Morphological Study before and after Thermal Treatment of Polymer-Polymer Mixed-Matrix Membranes for Gas Separations.

A good integration of the polymer materials that form a mixed-matrix membrane (MMM) for gas separation is essential to reaching interesting permselective properties. In this work, a porous polymer network (PPN), obtained by combining triptycene and trifluoroacetophenone, has been used as a filler, which was blended with two o-hydroxypolyamides (HPAs) that act as polymer matrices. These polymer matrices have been thermally treated to induce a thermal rearrangement (TR) of the HPAs to polybenzoxazoles (ß-TR-PBOs) through a solid-state reaction. For its structural study, various techniques have been proposed that allow us to undertake a morphological investigation into the integration of these materials. To access the internal structure of the MMMs, three different methods were used: a polishing process for the material surface, the partial dissolution of the polymer matrix, or argon plasma etching. The argon plasma technique has not only revealed its potential to visualize the internal structure of these materials; it has also been proven to allow for the transformation of their permselective properties. Force modulation and phase contrast in lift-mode techniques, along with the topographic images obtained via the tapping mode using a scanning probe microscope (SPM), have allowed us to study the distribution of the filler particles and the interaction of the polymer and the filler. The morphological information obtained via SPM, along with that of other more commonly used techniques (SEM, TGA, DSC, FTIR, WASX, gas adsorption, and permeability measurements), has allowed us to postulate the most probable structural configuration in this type of system.

Forward Osmosis Application for the Removal of Emerging Contaminants from Municipal Wastewater: A Review.

Forward osmosis (FO) has attracted special attention in water and wastewater treatment due to its role in addressing the challenges of water scarcity and contamination. The presence of emerging contaminants in water sources raises concerns regarding their environmental and public health impacts. Conventional wastewater treatment methods cannot effectively remove these contaminants; thus, innovative approaches are required. FO membranes offer a promising solution for wastewater treatment and removal of the contaminants in wastewater. Several factors influence the performance of FO processes, including concentration polarization, membrane fouling, draw solute selection, and reverse salt flux. Therefore, understanding and optimizing these factors are crucial aspects for improving the efficiency and sustainability of the FO process. This review stresses the need for research to explore the potential and challenges of FO membranes to meet municipal wastewater treatment requirements, to optimize the process, to reduce energy consumption, and to promote scalability for potential industrial applications. In conclusion, FO shows promising performance for wastewater treatment, dealing with emerging pollutants and contributing to sustainable practices. By improving the FO process and addressing its challenges, we could contribute to improve the availability of water resources amid the global water scarcity concerns, as well as contribute to the circular economy.

Saline Retention and Permeability of Nanofiltration Membranes Versus Resistance and Capacitance as Obtained from Impedance Spectroscopy under a Concentration Gradient.

Impedance spectroscopy has been widely used for the study of the electrical properties of membranes for their characterization. The most common use of this technique is the measure of the conductivity of different electrolyte solutions to study the behavior and movement of electrically charged particles inside the pores of membranes. The objective of this investigation was to observe if there is a relation present between the retention that a nanofiltration membrane possesses to certain electrolytic solutions (NaCl, KCl, MgCl2, CaCl2, and Na2SO4) and the parameters that are obtained through IS measurements of the active layer of the membrane. To achieve our objective, different characterization techniques were performed to obtain the permeability, retention, and zeta potential values of a Desal-HL nanofiltration membrane. Impedance spectroscopy measurements were performed when a gradient concentration was present between both sides of the membrane to study the variation that the electrical parameters had with the time evolution.

Evaluation of Forward Osmosis and Low-Pressure Reverse Osmosis with a Tubular Membrane for the Concentration of Municipal Wastewater and the Production of Biogas.

Currently, freshwater scarcity is one of the main issues that the world population has to face. To address this issue, new wastewater treatment technologies have been developed such as membrane processes. Among them, due to the energy disadvantages of pressure-driven membrane processes, Forward Osmosis (FO) and Low-Pressure Reverse Osmosis (LPRO) have been introduced as promising alternatives. In this study, the behavior of a 2.3 m2 tubular membrane TFO-D90 when working with municipal wastewater has been studied. Its performances have been evaluated and compared in two operating modes such as FO and LPRO. Parameters such as fouling, flow rates, water flux, draw solution concentration, organic matter concentration, as well as its recovery have been studied. In addition, the biogas production capacity has been evaluated with the concentrated municipal wastewater obtained from each process. The results of this study indicate that the membrane can work in both processes (FO and LPRO) but, from the energy and productivity point of view, FO is considered more appropriate mainly due to its lower fouling level. This research may offer a new point of view on low-energy and energy recovery wastewater treatment and the applicability of FO and LPRO for wastewater concentration.

Gas Permeability through Polyimides: Unraveling the Influence of Free Volume, Intersegmental Distance and Glass Transition Temperature.

The relationships between gas permeability and free volume fraction, intersegmental distance, and glass transition temperature, are investigated. They are analyzed for He, CO2, O2, CH4, and N2 gases and for five similar polyimides with a wide range of permeabilities, from very low to extremely high ones. It has been established here that there is an exponential relationship between permeability and the free volume fraction, and between permeability and the most probable intersegmental distance as measured by WAXS; in both cases, with an exponential coefficient that depends on the kinetic gas diameter as a quadratic polynomial and with a preexponential positive constant. Moreover, it has been proven that the intersegmental distance increases linearly with the free volume fraction. Finally, it has been established that the free volume fraction increases with the glass transition temperature for the polymers tested, and that they depend on each other in an approximate linear way.

Thermally Rearranged Mixed Matrix Membranes from Copoly(o-hydroxyamide)s and Copoly(o-hydroxyamide-amide)s with a Porous Polymer Network as a Filler-A Comparison of Their Gas Separation Performances.

Copoly(o-hydroxyamide)s (HPA) and copoly(o-hydroxyamide-amide)s (PAA) have been synthesized to be used as continuous phases in mixed matrix membranes (MMMs). These polymeric matrices were blended with different loads (15 and 30 wt.%) of a relatively highly microporous porous polymer network (PPN). SEM images of the manufactured MMMs exhibited good compatibility between the two phases for all the membranes studied, and their mechanical properties have been shown to be good enough even after thermal treatment. The WAX results show that the addition of PPN as a filler up to 30% does not substantially change the intersegmental distance and the polymer packing. It seems that, for all the membranes studied, the free volume that determines gas transport is in the high end of the possible range. This means that gas flow occurs mainly between the microvoids in the polymer matrix around the filler. In general, both HPA- and PAA-based MMMs exhibited a notable improvement in gas permeability, due to the presence of PPN, for all gases tested, with an almost constant selectivity. In summary, although the thermal stability of the PAA is limited by the thermal stability of the polyamide side chain, their mechanical properties were better. The permeability was higher for the PAA membranes before their thermal rearrangement, and these values increased after the addition of moderate amounts of PPN.

Enhancement of swine manure anaerobic digestion using membrane-based NH3 extraction.

The influence of suspended solids and pH in anaerobically digested piggery wastewater on membrane-based NH3 extraction was evaluated in batch tests. The increase in pH in the anaerobic broth from 8 to 9 resulted in an increase in NH3 removal efficiencies from 15.8 % ± 0.1 % to 20.9 % ± 0.4 % regardless of the suspended solids. The influence of membrane based NH3 extraction on piggery wastewater treatment was also assessed in a CSTR interconnected with PTFE membrane modules. The decrease in TKN concentrations mediated by membrane operation induced an increase in CH4 yield from 380.4 ± 84.9 up to 566.1 ± 7.8 NmLCH4 g VS fed-1. Likewise, COD and VS removal efficiencies significantly increased from 33.0 % ± 2.0 % and 25.7 % ± 2.3 % up to 61.8 % ± 1.3 % and 37.9 % ± 1.8 %, respectively. Interestingly, the decrease in NH3 concentration entailed a complete assimilation of VFA.

Free Volume and Permeability of Mixed Matrix Membranes Made from a Terbutil-M-terphenyl Polyamide and a Porous Polymer Network.

A set of thermally rearranged mixed matrix membranes (TR-MMMs) was manufactured and tested for gas separation. These membranes were obtained through the thermal treatment of a precursor MMM with a microporous polymer network and an o-hydroxypolyamide,(HPA) created through a reaction of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (APAF) and 5'-terbutil-m-terfenilo-3,3″-dicarboxylic acid dichloride (tBTmCl). This HPA was blended with different percentages of a porous polymer network (PPN) filler, which produced gas separation MMMs with enhanced gas permeability but with decreased selectivity. The thermal treatment of these MMMs gave membranes with excellent gas separation properties that did not show the selectivity decreasing trend. It was observed that the use of the PPN load brought about a small decrease in the initial mass losses, which were lower for increasing PPN loads. Regarding the glass transition temperature, it was observed that the use of the filler translated to a slightly lower Tg value. When these MMMs and TR-MMMs were compared with the analogous materials created from the isomeric 5'-terbutil-m-terfenilo-4,4″-dicarboxylic acid dichloride (tBTpCl), the permeability was lower for that of tBTmCl, compared with the one from tBTpCl, although selectivity was quite similar. This fact could be attributed to a lower rigidity as roughly confirmed by the segmental length of the polymer chain as studied by WAXS. A model for FFV calculation was proposed and its predictions compared with those evaluated from density measurements assuming a matrix-filler interaction or ideal independence. It turns out that permeability as a function of FFV for TR-MMMs follows an interaction trend, while those not thermally treated follow the non-interaction trend until relatively high PPN loads were reached.

Membrane Dialysis for Partial Dealcoholization of White Wines.

Membrane dialysis is studied as a promising technique for partial dealcoholization of white wines. The performance of three membrane processes applied for the partial dealcoholization of white wines of the Verdejo variety has been studied in the present work. Combination of Nanofiltration with Pervaporation, single step Pervaporation and, finally, Dialysis, have been applied to white wines from same variety and different vintages. The resulting wines have been chemically and sensorially analyzed and results have been compared with initial characteristics of the wines. From the results obtained, we can conclude that all procedures lead to significant alcohol content reduction (2%, 0.9% and 1.23% v/v respectively). Nevertheless, the best procedure consists in the application of Dialysis to the wines which resulted in a reasonable alcohol content reduction while maintaining organoleptic properties (only 14 consumers were able to distinguish the filtered and original wines, with 17 consumers needed to be this differences significant) and consumer acceptability of the original wine. Therefore, membrane dialysis, as a method of partial dealcoholization of white wines, has undoubted advantages over other techniques based on membranes, which must be confirmed in subsequent studies under more industrial conditions. This work represents the first application of Dialysis for the reduction of alcohol content in wines.

Ecological Risk Evaluation and Removal of Emerging Pollutants in Urban Wastewater by a Hollow Fiber Forward Osmosis Membrane.

Forward osmosis (FO) is a promising technology for the treatment of urban wastewater. FO can produce high-quality effluents and preconcentrate urban wastewater for subsequent anaerobic treatment. This membrane technology makes it possible to eliminate the pollutants present in urban wastewater, which can cause adverse effects in the ecosystem even at low concentrations. In this study, a 0.6 m2 hollow fiber aquaporin forward osmosis membrane was used for the treatment of urban wastewater from the Valladolid wastewater treatment plant (WWTP). A total of 51 Contaminants of Emerging Concern (CECs) were investigated, of which 18 were found in the target urban wastewater. They were quantified, and their ecotoxicological risk impact was evaluated. Different salts with different concentrations were tested as draw solutions to evaluate the membrane performances when working with pretreated urban wastewater. NaCl was found to be the most appropriate salt since it leads to higher permeate fluxes and lower reverse saline fluxes. The membrane can eliminate or significantly reduce the pollutants present in the studied urban wastewater, producing water without ecotoxicological risk or essentially free of pollutants. In all cases, good recovery was achieved, which increased with molecular weight, although chemical and electrostatic interactions also played a role.

Gas Permeability, Fractional Free Volume and Molecular Kinetic Diameters: The Effect of Thermal Rearrangement on ortho-hydroxy Polyamide Membranes Loaded with a Porous Polymer Network.

Mixed-matrix membranes (MMMs) consisting of an ortho-hydroxy polyamide (HPA) matrix, and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (ß-TR-PBO). Two different HPAs were synthesized to be used as a matrix, 6FCl-APAF and tBTpCl-APAF, while the PPN used as a filler was prepared by reacting triptycene and trifluoroacetophenone. The permeability of He, H2, N2, O2, CH4 and CO2 gases through these MMMs are analyzed as a function of the fraction of free volume (FFV) of the membrane and the kinetic diameter of the gas, allowing for the evaluation of the free volume. Thermal rearrangement entails an increase in the FFV. Both before and after thermal rearrangement, the free volume increases with the PPN content very similarly for both polymeric matrices. It is shown that there is a portion of free volume that is inaccessible to permeation (occluded volume), probably due to it being trapped within the filler. In fact, permeability and selectivity change below what could be expected according to densities, when the fraction of occluded volume increases. A higher filler load increases the percentage of inaccessible or trapped free volume, probably due to the increasing agglomeration of the filler. On the other hand, the phenomenon is slightly affected by thermal rearrangement. The fraction of trapped free volume seems to be lower for membranes in which the tBTpCl-APAF is used as a matrix than for those with a 6FCl-APAF matrix, possibly because tBTpCl-APAF could approach the PPN better. The application of an effective medium theory for permeability allowed us to extrapolate for a 100% filler, giving the same value for both thermally rearranged and non-rearranged MMMs. The pure filler could also be extrapolated by assuming the same tendency as in the Robeson's plots for MMMs with low filler content.

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement.

Mixed matrix membranes (MMMs) consisting of a blend of a hydroxypolyamide (HPA) matrix and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (ß-TR-PBO). Here, the HPA matrix was a hydroxypolyamide having two hexafluoropropyilidene moieties, 6FCl-APAF, while the PPN was prepared by reacting triptycene (TRP) and trifluoroacetophenone (TFAP) in a superacid solution. The most probable size of the PPN particles was 75 nm with quite large distributions. The resulting membranes were analyzed by SEM and AFM. Up to 30% PPN loads, both SEM and AFM images confirmed quite planar surfaces, at low scale, with limited roughness. Membranes with high hydrogen permeability and good selectivity for the gas pairs H2/CH4 and H2/N2 were obtained. For H2/CO2, selectivity almost vanished after thermal rearrangement. In all cases, their hydrogen permeability increased with increasing loads of PPN until around 30% PPN with ulterior fairly abrupt decreasing of permeability for all gases studied. Thermal rearrangement of the MMMs resulted in higher permeabilities but lower selectivities. For all the membranes and gas pairs studied, the balance of permeability vs. selectivity surpassed the 1991 Robeson's upper bound, and approached or even exceeded the 2008 line, for MMMs having 30% PPN loads. In all cases, the HPA-MMMs before thermal rearrangement provided good selectivity versus permeability compromise, similar to their thermally rearranged counterparts but in the zone of high selectivity. For H2/CH4, H2/N2, these nonthermally rearranged MMMs approach the 2008 Robeson's upper bound while H2/CO2 gives selective transport favoring H2 on the 1991 Robeson's bound. Thus, attending to the energy cost of thermal rearrangement, it could be avoided in some cases especially when high selectivity is the target rather than high permeability.

Gas Separation by Mixed Matrix Membranes with Porous Organic Polymer Inclusions within o-Hydroxypolyamides Containing m-Terphenyl Moieties.

A hydroxypolyamide (HPA) manufactured from 2,2-bis(3-amino-4-hydroxy phenyl)-hexafluoropropane (APAF) diamine and 5'-terbutyl-m-terphenyl-4,4''-dicarboxylic acid chloride (tBTpCl), and a copolyimide produced by stochiometric copolymerization of APAF and 4,4'-(hexafluoroisopropylidene) diamine (6FpDA), using the same diacid chloride, were obtained and used as polymeric matrixes in mixed matrix membranes (MMMs) loaded with 20% (w/w) of two porous polymer networks (triptycene-isatin, PPN-1, and triptycene-trifluoroacetophenone, PPN-2). These MMMs, and also the thermally rearranged membranes (TR-MMMs) that underwent a thermal treatment process to convert the o-hydroxypolyamide moieties to polybenzoxazole ones, were characterized, and their gas separation properties evaluated for H2, N2, O2, CH4, and CO2. Both TR process and the addition of PPN increased permeability with minor decreases in selectivity for all gases tested. Excellent results were obtained, in terms of the permeability versus selectivity compromise, for H2/CH4 and H2/N2 separations with membranes approaching the 2008 Robeson's trade-off line. The best gas separation properties were obtained when PPN-2 was used. Finally, gas permeation was characterized in terms of chain intersegmental distance and fraction of free volume of the membrane along with the kinetic diameters of the permeated gases. The intersegmental distance increased after TR and/or the addition of PPN-2. Permeability followed an exponential dependence with free volume and a quadratic function of the kinetic diameter of the gas.

A Systematic Study of Ammonia Recovery from Anaerobic Digestate Using Membrane-Based Separation.

Ammonia recovery from synthetic and real anaerobic digestates was accomplished using hydrophobic flat sheet membranes operated with H2SO4 solutions to convert ammonia into ammonium sulphate. The influence of the membrane material, flow rate (0.007, 0.015, 0.030 and 0.045 m3 h-1) and pH (7.6, 8.9, 10 and 11) of the digestate on ammonia recovery was investigated. The process was carried out with a flat sheet configuration at a temperature of 35 °C and with a 1 M, or 0.005 M, H2SO4 solution on the other side of the membrane. Polytetrafluoroethylene membranes with a nominal pore radius of 0.22 µm provided ammonia recoveries from synthetic and real digestates of 84.6% ± 1.0% and 71.6% ± 0.3%, respectively, for a membrane area of 8.6 × 10-4 m2 and a reservoir volume of 0.5 L, in 3.5 h with a 1 M H2SO4 solution and a recirculation flow on the feed side of the membrane of 0.030 m3 h-1. NH3 recovery followed first order kinetics and was faster at higher pHs of the H2SO4 solution and recirculation flow rate on the membrane feed side. Fouling resulted in changes in membrane surface morphology and pore size, which were confirmed by Atomic Force Microscopy and Air Displacement Porometry.

Morphological, Electrical, and Chemical Characteristics of Poly(sodium 4-styrenesulfonate) Coated PVDF Ultrafiltration Membranes after Plasma Treatment.

A commercial ultrafiltration (UF) membrane (HFM-183 de Koch Membrane Systems) made of poly(vinylidene fluoride) (PVDF), was recovered with a negatively-charged polyelectrolyte (poly(sodium 4-styrenesulfonate)) (PSS), and the effects on its electric, chemical, and morphological properties were analyzed. Atomic force microscopy (AFM), liquid-liquid displacement porometry, Electrical Impedance Spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy were used to investigate the modifications induced by the deposition of PSS on the PVDF positively-charged membrane and after its treatment by a radio frequency Ar-plasma. These techniques confirmed a real deposition and posterior compaction of PSS with increasing roughness and decreasing pore sizes. The evolution of the electric resistances of the membranes confirmed crosslinking and compaction with shielding of the sulfonated groups from PSS. In this way, a membrane with a negatively-charged active layer and a pore size which was 60% lower than the original membrane was obtained. The composition of the additive used by manufacturers to modify PVDF to make it positively charged was obtained by different procedures, all of which depended upon the results of X-ray photoelectron spectroscopy, leading to fairly consistent results. This polymer, carrying positive charges, contains quaternary nitrogen, as confirmed by XPS. Moreover, Raman spectroscopy confirmed that PVDF changes from mostly the to the α phase, which is more stable as a substrate for the deposited PSS. The aim of the tested modifications was to increase the retention of divalent anions without reducing permeability.

Comparison of the volume charge density of nanofiltration membranes obtained from retention and conductivity experiments.

A version of the Donnan steric-partitioning pore model with dielectrical exclusion (DSPM-DE) has been used to get information on the pore size and charge density of a commercial membrane, NF45 from FilmTec, from its retention of KCl solutions. The conductivity inside the pores has been measured by impedance spectroscopy, and the electric potential drop during retention experiments has also been measured. These experimental data on conductivity and electric potential are analyzed, by using the thermodynamics of irreversible processes and the space charge model, to obtain the pore charge density of the membrane. These two methods give results in fair accordance which probes that the sometimes controversial method of DSPM-DE can give accurate results for the charge as well as for the mean pore size of a nanofiltration membrane. Some clues to improve the way this model can be used are given as well.