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Electromembrane Processes: From Fundamentals to Applications

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A special issue of Membranes (ISSN 2077-0375). This special issue belongs to the section "Membrane Chemistry".

Deadline for manuscript submissions: closed (30 January 2024) | Viewed by 19622

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Dr. Stanislav S. Melnikov

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Faculty of Chemistry and High Technologies, Kuban State University, 350040 Krasnodar, Russia
Interests: electrodialysis; ion exchange membranes; bipolar electrodialysis; lithium hydroxide production; electromembrane processes in non-aqueous systems; dialysis; proton-blocking membranes

Special Issue Information

Dear Colleagues,

Nowadays, electromembrane processes are used for in processing of dairy products and juices and in wine conditioning; in new directions of “green chemistry”, e.g., the separation of biomass fermentation products (amino acids, biofuel, monomers for the production of plastics, including biodegradable); in the chemical industry (correction of pH, synthesis of acids and alkali from salts contained in the processing solutions, recycling and concentration of salts); in the medical industry (obtaining of biologically active substances and pharmaceuticals); in analytical chemistry (preliminary concentration of solutions, background suppression in ion chromatography, membrane sensors). These processes include conventional and bipolar electrodialysis, dialysis, and membrane electrolysis as well as hybrid technologies involving the use of reverse osmosis, nanofiltration, and gas separation.

The transfer of ions and water molecules in these processes occurs under the action of several driving forces (concentration gradients, electric potential, and pressure) in multicomponent systems. Usually, this transport is accompanied by chemical reactions in the membrane bulk and at its interfaces. Study of transport process regularities requires a multidisciplinary approach using knowledge of chemistry, material science, physics, hydrodynamics, chemical engineering, and applied mathematics.

The main aim of this Special Issue is to provide readers with new knowledge about the mechanisms of ion and water molecule transport in membrane systems at different spatial scales (from nanometer to millimeter), elucidation of their interaction and the dependence of these mechanisms on the chemical nature of treated matter, the chemical composition and structure of the volume and surface of ion exchange membranes, the possibilities for controlling membrane properties, and processes of H⁺ and OH⁻ ion generation and ion and water transport in membrane systems as well as to present new trends in the application of electromembrane processes for the treatment of complex solutions from the food, chemical, and hydrometallurgy industries.

For this Special Issue, original research articles and reviews are welcome. Research areas of interest include (but are not limited to) the following:

Transport characteristics and structure–property relationships in ion exchange membranes;
The impact of the concentration polarization phenomenon on electromembrane systems and process performance (including pH shifts, chemical transformations in the treated solution, scaling);
The behavior of ion exchange membranes and membrane modules in various processes (dialysis, electrodialysis, electrolysis, capacitive deionization, fuel cells, microfluidic devices, bioreactors, potentiometric sensors, etc.);
Ion exchange membrane fouling and scaling and ways to counter these phenomena;
New areas for the application of ion exchange membranes.

Dr. Stanislav S. Melnikov
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Membranes is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2200 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

electrodialysis
dialysis
bipolar electrodialysis
ion exchange membranes
electrolysis
mathematical modeling
concentration polarization
electromembrane synthesis
electromembrane process

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Published Papers (9 papers)

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12 pages, 2830 KiB

Open AccessArticle

Electrotransport Properties of Perfluorinated Cation-Exchange Membranes of Various Thickness

by Irina Falina, Natalia Loza, Marina Brovkina, Ekaterina Titskaya, Sergey Timofeev and Natalia Kononenko

Membranes 2023, 13(11), 873; https://doi.org/10.3390/membranes13110873 - 3 Nov 2023

Viewed by 1668

Abstract

The present work discusses the influence of the thickness of MF-4SK perfluorinated sulfonic cation-exchange membranes on their electrotransport properties in hydrochloric acid solutions. It is found that diffusion permeability and conductivity are primarily determined with the specific water content of the membranes and increase with their increase. Analysis of the contribution of reverse diffusion through the membrane to the value of the limiting current shows that it can reach 20% for membranes with a thickness of 60 μm. A study of the characteristics of the fuel cell with perfluorinated membranes of different thicknesses shows that the membrane thickness affects both the ohmic resistance of the membrane-electrode assembly and the diffusion limitations of proton transport in polymer electrolytes. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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25 pages, 6946 KiB

Open AccessArticle

Ion Transport and Process of Water Dissociation in Electromembrane System with Bipolar Membrane: Modelling of Symmetrical Case

by Stanislav Melnikov

Membranes 2023, 13(1), 47; https://doi.org/10.3390/membranes13010047 - 29 Dec 2022

Cited by 5 | Viewed by 2549

Abstract

A model is proposed that describes the transfer of ions and the process of water dissociation in a system with a bipolar membrane and adjacent diffusion layers. The model considers the transfer of four types of ions: the cation and anion of salt and the products of water dissociation—hydrogen and hydroxyl ions. To describe the process of water dissociation, a model for accelerating the dissociation reaction with the participation of ionogenic groups of the membrane is adopted. The boundary value problem is solved numerically using COMSOL^® Multiphysics 5.5 software. An analysis of the results of a numerical experiment shows that, at least in a symmetric electromembrane system, there is a kinetic limitation of the water dissociation process, apparently associated with the occurrence of water recombination reaction at the of the bipolar region. An interpretation of the entropy factor (β) is given as a characteristic length, which shows the possibility of an ion that appeared because of the water dissociation reaction to be removed from the reaction zone without participating in recombination reactions. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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18 pages, 3193 KiB

Open AccessArticle

Effect of Co-Existing Ions on Salinity Gradient Power Generation by Reverse Electrodialysis Using Different Ion Exchange Membrane Pairs

by Tuğçe Zeynep Kaya, Esra Altıok, Enver Güler and Nalan Kabay

Membranes 2022, 12(12), 1240; https://doi.org/10.3390/membranes12121240 - 7 Dec 2022

Cited by 6 | Viewed by 1965

Abstract

This study investigates the influence of co-existing ions on the salinity gradient power generation performance of the reverse electrodialysis (RED) using three different commercial ion exchange membrane pairs. The feed solutions, including the mixture of two different salts, were prepared with 90 wt.% of NaCl and 10 wt.% of LiCl, KCl, CaCl₂, MgCl₂ or Na₂SO₄ by keeping the salt ratio between high concentrate solution and low concentrate solution constant as 1:30 (g/g) at various flow velocities (50, 125 and 200 mL/min). It was observed that the divalent ions exhibited a negative impact on the performance of the RED system due to their high valence and low ionic mobility depending on their high hydrated radius and low diffusion coefficients compared to those of the monovalent ions. On the other hand, the effect of the monovalent ions differed according to the properties of ion exchange membranes used in the RED stack. When the power generation performances of ion exchange membrane pairs employed in the RED stack were compared, it was considered that Neosepta AMX and CMX membranes provided the highest power density due to their low membrane thicknesses, low electrical resistances, and relatively high ion exchange capacities compared to other two commercial ion exchange membrane pairs. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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14 pages, 2871 KiB

Open AccessArticle

Hybrid Membrane Technology for Acid Recovery from Wastewater in Coated Steel Wire Production: A Pilot Scale Study

by Sergey Loza, Natalia Loza, Alexander Korzhov, Nazar Romanyuk, Nikita Kovalchuk and Stanislav Melnikov

Membranes 2022, 12(12), 1196; https://doi.org/10.3390/membranes12121196 - 27 Nov 2022

Cited by 5 | Viewed by 2519

Abstract

In the present study, the problem of sulfuric acid recycling from spent copper plating solution was solved using a hybrid membrane technology, including diffusion dialysis and electrodialysis. A real solution from the production of copper-coated steel wire, containing 1.45 mol/L of sulfuric acid, 0.67 mol/L of ferrous sulfate and 0.176 mol/L of copper sulfate, was processed. Diffusion dialysis with anion-exchange membranes was used to separate sulfuric acid and salts of heavy metals. Then, purified dilute sulfuric acid was concentrated by electrodialysis. The energy consumption for sulfuric acid electrodialysis concentration at a current density of 400 A/m² was 162 W·h/mol, with a current efficiency of 16%. After processing according to the hybrid membrane scheme, the solution contained 1.13 mol/L sulfuric acid, 0.077 mol/L ferrous sulfate and 0.022 mol/L copper sulfate. According to established requirements, the solution of a copper plating bath had to contain from 0.75 to 1.25 M sulfuric acid, 0.16–0.18 M of copper sulfate and ferrous sulfate not more than 0.15 M. The resulting acid solution with a small amount of ferrous sulfate and copper sulfate could be used to prepare a copper plating bath solution. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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18 pages, 4788 KiB

Open AccessArticle

Investigation of Transport Processes through Ion-Exchange Membranes Used in the Production of Amines from Their Salts Using Bipolar Electrodialysis

by Tatyana Karpenko, Nikita Kovalev, Vladislava Shramenko and Nikolay Sheldeshov

Membranes 2022, 12(11), 1126; https://doi.org/10.3390/membranes12111126 - 10 Nov 2022

Cited by 2 | Viewed by 1644

Abstract

The influence of the nature of amine solutions on the frequency spectrum of the electrochemical impedance of the bipolar membrane aMB-2m is investigated. Moreover, the effect of the circulation rate of solutions in the electrodialyzer chambers on the volt-ampere characteristics of the Ralex AMH and MA-40L anion-exchange membranes and the aMB-2m bipolar membrane has been investigated. The diffusion characteristics of various types of anion-exchange membranes in a system containing dimethylammonium sulfate ((DEA)₂H₂SO₄), as well as the diffusion characteristics of the Ralex AMH membrane in systems with methylammonium sulfate, dimethylammonium sulfate, diethylammonium sulfate, and ethylenediammonium sulfate ((MA)₂H₂SO₄, (DMA)₂H₂SO₄, (DEA)₂H₂SO₄, EDAH₂SO₄) have been studied. It is shown that diffusion permeability depends on the structure and composition of anion-exchange membranes, as well as on the nature of amines. The technical and economic characteristics of the electromembrane processes for the production of amines and sulfuric acid from amine salts are determined. It is shown that when using Ralex AMH anion-exchange membranes in an electrodialyzer together with bipolar aMB-2m membranes, higher concentrations of diethylamine and sulfuric acid are achieved, compared with the use of MA-40L anion-exchange membranes. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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26 pages, 2702 KiB

Open AccessArticle

Electrodialysis Desalination with Simultaneous pH Adjustment Using Bilayer and Bipolar Membranes, Modeling and Experiment

by Elena Nosova, Aslan Achoh, Victor Zabolotsky and Stanislav Melnikov

Membranes 2022, 12(11), 1102; https://doi.org/10.3390/membranes12111102 - 4 Nov 2022

Cited by 8 | Viewed by 3174

Abstract

A kinetic model of the bipolar electrodialysis process with a two-chamber unit cell formed by a bilayer (bipolar or asymmetric bipolar) and cation-exchange membrane is proposed. The model allows describing various processes: pH adjustment of strong electrolyte solutions, the conversion of a salt of a weak acid, pH adjustment of a mixture of strong and weak electrolytes. The model considers the non-ideal selectivity of the bilayer membrane, as well as the competitive transfer of cations (hydrogen and sodium ions) through the cation-exchange membrane. Analytical expressions are obtained that describe the kinetic dependences of pH and concentration of ionic components in the desalination (acidification) compartment for various cases. Comparison of experimental data with calculations results show a good qualitative and, in some cases, quantitative agreement between experimental and calculated data. The model can be used to predict the performance of small bipolar membrane electrodialysis modules designed for pH adjustment processes. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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19 pages, 4049 KiB

Open AccessArticle

Current-Voltage Characteristics of Membranes with Different Cation-Exchanger Content in Mineral Salt—Neutral Amino Acid Solutions under Electrodialysis

by Vera I. Vasil’eva, Elmara M. Akberova, Ali M. Saud and Victor I. Zabolotsky

Membranes 2022, 12(11), 1092; https://doi.org/10.3390/membranes12111092 - 2 Nov 2022

Cited by 1 | Viewed by 1788

Abstract

The features of the electrochemical behavior of experimental heterogeneous ion-exchange membranes with different mass fractions of sulfonated cation-exchange resin (from 45 to 65 wt%) have been studied by voltammetry during electrodialysis. Electromembrane systems with 0.01 M NaCl solution and with a mixed 0.01 M NaCl + 0.05 M phenylalanine (Phe) solution have been investigated. A significant influence of the ion-exchanger content on the parameters of current-voltage curves (CVCs) was established for the first time. Electrodialysis of the sodium chloride solution revealed a decrease in the length of the limiting current plateau and in the resistances of the second and third sections of the CVCs with an increase in the resin content in the membrane. The fact of the specific shape of the CVCs of all studied cation-exchange membrane samples in mixed solutions of the mineral salt and the amino acid was established. A specific feature of current-voltage curves is the presence of two plateaus of the limiting current and two values of the limiting current, respectively. This phenomenon in electromembrane systems with neutral amino acids has not been found before. The value of the first limiting current is determined by cations of the mineral salt, which are the main current carriers in the system. The presence of the second plateau and the corresponding second limiting current is due to the appearance of additional carriers due to the ability of phenylalanine as an organic ampholyte to participate in protolytic reactions. In the cation-exchange electromembrane system with the phenylalanine containing solution, two mechanisms of H⁺/OH⁻ ion generation through water splitting and acid dissociation are shown. The possibility of the generation of H⁺/OH⁻ ions at the enriched solution/cation-exchange membrane interface during electrodialysis of amino acid containing solutions is shown for the first time. The results of this study can be used to improve the process of electromembrane demineralization of neutral amino acid solutions by both targeted selection or the creation of new membranes and the selection of effective current operating modes. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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12 pages, 2528 KiB

Open AccessArticle

Structural and Electrotransport Properties of Perfluorinated Sulfocationic Membranes Modified by Silica and Zirconium Hydrophosphate

by Svetlana A. Shkirskaya, Natalia A. Kononenko and Sergej V. Timofeev

Membranes 2022, 12(10), 979; https://doi.org/10.3390/membranes12100979 - 8 Oct 2022

Cited by 5 | Viewed by 1473

Abstract

A correlation between changes in structural and electrotransport properties of membranes after modification by silica and zirconium hydrophosphate was established. The total water volume, volume fraction of the free water in the membrane and the volume fraction of the water having high binding energy were considered as structural characteristics, which were found from the curves of water distribution on the water binding energy and the effective pore radii. The conductivity, diffusion and electroosmotic permeabilities were investigated as electrotransport properties. The influence of the modifier type on the current flow paths in the membrane was analyzed within the framework of the extended three-wire model. It has been established that the treatment of membranes with alcohol before the intercalation of a modifier leads to the appearance of cavities with an effective size of more than 100 nm filled with free water with the binding energy less than 10 J/mol. It is accompanied with an increase in the diffusion permeability of hybrid membranes by approximately 3–6 times in NaCl and HCl solutions, which limits the application of such materials in proton exchange membrane fuel cells. The different conditions of modification of perfluorinated membranes with similar properties by the dopant with same type allow for the preparation of the hybrid materials for various applications such as electrodialysis concentration or electric current generation devices. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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Review

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17 pages, 345 KiB

Open AccessReview

Environmental Applications of Electromembrane Extraction: A Review

by Linping Shi, Mantang Chen, Ge Zhao, Xiaoyu Wang, Meijuan Fan, Ruihong Liu and Fuwei Xie

Membranes 2023, 13(8), 705; https://doi.org/10.3390/membranes13080705 - 28 Jul 2023

Cited by 8 | Viewed by 1622

Abstract

Electromembrane extraction (EME) is a miniaturized extraction technique that has been widely used in recent years for the analysis and removal of pollutants in the environment. It is based on electrokinetic migration across a supported liquid membrane (SLM) under the influence of an external electrical field between two aqueous compartments. Based on the features of the SLM and the electrical field, EME offers quick extraction, effective sample clean-up, and good selectivity, and limits the amount of organic solvent used per sample to a few microliters. In this paper, the basic devices (membrane materials and types of organic solvents) and influencing factors of EME are first introduced, and the applications of EME in the analysis and removal of environmental inorganic ions and organic pollutants are systematically reviewed. An outlook on the future development of EME for environmental applications is also given. Full article

(This article belongs to the Special Issue Electromembrane Processes: From Fundamentals to Applications)

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