2 selectivity.

Investigation of the Side Chain Effect on Gas and Water Vapor Transport Properties of Anthracene-Maleimide Based Polymers of Intrinsic Microporosity.

In the present work, a set of anthracene maleimide monomers with different aliphatic side groups obtained by Diels Alder reactions were used as precursors for a series of polymers of intrinsic microporosity (PIM) based homo- and copolymers that were successfully synthesized and characterized. Polymers with different sizes and shapes of aliphatic side groups were characterized by size-exclusion chromatography (SEC), (nuclear magnetic resonance) 1H-NMR, thermogravimetric (TG) analysis coupled with Fourier-Transform-Infrared (FTIR) spectroscopy (TG-FTIR) and density measurements. The TG-FTIR measurement of the monomer-containing methyl side group revealed that the maleimide group decomposes prior to the anthracene backbone. Thermal treatment of homopolymer methyl-100 thick film was conducted to establish retro-Diels Alder rearrangement of the homopolymer. Gas and water vapor transport properties of homopolymers and copolymers were investigated by time-lag measurements. Homopolymers with bulky side groups (i-propyl-100 and t-butyl-100) experienced a strong impact of these side groups in fractional free volume (FFV) and penetrant permeability, compared to the homopolymers with linear alkyl side chains. The effect of anthracene maleimide derivatives with a variety of aliphatic side groups on water vapor transport is discussed. The maleimide moiety increased the water affinity of the homopolymers. Phenyl-100 exhibited a high water solubility, which is related to a higher amount of aromatic rings in the polymer. Copolymers (methyl-50 and t-butyl-50) showed higher CO2 and CH4 permeability compared to PIM-1. In summary, the introduction of bulky substituents increased free volume and permeability whilst the maleimide moiety enhanced the water vapor affinity of the polymers.

Modification of Poly(4-methyl-2-pentyne) in the Supercritical Fluid Medium for Selective Membrane Separation of CO2 from Various Gas Mixtures.

The modification of highly permeable films of brominated 1,2-disubstituted polyacetylene, poly(4-methyl-2-penthyne), via incorporation of in situ formed butylimidazolium bromide is reported for the first time. Principal possibility and efficiency of supercritical CO2 and CHF3 use as reaction media for the corresponding process, namely for quaternization of butylimidazole by brominated polymer are revealed. As a result, we prepared new membrane materials possessing promising properties such as stability toward organic solvents, good mechanical properties and significantly improved CO2-selectivity while maintaining gas permeability at high values. Comparative analysis of the results allowed us to determine content and conditions for the incorporation of butylimidazolium groups optimal for most efficient separation of CO2 from industrial gas mixtures. These results are of interest for the designing of new CO2 selective membranes.

Synthesis, Transfer, and Gas Separation Characteristics of MOF-Templated Polymer Membranes.

This paper discusses the potential of polymer networks, templated by crystalline metal-organic framework (MOF), as novel selective layer material in thin film composite membranes. The ability to create mechanically stable membranes with an ultra-thin selective layer of advanced polymer materials is highly desirable in membrane technology. Here, we describe a novel polymeric membrane, which is synthesized via the conversion of a surface anchored metal-organic framework (SURMOF) into a surface anchored gel (SURGEL). The SURGEL membranes combine the high variability in the building blocks and the possibility to control the network topology and membrane thickness of the SURMOF synthesis with high mechanical and chemical stability of polymers. Next to the material design, the transfer of membranes to suitable supports is also usually a challenging task, due to the fragile nature of the ultra-thin films. To overcome this issue, we utilized a porous support on top of the membrane, which is mechanically stable enough to allow for the easy membrane transfer from the synthesis substrate to the final membrane support. To demonstrate the potential for gas separation of the synthesized SURGEL membranes, as well as the suitability of the transfer method, we determined the permeance for eight gases with different kinetic diameters.

Chemical Modification of Poly(1-Trimethylsylil-1-Propyne) for the Creation of Highly Efficient CO2-Selective Membrane Materials.

The work is devoted to the chemical modification of a polymer that is promising for the creation of gas separation membranes, aimed at increasing the selectivity with respect to CO2. The introduction of ionic liquids into the structure of poly(1-trimethylsilyl-1-propyne) is realized by a two-step process: bromination of the initial polymer with N-bromosuccinimide and subsequent addition of tertiary amine (N-butylimidazole) to it. Depending on the process conditions, the method allows polymers with different contents of the ionic liquid to be obtained. The obtained polymers show good film-forming properties and thermal stability. Depending on the content of the ionic liquid in the polymer matrix, the resistance to aliphatic alicyclic to the majority of halogenated, as well as aromatic hydrocarbons, increases. With an increase of the ionic liquid content in the polymer, the ideal selectivities of CO2/N2 and CO2/CH4 gas pairs increases while maintaining a high level of permeability.

Novel Polymeric Thin-Film Composite Membranes for High-Temperature Gas Separations.

Novel selective polymeric thin-film composite membranes (TFCMs) for applications at elevated temperatures were developed. Thin selective layers of the polyimides Matrimid 5218® and 6FDA-6FpDA were cast on a developed polybenzimidazole (PBI) porous support prepared by a phase inversion process. The TFCM properties were investigated with different gases in a wide temperature range, including temperatures up to 270 °C. The membranes showed very high thermal stability and performed well at the elevated temperatures. The development of highly thermally resistant polymeric membranes such as these TFCMs opens opportunities for application in high-temperature integrated processes, such as catalytic membrane reactors for the water-gas shift reaction in order to maximize H2 yield.

Separation of Carbon Dioxide from Real Power Plant Flue Gases by Gas Permeation Using a Supported Ionic Liquid Membrane: An Investigation of Membrane Stability.

The separation of carbon dioxide from coal-fired power plant flue gases using a CO2/N2-selective supported ionic liquid membrane (SILM) was investigated and the performance and stability of the membrane during operation are reported. The membrane is composed of a polyacrylonitrile (PAN) ultrafiltration membrane as a support and a selective layer of an ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM Tf2N). The feasibility of large-scale SILM production was demonstrated by the formation of a square-meter-scale membrane and preparation of a membrane module. A flat-sheet envelope-type SILM module containing 0.67 m² of the membrane was assembled. Prior to real flue gas operation, the separation behaviour of the membrane was investigated with single gases. The stability of the SILM during the test stand and pilot plant operation using real power plant flue gases is reported. The volume fraction of carbon dioxide in the flue gas was raised from approx. 14 vol. % (feed) to 40 vol. % (permeate). However, issues concerning the membrane stability were found when SO3 aerosols in large quantities were present in the flue gas.

Characteristics of Gas Permeation Behaviour in Multilayer Thin Film Composite Membranes for CO2 Separation.

Porous, porous/gutter layer and porous/gutter layer/selective layer types of membranes were investigated for their gas transport properties in order to derive an improved description of the transport performance of thin film composite membranes (TFCM). A model describing the individual contributions of the different layers' mass transfer resistances was developed. The proposed method allows for the prediction of permeation behaviour with standard deviations (SD) up to 10%. The porous support structures were described using the Dusty Gas Model (based on the Maxwell⁻Stefan multicomponent mass transfer approach) whilst the permeation in the dense gutter and separation layers was described by applicable models such as the Free-Volume model, using parameters derived from single gas time lag measurements. The model also accounts for the thermal expansion of the dense layers at pressure differences below 100 kPa. Using the model, the thickness of a silicone-based gutter layer was calculated from permeation measurements. The resulting value differed by a maximum of 30 nm to the thickness determined by scanning electron microscopy.

Study of the Effect of Inorganic Particles on the Gas Transport Properties of Glassy Polyimides for Selective CO2 and H2O Separation.

Three polyimides and six inorganic fillers in a form of nanometer-sized particles were studied as thick film solution cast mixed matrix membranes (MMMs) for the transport of CO2, CH4, and H2O. Gas transport properties and electron microscopy images indicate good polymer-filler compatibility for all membranes. The only filler type thatdemonstrated good distribution throughout the membrane thickness at 10 wt. % loading was BaCe0.2Zr0.7Y0.1O3 (BCZY). The influence of this filler on MMM gas transport properties was studied in detail for 6FDA-6FpDA in a filler content range from one to 20 wt. % and for Matrimid® and P84® at 10 wt. % loading. The most promising result was obtained for Matrimid®-10wt. % BCZY MMM, which showed improvement in CO2 and H2O permeabilities accompanied by increased CO2/CH4 selectivity and high water selective membrane at elevated temperatures without H2O/permanent gas selectivity loss.

Covalently Modified Graphene Oxide and Polymer of Intrinsic Microporosity (PIM-1) in Mixed Matrix Thin-Film Composite Membranes.

In this study, mixed matrix membranes (MMMs) consisting of graphene oxide (GO) and functionalized graphene oxide (FGO) incorporated in a polymer of intrinsic microporosity (PIM-1) serving as a polymer matrix have been fabricated by dip-coating method, and their single gas transport properties were investigated. Successfully surface-modified GOs were characterized by Fourier transform infrared spectroscopy (FTIR), UV-Vis spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The effect of FGO loading on MMM morphology and performance was investigated by varying the FGO content in polymer matrix from 9 to 84 wt.%. Use of high FGO content in the polymer matrix helped to reveal difference in interaction of functionalized fillers with PIM-1 and even to discuss the change of FGO stiffness and filler alignment to the membrane surface depending on functional group nature.

CO2 Selective PolyActive Membrane: Thermal Transitions and Gas Permeance as a Function of Thickness.

It is generally accepted that the melting point of a semicrystalline polymer is associated with the thickness of the crystalline lamellae (Gibbs-Thomson equation). In this study, a commercially available multiblock copolymer PolyActive composed of 77 wt % of poly(ethylene glycol terephthalate) and 23 wt % of poly(butylene terephthalate) was dip-coated on top of a multilayer microporous support. The thickness was changed between 0.2 and 8 µm using coating solutions containing 0.75-7.5 wt % PolyActive. The surface temperature of the membrane during dip-coating was monitored using an infrared camera. Single gas permeances of N2, H2, CH4, and CO2 were measured between 20 and 80 °C at temperature steps of 2 °C. Spherulitic superstructures composed of radially directed lamellae were observed in the polarized light microscope in the prepared membranes. Atomic force microscopy studies showed that the thickness of the crystalline lamellae was in the order of 10 nm or 0.01 µm at the surface of the membrane. Therefore, according to the Gibbs-Thomson equation, the melting point should not change in the thickness range 0.2-8 µm. However, the gas permeance data showed that the melting point of the polyether domains of the 0.2 µm PolyActive layer was 10 °C lower compared to that of the 8 µm layer. The results can be explained by considering that the width of many crystalline lamellae significantly reduces as a function of film thickness, thereby reducing the average fold surface free energy/lateral surface free energy ratio.

Applicability of PolyActive™ Thin Film Composite Membranes for CO2 Separation from C2H4 Containing Multi-Component Gas Mixtures at Pressures up to 30 Bar.

The PolyActive™ thin film composite membrane (TFCM) has already been successfully applied for CO2 separation tasks at feed pressures up to 10 bar. To investigate the applicability at higher pressures, measurements were undertaken with C2H4 containing gas mixtures with a composition comparable to the product stream of the oxidative coupling of methane process, as well as single gases up to a feed pressure of 30 bar. Furthermore, the permeances of the conducted gas mixture experiments were simulated. The results show a strong swelling influence of CO2 on the used membrane depending on the CO2 fugacity. This swelling effect leads to a pronounced decrease in selectivity. The observed membrane behavior at high pressures could not be predicted by the Free Volume Model (FVM). Two different simulations were conducted: one based on parameters calculated from single gas data measured at pressures up to 2 bar; and a second based on parameters calculated from single gas data measured at pressures from 2 to 30 bar. The two simulations differ in their prediction accuracy. However, they confirm that it is possible to predict the measured permeances in the pressure range up to an average CO2 fugacity of 6 bar.

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications.

Novel selective ceramic-supported thin polyimide films produced in a single dip coating step are proposed for membrane applications at elevated temperatures. Layers of the polyimides P84®, Matrimid 5218®, and 6FDA-6FpDA were successfully deposited onto porous alumina supports. In order to tackle the poor compatibility between ceramic support and polymer, and to get defect-free thin films, the effect of the viscosity of the polymer solution was studied, giving the entanglement concentration (C*) for each polymer. The C* values were 3.09 wt. % for the 6FDA-6FpDA, 3.52 wt. % for Matrimid®, and 4.30 wt. % for P84®. A minimum polymer solution concentration necessary for defect-free film formation was found for each polymer, with the inverse order to the intrinsic viscosities (P84® ≥ Matrimid® >> 6FDA-6FpDA). The effect of the temperature on the permeance of prepared membranes was studied for H2, CH4, N2, O2, and CO2. As expected, activation energy of permeance for hydrogen was higher than for CO2, resulting in H2/CO2 selectivity increase with temperature. More densely packed polymers lead to materials that are more selective at elevated temperatures.

Mixed Matrix Membranes of Boron Icosahedron and Polymers of Intrinsic Microporosity (PIM-1) for Gas Separation.

This work reports on the preparation and gas transport performance of mixed matrix membranes (MMMs) based on the polymer of intrinsic microporosity (PIM-1) and potassium dodecahydrododecaborate (K2B12H12) as inorganic particles (IPs). The effect of IP loading on the gas separation performance of these MMMs was investigated by varying the IP content (2.5, 5, 10 and 20 wt %) in a PIM-1 polymer matrix. The derived MMMs were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), single gas permeation tests and sorption measurement. The PIM1/K2B12H12 MMMs show good dispersion of the IPs (from 2.5 to 10 wt %) in the polymer matrix. The gas permeability of PIM1/K2B12H12 MMMs increases as the loading of IPs increases (up to 10 wt %) without sacrificing permselectivity. The sorption isotherm in PIM-1 and PIM1/K2B12H12 MMMs demonstrate typical dual-mode sorption behaviors for the gases CO2 and CH4.

Development and Characterization of Defect-Free Matrimid® Mixed-Matrix Membranes Containing Activated Carbon Particles for Gas Separation.

In this work, mixed-matrix membranes (MMMs) for gas separation in the form of thick films were prepared via the combination of the polymer Matrimid® 5218 and activated carbons (AC). The AC particles had a mean particle size of 1.5 µm and a mean pore diameter of 1.9 nm. The films were prepared by slow solvent evaporation from casting solutions in chloroform, which had a varying polymer⁻AC ratio. It was possible to produce stable films with up to a content of 50 vol % of AC. Thorough characterization experiments were accomplished via differential scanning calorimetry and thermogravimetric analysis, while the morphology of the MMMs was also investigated via scanning electron microscopy. The gas transport properties were revealed by employing time-lag measurements for different pure gases as well as sorption balance experiments for the filler particles. It was found that defect free Matrimid® MMMs with AC were prepared and the increase of the filler content led to a higher effective permeability for different gases. The single gas selectivity αij of different gas pairs maintained stable values with the increase of AC content, regardless of the steep increase in the effective permeability of the pure gases. Estimation of the solubilities and the diffusivities of the Matrimid®, AC, and MMMs allowed for the explanation of the increasing permeabilities of the MMMs, with the increase of AC content by modelling.