Advances in mixed-matrix membranes for biorefining of biogas from anaerobic digestion.

This article provides a comprehensive review of the state-of-the-art technology of polymeric mixed-matrix membranes for CO2/CH4 separation that can be applied in medium, small, and domestic biogas systems operating at low pressures (0.2-6 kPa). Critical data from the latest publications of CO2/CH4 separation membranes were analyzed, considering the ratio of CO2/CH4 permeabilities, the CO2 selectivity, the operating pressures at which the membranes were tested, the chemistry of the polymers studied and their gas separation mechanisms. And the different nanomaterials as fillers. The intrinsic microporous polymers (PIMs) were identified as potential candidates for biomethane purification due to their high permeability and selectivity, which are compatible with operation pressures below 1 bar, and as low as 0.2 bar. This scenario contrasts with other polymers that require pressures above 1 bar for operation, with some reaching 20 bar. Furthermore, the combination of PIM with GO in MMMs was found to not influence the permeability significantly, but to contribute to the membrane stability over time, by preventing the structural collapse of the membrane caused by aging. The systematic analysis here presented is a valuable resource for defining the future technological development of CO2/CH4 separation membranes for biogas biorefining.

Ti3C2 MXene Membranes for Gas Separation: Influence of Heat Treatment Conditions on D-Spacing and Surface Functionalization.

Two-dimensional (2D) MXene materials have recently been the focus of membrane research due to their unique properties, such as their single-atomic-layer thickness, flexibility, molecular filtration abilities and microstructural similarities with graphene, which is currently the most efficient precursor material for gas separation applications. In addition, the potential to process nanoscale channels has motivated investigations of parameters which can improve membrane permeability and selectivity. Interlayer spacing and defects, which are still challenging to control, are among the most crucial parameters for membrane performance. Herein, the effect of heat treatment on the d-spacing of MXene nanosheets and the surface functionalization of nanolayers was shown regarding its impact on the gas diffusion mechanism. The distance of the layers was reduced by a factor of over 10 from 0.345 nm to 0.024 nm, the defects were reduced, and the surface functionalization was maintained upon treatment of the Ti3C2 membrane at 500 °C under an Ar/H2 atmosphere as compared to 80 °C under vacuum. This led to a change from Knudsen diffusion to molecular sieving, as demonstrated by single-gas permeation tests at room temperature. Overall, this work shows a simple and promising way to improve H2/CO2 selectivity via temperature treatment under a controlled atmosphere.

A Bibliometric Survey of Paraffin/Olefin Separation Using Membranes.

Bibliometric studies allow to collect, organize and process information that can be used to guide the development of research and innovation and to provide basis for decision-making. Paraffin/olefin separations constitute an important industrial issue because cryogenic separation methods are frequently needed in industrial sites and are very expensive. As a consequence, the use of membrane separation processes has been extensively encouraged and has become an attractive alternative for commercial separation processes, as this may lead to reduction of production costs, equipment size, energy consumption and waste generation. For these reasons, a bibliometric survey of paraffin/olefin membrane separation processes is carried out in the present study in order to evaluate the maturity of the technology for this specific application. Although different studies have proposed the use of distinct alternatives for olefin/paraffin separations, the present work makes clear that consensus has yet to be reached among researchers and technicians regarding the specific membranes and operation conditions that will make these processes scalable for large-scale commercial applications.

Tuning of Nano-Based Materials for Embedding Into Low-Permeability Polyimides for a Featured Gas Separation.

Several concepts of membranes have emerged, aiming at the enhancement of separation performance, as well as some other physicochemical properties, of the existing membrane materials. One of these concepts is the well-known mixed matrix membranes (MMMs), which combine the features of inorganic (e.g., zeolites, metal-organic frameworks, graphene, and carbon-based materials) and polymeric (e.g., polyimides, polymers of intrinsic microporosity, polysulfone, and cellulose acetate) materials. To date, it is likely that such a concept has been widely explored and developed toward low-permeability polyimides for gas separation, such as oxydianiline (ODA), tetracarboxylic dianhydride-diaminophenylindane (BTDA-DAPI), m-phenylenediamine (m-PDA), and hydroxybenzoic acid (HBA). When dealing with the gas separation performance of polyimide-based MMMs, these membranes tend to display some deficiency according to the poor polyimide-filler compatibility, which has promoted the tuning of chemical properties of those filling materials. This approach has indeed enhanced the polymer-filler interfaces, providing synergic MMMs with superior gas separation performance. Herein, the goal of this review paper is to give a critical overview of the current insights in fabricating MMMs based on chemically modified filling nanomaterials and low-permeability polyimides for selective gas separation. Special interest has been paid to the chemical modification protocols of the fillers (including good filler dispersion) and thus the relevant experimental results provoked by such approaches. Moreover, some principles, as well as the main drawbacks, occurring during the MMM preparation are also given.

Gas Permeation Properties of Soluble Aromatic Polyimides Based on 4-Fluoro-4,4'-Diaminotriphenylmethane.

A series of new organic polyimides were synthesized from 4-fluoro-4'4"-diaminotriphenylmethane and four different aromatic dianhydrides through a one-step, high-temperature, direct polycondensation in m-cresol at 180-200 °C, resulting in the formation of high-molecular-weight polyimides (inherent viscosities ~ 1.0-1.3 dL/g). All the resulting polyimides exhibited good thermal stability with initial decomposition temperatures above 434 °C, glass-transition temperatures between 285 and 316 °C, and good solubility in polar aprotic solvents. Wide-angle X-ray scattering data indicated that the polyimides were amorphous. Dense membranes were prepared by solution casting and solvent evaporation to evaluate their gas transport properties (permeability, diffusivity, and solubility coefficients) toward pure hydrogen, helium, oxygen, nitrogen, methane, and carbon dioxide gases. In general, the gas permeability was increased as both the fractional free volume and d-spacing were also increased. A good combination of permeability and selectivity was promoted efficiently by the bulky hexafluoroisopropylidene and 4-fluoro-phenyl groups introduced into the polyimides. The results indicate that the gas transport properties of these films depend on both the structure of the anhydride moiety, which controls the intrinsic intramolecular rigidity, and the 4-fluoro-phenyl pendant group, which disrupts the intermolecular packing.