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1.
Int J Mol Sci ; 25(1)2024 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-38203772

RESUMO

Fluorinated proton-exchange membranes (PEMs) based on graft copolymers of dehydrofluorinated polyvinylidene fluoride (D-PVDF), 3-sulfopropyl acrylate (SPA), and 1H, 1H, 2H-perfluoro-1-hexene (PFH) were prepared via free radical copolymerization and characterized for fuel cell application. The membrane morphology and physical properties were studied via small-(SAXS) and wide-angle X-ray scattering (WAXS), SEM, and DSC. It was found that the crystallinity degree is 17% for PEM-RCF (co-polymer with SPA) and 16% for PEM-RCF-2 (copolymer with SPA and PFH). The designed membranes possess crystallite grains of 5-6 nm in diameter. SEM images reveal a structure with open pores on the surface of diameters from 20 to 140 nm. Their transport and electrochemical characterization shows that the lowest membrane area resistance (0.9 Ωcm2) is comparable to perfluorosulfonic acid PEMs (such as Nafion®) and polyvinylidene fluoride (PVDF) based CJMC cation-exchange membranes (ChemJoy Polymer Materials, China). Key transport and physicochemical properties of new and commercial membranes were compared. The PEM-RCF permeability to NaCl diffusion is rather high, which is due to a relatively low concentration of fixed sulfonate groups. Voltammetry confers that the electrochemical behavior of new PEM correlates to that of commercial cation-exchange membranes, while the ionic conductivity reveals an impact of the extended pores, as in track-etched membranes.


Assuntos
Alcenos , Polímeros de Fluorcarboneto , Polímeros , Polivinil , Prótons , Porosidade , Espalhamento a Baixo Ângulo , Difração de Raios X , Acrilatos
2.
Int J Mol Sci ; 24(9)2023 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-37175918

RESUMO

This book is a collection of papers published in the 3rd and 4th Special Issues of the International Journal of Molecular Sciences under the standard title, "Ion and Molecule Transport in Membrane Systems" [...].


Assuntos
Publicações , Transporte Biológico
3.
Int J Mol Sci ; 23(9)2022 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-35563102

RESUMO

Modification of an ion-exchange membrane with a thin layer, the charge of which is opposite to the charge of the substrate membrane, has proven to be an effective approach to obtaining a composite membrane with permselectivity towards monovalent ions. However, the mechanism of permselectivity is not clear enough. We report a 1D model based on the Nernst-Planck-Poisson equation system. Unlike other similar models, we introduce activity coefficients, which change when passing from one layer of the membrane to another. This makes it possible to accurately take into account the fact that the substrate membranes usually selectively sorb multiply charged counterions. We show that the main cause for the change in the permselectivity coefficient, P1/2, with increasing current density, j, is the change in the membrane/solution layer, which controls the fluxes of the competing mono- and divalent ions. At low current densities, counterion fluxes are controlled by transfer through the substrate membrane, which causes selective divalent ion transfer. When the current increases, the kinetic control goes first to the modification layer (which leads to the predominant transfer of monovalent ions) and then, at currents close to the limiting current, to the depleted diffusion layer (which results in a complete loss of the permselectivity). Thus, the dependence P1/2 - j passes through a maximum. An analytical solution is obtained for approximate assessment of the maximum value of P1/2 and the corresponding fluxes of the competing ions. The maximum P1/2 values, plotted as a function of the Na+ ion current density at which this maximum is reached, gives the theoretical trade-off curve between the membrane permselectivity and permeability of the bilayer monovalent selective ion-exchange membrane under consideration.


Assuntos
Membranas Artificiais , Difusão , Troca Iônica , Íons , Membranas
4.
Int J Mol Sci ; 23(4)2022 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-35216352

RESUMO

In this paper, we simulate the changes in the structure and transport properties of an anion-exchange membrane (CJMA-7, Hefei Chemjoy Polymer Materials Co. Ltd., China) caused by its modification with a perfluorosulfonated ionomer (PFSI). The modification was made in several stages and included keeping the membrane at a low temperature, applying a PFSI solution on its surface, and, subsequently, drying it at an elevated temperature. We applied the known microheterogeneous model with some new amendments to simulate each stage of the membrane modification. It has been shown that the PFSI film formed on the membrane-substrate does not affect significantly its properties due to the small thickness of the film (≈4 µm) and similar properties of the film and substrate. The main effect is caused by the fact that PFSI material "clogs" the macropores of the CJMA-7 membrane, thereby, blocking the transport of coions through the membrane. In this case, the membrane microporous gel phase, which exhibits a high selectivity to counterions, remains the primary pathway for both counterions and coions. Due to the above modification of the CJMA-7 membrane, the coion (Na+) transport number in the membrane equilibrated with 1 M NaCl solution decreased from 0.11 to 0.03. Thus, the modified membrane became comparable in its transport characteristics with more expensive IEMs available on the market.


Assuntos
Ânions/química , Polímeros/química , Troca Iônica , Membranas Artificiais , Modelos Teóricos , Sódio/química
5.
Int J Mol Sci ; 24(1)2022 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-36613476

RESUMO

Artificial ion-exchange and other charged membranes, such as biomembranes, are self-organizing nanomaterials built from macromolecules. The interactions of fragments of macromolecules results in phase separation and the formation of ion-conducting channels. The properties conditioned by the structure of charged membranes determine their application in separation processes (water treatment, electrolyte concentration, food industry and others), energy (reverse electrodialysis, fuel cells and others), and chlore-alkali production and others. The purpose of this review is to provide guidelines for modeling the transport of ions and water in charged membranes, as well as to describe the latest advances in this field with a focus on power generation systems. We briefly describe the main structural elements of charged membranes which determine their ion and water transport characteristics. The main governing equations and the most commonly used theories and assumptions are presented and analyzed. The known models are classified and then described based on the information about the equations and the assumptions they are based on. Most attention is paid to the models which have the greatest impact and are most frequently used in the literature. Among them, we focus on recent models developed for proton-exchange membranes used in fuel cells and for membranes applied in reverse electrodialysis.


Assuntos
Membranas Artificiais , Prótons , Íons/química , Transporte Biológico , Troca Iônica
6.
Int J Mol Sci ; 23(10)2022 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-35628589

RESUMO

It is known that ammonium has a higher permeability through anion exchange and bipolar membranes compared to K+ cation that has the same mobility in water. However, the mechanism of this high permeability is not clear enough. In this study, we develop a mathematical model based on the Nernst−Planck and Poisson's equations for the diffusion of ammonium chloride through an anion-exchange membrane; proton-exchange reactions between ammonium, water and ammonia are taken into account. It is assumed that ammonium, chloride and OH− ions can only pass through membrane hydrophilic pores, while ammonia can also dissolve in membrane matrix fragments not containing water and diffuse through these fragments. It is found that due to the Donnan exclusion of H+ ions as coions, the pH in the membrane internal solution increases when approaching the membrane side facing distilled water. Consequently, there is a change in the principal nitrogen-atom carrier in the membrane: in the part close to the side facing the feed NH4Cl solution (pH < 8.8), it is the NH4+ cation, and in the part close to distilled water, NH3 molecules. The concentration of NH4+ reaches almost zero at a point close to the middle of the membrane cross-section, which approximately halves the effective thickness of the diffusion layer for the transport of this ion. When NH3 takes over the nitrogen transport, it only needs to pass through the other half of the membrane. Leaving the membrane, it captures an H+ ion from water, and the released OH− moves towards the membrane side facing the feed solution to meet the NH4+ ions. The comparison of the simulation with experiment shows a satisfactory agreement.


Assuntos
Amônia , Compostos de Amônio , Cloreto de Amônio , Ânions , Cloretos , Nitrogênio , Permeabilidade , Água
7.
Int J Mol Sci ; 22(7)2021 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-33805500

RESUMO

In this book, the papers published in the second issue, "Ion and Molecule Transport in Membrane Systems 2 [...].


Assuntos
Membrana Celular/metabolismo , Íons/metabolismo , Membranas Artificiais , Animais , Transporte Biológico , Água/metabolismo
9.
Int J Mol Sci ; 22(11)2021 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-34067406

RESUMO

The use of reactive electrochemical membranes (REM) in flow-through mode during the anodic oxidation of organic compounds makes it possible to overcome the limitations of plate anodes: in the case of REM, the area of the electrochemically active surface is several orders of magnitude larger, and the delivery of organic compounds to the reaction zone is controlled by convective flow rather than diffusion. The main problem with REM is the formation of fouling and gas bubbles in the pores, which leads to a decrease in the efficiency of the process because the hydraulic resistance increases and the electrochemically active surface is shielded. This work aims to study the processes underlying the reduction in the efficiency of anodic oxidation, and in particular the formation of gas bubbles and the recharge of the REM pore surface at a current density exceeding the limiting kinetic value. We propose a simple one-dimensional non-stationary model of the transport of diluted species during the anodic oxidation of paracetamol using REM to describe the above effects. The processing of the experimental data was carried out. It was found that the absolute value of the zeta potential of the pore surface decreases with time, which leads to a decrease in the permeate flux due to a reduction in the electroosmotic flow. It was shown that in the solution that does not contain organic components, gas bubbles form faster and occupy a larger pore fraction than in the case of the presence of paracetamol; with an increase in the paracetamol concentration, the gas fraction decreases. This behavior is due to a decrease in the generation of oxygen during the recombination reaction of the hydroxyl radicals, which are consumed in the oxidation reaction of the organic compounds. Because the presence of bubbles increases the hydraulic resistance, the residence time of paracetamol-and consequently its degradation degree-increases, but the productivity goes down. The model has predictive power and, after simple calibration, can be used to predict the performance of REM anodic oxidation systems.


Assuntos
Gases/química , Compostos Orgânicos/química , Eletrodos , Radical Hidroxila/química , Membranas Artificiais , Oxirredução , Poluentes Químicos da Água/química
10.
Int J Mol Sci ; 22(24)2021 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-34948329

RESUMO

Visualization of electroconvective (EC) vortices at the undulated surface of an AMX anion-exchange membrane (Astom, Osaka, Japan) was carried out in parallel with the measurement of chronopotentiograms. Weak polybasic acid salts, including 0.02 M solutions of tartaric (NaHT), phosphoric (NaH2PO4), and citric (NaH2Cit) acids salts, and NaCl were investigated. It was shown that, for a given current density normalized to the theoretical limiting current calculated by the Leveque equation (i/ilimtheor), EC vortex zone thickness, dEC, decreases in the order NaCl > NaHT > NaH2PO4 > NaH2Cit. This order is inverse to the increase in the intensity of proton generation in the membrane systems under study. The higher the intensity of proton generation, the lower the electroconvection. This is due to the fact that protons released into the depleted solution reduce the space charge density, which is the driver of EC. In all studied systems, a region in chronopotentiograms between the rapid growth of the potential drop and the attainment of its stationary values corresponds to the appearance of EC vortex clusters. The amplitude of the potential drop oscillations in the chronopotentiograms is proportional to the size of the observed vortex clusters.


Assuntos
Ácidos/química , Ânions/química , Membranas/química , Sais/química , Técnicas Eletroquímicas/métodos , Troca Iônica , Membranas Artificiais
11.
Int J Mol Sci ; 22(3)2021 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-33572516

RESUMO

The interplay between the ion exchange capacity, water content and concentration dependences of conductivity, diffusion permeability, and counterion transport numbers (counterion permselectivity) of CJMA-3, CJMA-6 and CJMA-7 (Hefei Chemjoy Polymer Materials Co. Ltd., China) anion-exchange membranes (AEMs) is analyzed using the application of the microheterogeneous model to experimental data. The structure-properties relationship for these membranes is examined when they are bathed by NaCl and Na2SO4 solutions. These results are compared with the characteristics of the well-studied homogenous Neosepta AMX (ASTOM Corporation, Japan) and heterogeneous AMH-PES (Mega a.s., Czech Republic) anion-exchange membranes. It is found that the CJMA-6 membrane has the highest counterion permselectivity (chlorides, sulfates) among the CJMAED series membranes, very close to that of the AMX membrane. The CJMA-3 membrane has the transport characteristics close to the AMH-PES membrane. The CJMA-7 membrane has the lowest exchange capacity and the highest volume fraction of the intergel spaces filled with an equilibrium electroneutral solution. These properties predetermine the lowest counterion transport number in CJMA-7 among other investigated AEMs, which nevertheless does not fall below 0.87 even in 1.0 eq L-1 solutions of NaCl or Na2SO4. One of the reasons for the decrease in the permselectivity of CJMAED membranes is the extended macropores, which are localized at the ion-exchange material/reinforcing cloth boundaries. In relatively concentrated solutions, the electric current prefers to pass through these well-conductive but nonselective macropores rather than the highly selective but low-conductive elements of the gel phase. It is shown that the counterion permselectivity of the CJMA-7 membrane can be significantly improved by coating its surface with a dense homogeneous ion-exchange film.


Assuntos
Ânions/química , Condutividade Elétrica , Membranas Artificiais , Cloretos/química , Difusão , Compostos Férricos/química , Ácido Hialurônico/química , Troca Iônica , Permeabilidade , Cloreto de Sódio/química , Sulfatos/química , Água/química
12.
Int J Mol Sci ; 21(15)2020 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-32752236

RESUMO

Nowadays, ion-exchange membranes have numerous applications in water desalination, electrolysis, chemistry, food, health, energy, environment and other fields. All of these applications require high selectivity of ion transfer, i.e., high membrane permselectivity. The transport properties of ion-exchange membranes are determined by their structure, composition and preparation method. For various applications, the selectivity of transfer processes can be characterized by different parameters, for example, by the transport number of counterions (permselectivity in electrodialysis) or by the ratio of ionic conductivity to the permeability of some gases (crossover in fuel cells). However, in most cases there is a correlation: the higher the flux density of the target component through the membrane, the lower the selectivity of the process. This correlation has two aspects: first, it follows from the membrane material properties, often expressed as the trade-off between membrane permeability and permselectivity; and, second, it is due to the concentration polarization phenomenon, which increases with an increase in the applied driving force. In this review, both aspects are considered. Recent research and progress in the membrane selectivity improvement, mainly including a number of approaches as crosslinking, nanoparticle doping, surface modification, and the use of special synthetic methods (e.g., synthesis of grafted membranes or membranes with a fairly rigid three-dimensional matrix) are summarized. These approaches are promising for the ion-exchange membranes synthesis for electrodialysis, alternative energy, and the valuable component extraction from natural or waste-water. Perspectives on future development in this research field are also discussed.


Assuntos
Íons/química , Membranas Artificiais , Nanopartículas/química , Polímeros/química , Troca Iônica , Transporte de Íons , Estrutura Molecular , Permeabilidade , Porosidade , Água/química
13.
Int J Mol Sci ; 21(3)2020 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-32024103

RESUMO

Electrodialysis (ED) has been demonstrated as an effective membrane method for desalination, concentration, and separation. Electroconvection (EC) is a phenomenon which can essentially increase the mass transfer rate and reduce the undesirable water splitting effect. Efforts by a number of researchers are ongoing to create conditions for developing EC, in particular, through the formation of electrical heterogeneity on the membrane surface. We attempt, for the first time, to optimize the parameters of surface electrical heterogeneity for ion-exchange membranes used in a laboratory ED cell. Thirteen different patterns on the surface of two Neosepta anion-exchange membranes, AMX and AMX-Sb, were tested. Low-conductive fluoropolymer spots were formed on the membrane surface using the electrospinning technique. Spots in the form of squares, rectangles, and circles with different sizes and distances between them were applied. We found that the spots' shape did not have a visible effect. The best effect, i.e., the maximum mass transfer rate and the minimum water splitting rate, was found when the spots' size was close to that of the diffusion layer thickness, δ (about 250 µm in the experimental conditions), and the distance between the spots was slightly larger than δ, such that the fraction of the screened surface was about 20%.


Assuntos
Diálise/métodos , Eletricidade , Filtração/instrumentação , Membranas Artificiais , Água/química , Diálise/instrumentação , Técnicas Eletroquímicas , Troca Iônica , Propriedades de Superfície
14.
Int J Mol Sci ; 20(14)2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31340475

RESUMO

Electrodialysis (ED) with ion-exchange membranes is a promising method for the extraction of phosphates from municipal and other wastewater in order to obtain cheap mineral fertilizers. Phosphorus is transported through an anion-exchange membrane (AEM) by anions of phosphoric acid. However, which phosphoric acid anions carry the phosphorus in the membrane and the boundary solution, that is, the mechanism of phosphorus transport, is not yet clear. Some authors report an unexpectedly low current efficiency of this process and high energy consumption. In this paper, we report the partial currents of H2PO4-, HPO42-, and PO43- through Neosepta AMX and Fujifilm AEM Type X membranes, as well as the partial currents of H2PO4- and H+ ions through a depleted diffusion layer of a 0.02 M NaH2PO4 feed solution measured as functions of the applied potential difference across the membrane under study. It was shown that the fraction of the current transported by anions through AEMs depend on the total current density/potential difference. This was due to the fact that the pH of the internal solution in the membrane increases with the growing current due to the increasing concentration polarization (a lower electrolyte concentration at the membrane surface leads to higher pH shift in the membrane). The HPO42- ions contributed to the charge transfer even when a low current passed through the membrane; with an increasing current, the contribution of the HPO42- ions grew, and when the current was about 2.5 ilimLev (ilimLev was the theoretical limiting current density), the PO43- ions started to carry the charge through the membrane. However, in the feed solution, the pH was 4.6 and only H2PO4- ions were present. When H2PO4- ions entered the membrane, a part of them transformed into doubly and triply charged anions; the H+ ions were released in this transformation and returned to the depleted diffusion layer. Thus, the phosphorus total flux, jP (equal to the sum of the fluxes of all phosphorus-bearing species) was limited by the H2PO4- transport from the bulk of feed solution to the membrane surface. The value of jP was close to ilimLev/F (F is the Faraday constant). A slight excess of jP over ilimLev/F was observed, which is due to the electroconvection and exaltation effects. The visualization showed that electroconvection in the studied systems was essentially weaker than in systems with strong electrolytes, such as NaCl.


Assuntos
Técnicas Eletroquímicas , Ácidos Fosfóricos/isolamento & purificação , Águas Residuárias/química , Ânions , Diálise/métodos , Difusão , Humanos , Concentração de Íons de Hidrogênio , Troca Iônica , Cinética , Membranas Artificiais , Eletricidade Estática
15.
Membranes (Basel) ; 13(1)2023 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-36676891

RESUMO

The application of electrodialysis for tartrate stabilization and reagent-free acidity correction of wine and juices is attracting increasing interest. New aliphatic membranes CJMC-3 and CJMA-3 and aromatic membranes CSE and ASE were tested to determine their suitability for use in these electrodialysis processes and to evaluate the fouling of these membranes by wine components for a short (6-8 h) operating time. Using IR spectroscopy, optical indication and measurement of surface contact angles, the chemical composition of the studied membranes, as well as some details about their fouling by wine components, was clarified. The current-voltage charsacteristics, conductivity and water-splitting capacity of the membranes before and after electrodialysis were analyzed. We found that in the case of cation-exchange membranes, complexes of anthocyanins with metal ions penetrate into the bulk (CJMC-3) or are localized on the surface (CSE), depending on the degree of crosslinking of the polymer matrix. Adsorption of wine components by the surface of anion-exchange membranes CJMA-3 and ASE causes an increase in water splitting. Despite fouling under identical conditions of electrodialysis, membrane pair CJMC-3 and CJMA-3 provided 18 ± 1 tartrate recovery with 31 · 10-3 energy consumption, whereas CSE and ASE provided 20 ± 1% tartrate recovery with an energy consumption of 28 · 10-3 Wh, in addition to reducing the conductivity of wine by 20 ± 1%. The casting of aliphatic polyelectrolyte films on the surface of aromatic membranes reduces fouling with a relatively small increase in energy consumption and approximately the same degree of tartrate recovery compared to pristine CSE and ASE.

16.
Membranes (Basel) ; 13(1)2023 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-36676909

RESUMO

In spite of wide variety of commercial ion-exchange membranes, their characteristics, in particular, electrical conductivity and counterion permselectivity, are unsatisfactory for some applications, such as electrolyte solution concentration. This study is aimed at obtaining an anion-exchange membrane (AEM) of high performance in concentrated solutions. An AEM is prepared with a polypyrrole (PPy)-based modification of a heterogeneous AEM with quaternary ammonium functional groups. Concentration dependences of the conductivity, diffusion permeability and Cl− transport number in NaCl solutions are measured and simulated using a new version of the microheterogeneous model. The model describes changes in membrane swelling with increasing concentration and the effect of these changes on the transport characteristics. It is assumed that PPy occupies macro- and mesopores of the host membrane where it replaces non-selective electroneutral solution. Increasing conductivity and selectivity are explained by the presence of positively charged PPy groups. It is found that the conductivity of a freshly prepared membrane reaches 20 mS/cm and the chloride transport number > 0.99 in 4 M NaCl. A choice of input parameters allows quantitative agreement between the experimental and simulation results. However, PPy has shown itself to be an unstable material. This article discusses what parameters a membrane can have to show such exceptional characteristics.

17.
Membranes (Basel) ; 13(5)2023 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-37233570

RESUMO

New processes for recycling valuable materials from used lithium-ion batteries (LIBs) need to be developed. This is critical to both meeting growing global demand and mitigating the electronic waste crisis. In contrast to the use of reagent-based processes, this work shows the results of testing a hybrid electrobaromembrane (EBM) method for the selective separation of Li+ and Co2+ ions. Separation is carried out using a track-etched membrane with a pore diameter of 35 nm, which can create conditions for separation if an electric field and an oppositely directed pressure field are applied simultaneously. It is shown that the efficiency of ion separation for a lithium/cobalt pair can be very high due to the possibility of directing the fluxes of separated ions to opposite sides. The flux of lithium through the membrane is about 0.3 mol/(m2 × h). The presence of coexisting nickel ions in the feed solution does not affect the flux of lithium. It is shown that the EBM separation conditions can be chosen so that only lithium is extracted from the feed solution, while cobalt and nickel remain in it.

18.
Membranes (Basel) ; 13(7)2023 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-37505013

RESUMO

Phosphate recovery from different second streams using electrodialysis (ED) is a promising step to a nutrients circular economy. However, the relatively low ED performance hinders the widespread adoption of this environmentally sound method. The formation of "bonded species" between phosphates and the weakly basic fixed groups (primary and secondary amines) of the anion exchange membrane can be the cause of decrease in current efficiency and increase in energy consumption. ED processing of NaxH(3-x)PO4 alkaline solutions and the use of intense current modes promote the formation of a bipolar junction from negatively charged bound species and positively charged fixed groups. This phenomenon causes a change in the shape of current-voltage curves, increase in resistance, and an enhancement in proton generation during long-term operation of anion-exchange membrane with weakly basic fixed groups. Shielding of primary and secondary amines with a modifier containing quaternary ammonium bases significantly improves ED performance in the recovery of phosphates from NaxH(3-x)PO4 solution with pH 4.5. Indeed, in the limiting and underlimiting current modes, 40% of phosphates are recovered 1.3 times faster, and energy consumption is reduced by 1.9 times in the case of the modified membrane compared to the pristine one. Studies were performed using a new commercial anion exchange membrane CJMA-2.

19.
Membranes (Basel) ; 13(5)2023 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-37233516

RESUMO

The entrance of even a small amount of phosphorus compounds into natural waters leads to global problems that require the use of modern purification technologies. This paper presents the results of testing a hybrid electrobaromembrane (EBM) method for the selective separation of Cl- (always present in phosphorus-containing waters) and H2PO4- anions. Separated ions of the same charge sign move in an electric field through the pores of a nanoporous membrane to the corresponding electrode, while a commensurate counter-convective flow in the pores is created by a pressure drop across the membrane. It has been shown that EBM technology provides high fluxes of ions being separated across the membrane as well as a high selectivity coefficient compared to other membrane methods. During the processing of solution containing 0.05 M NaCl and 0.05 M NaH2PO4, the flux of phosphates through a track-etched membrane can reach 0.29 mol/(m2×h). Another possibility for separation is the EBM extraction of chlorides from the solution. Its flux can reach 0.40 mol/(m2×h) through the track-etched membrane and 0.33 mol/(m2×h) through a porous aluminum membrane. The separation efficiency can be very high by using both the porous anodic alumina membrane with positive fixed charges and the track-etched membrane with negative fixed charges due to the possibility of directing the fluxes of separated ions in opposite sides.

20.
Polymers (Basel) ; 15(10)2023 May 12.
Artigo em Inglês | MEDLINE | ID: mdl-37242863

RESUMO

Innovative ion exchange membranes have become commercially available in recent years. However, information about their structural and transport characteristics is often extremely insufficient. To address this issue, homogeneous anion exchange membranes with the trade names ASE, CJMA-3 and CJMA-6 have been investigated in NaxH(3-x)PO4 solutions with pH 4.4 ± 0.1, 6.6 and 10.0 ± 0.2, as well as NaCl solutions with pH 5.5 ± 0.1. Using IR spectroscopy and processing the concentration dependences of the electrical conductivity of these membranes in NaCl solutions, it was shown that ASE has a highly cross-linked aromatic matrix and mainly contains quaternary ammonium groups. Other membranes have a less cross-linked aliphatic matrix based on polyvinylidene fluoride (CJMA-3) or polyolefin (CJMA-6) and contain quaternary amines (CJMA-3) or a mixture of strongly basic (quaternary) and weakly basic (secondary) amines (CJMA-6). As expected, in dilute solutions of NaCl, the conductivity of membranes increases with an increase in their ion-exchange capacity: CJMA-6 < CJMA-3 << ASE. Weakly basic amines appear to form bound species with proton-containing phosphoric acid anions. This phenomenon causes a decrease in the electrical conductivity of CJMA-6 membranes compared to other studied membranes in phosphate-containing solutions. In addition, the formation of the neutral and negatively charged bound species suppresses the generation of protons by the "acid dissociation" mechanism. Moreover, when the membrane is operated in overlimiting current modes and/or in alkaline solutions, a bipolar junction is formed at the CJMA- 6/depleted solution interface. The CJMA-6 current-voltage curve becomes similar to the well-known curves for bipolar membranes, and water splitting intensifies in underlimiting and overlimiting modes. As a result, energy consumption for electrodialysis recovery of phosphates from aqueous solutions almost doubles when using the CJMA-6 membrane compared to the CJMA-3 membrane.

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