Is It Possible to Prepare a "Super" Anion-Exchange Membrane by a Polypyrrole-Based Modification?

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.

Electrodialysis Tartrate Stabilization of Wine Materials: Fouling and a New Approach to the Cleaning of Aliphatic Anion-Exchange Membranes.

Electrodialysis (ED) is an attractive method of tartrate stabilization of wine due to its rapidity and reagentlessness. At the same time, fouling of ion-exchange membranes by the components of wine materials is still an unsolved problem. The effect of ethanol, polyphenols (mainly anthocyanins and proanthocyanidins) and saccharides (fructose) on the fouling of aliphatic ion-exchange membranes CJMA-6 and CJMC-5 (manufactured by Hefei Chemjoy Polymer Materials Co. Ltd., Hefei, China) was analyzed using model solutions. It was shown that the mechanism and consequences of fouling are different in the absence of an electric field and during electrodialysis. In particular, a layer of colloidal particles is deposited on the surface of the CJMA-6 anion-exchange membrane in underlimiting current modes. Its thickness increases with increasing current density, apparently due to the implementation of a trap mechanism involving tartaric acid anions, as well as protons, which are products of water splitting and "acid dissociation". A successful attempt was made to clean CJMA-6 in operando by pumping a water-alcohol solution of KCl through the desalination compartment and changing electric field direction. It has been established that such a cleaning process suppresses the subsequent biofouling of ion-exchange membranes. In addition, selective recovery of polyphenols with high antioxidant activity is possible.

A Review on Ion-Exchange Membrane Fouling during the Electrodialysis Process in the Food Industry, Part 1: Types, Effects, Characterization Methods, Fouling Mechanisms and Interactions.

Electrodialysis (ED) was first established for water desalination and is still highly recommended in this field for its high water recovery, long lifetime and acceptable electricity consumption. Today, thanks to technological progress in ED processes and the emergence of new ion-exchange membranes (IEMs), ED has been extended to many other applications in the food industry. This expansion of uses has also generated several problems such as IEMs' lifetime limitation due to different ageing phenomena (because of organic and/or mineral compounds). The current commercial IEMs show excellent performance in ED processes; however, organic foulants such as proteins, surfactants, polyphenols or other natural organic matters can adhere on their surface (especially when using anion-exchange membranes: AEMs) forming a colloid layer or can infiltrate the membrane matrix, which leads to the increase in electrical resistance, resulting in higher energy consumption, lower water recovery, loss of membrane permselectivity and current efficiency as well as lifetime limitation. If these aspects are not sufficiently controlled and mastered, the use and the efficiency of ED processes will be limited since, it will no longer be competitive or profitable compared to other separation methods. In this work we reviewed a significant amount of recent scientific publications, research and reviews studying the phenomena of IEM fouling during the ED process in food industry with a special focus on the last decade. We first classified the different types of fouling according to the most commonly used classifications. Then, the fouling effects, the characterization methods and techniques as well as the different fouling mechanisms and interactions as well as their influence on IEM matrix and fixed groups were presented, analyzed, discussed and illustrated.

Understanding of Adsorption and Desorption Mechanisms of Anthocyanins and Proanthocyanidins on Heterogeneous and Homogeneous Cation-Exchange Membranes.

The presence of membrane fouling is the main drawback in membrane processes, and it is related to the premature use and high cost for the replacement of membranes. Polyphenols in cranberry juice are associated with ion-exchange membrane fouling, and it results in a loss of these beneficial compounds in the juice when treated by membrane processes such as electrodialysis. In the present work, four heterogeneous or pseudohomogeneous cation-exchange membranes (CSE-fg, MK-40, CEM Type-II, and CJMC-5), different in terms of the polymer matrix (aromatic, aliphatic), exchange capacity, size, and location of meso and macropores, were studied to understand the impact of the membrane structure and physico-chemical properties on adsorption and desorption of phenolic compounds (anthocyanins and proanthocyanidins) from cranberry juice. It appeared from these results that MK-40, CEM Type-II, and CSE-fg were more prone to fouling due to their high ion-exchange capacity, their thickness, and the presence of meso and macropores in their structure. Indeed, electrostatic interactions occurred between fixed groups of membranes and polyphenolic ions. Desorption of the entire membrane and cryogenic grinding with pH adjusted to 10 allowed a better recovery of anthocyanins and proanthocyanidins (PACs), respectively, since hydroxide ions competed with polyphenols and membrane that induced desorption of polyphenols. In the future, this new knowledge will become the basis for a more sensible choice of membranes and for the development of protocols for extending their life cycle.

Adsorption of Anthocyanins by Cation and Anion Exchange Resins with Aromatic and Aliphatic Polymer Matrices.

This study examines the mechanisms of adsorption of anthocyanins from model aqueous solutions at pH values of 3, 6, and 9 by ion-exchange resins making the main component of heterogeneous ion-exchange membranes. This is the first report demonstrating that the pH of the internal solution of a KU-2-8 aromatic cation-exchange resin is 2-3 units lower than the pH of the external bathing anthocyanin-containing solution, and the pH of the internal solution of some anion-exchange resins with an aromatic (AV-17-8, AV-17-2P) or aliphatic (EDE-10P) matrix is 2-4 units higher than the pH of the external solution. This pH shift is caused by the Donnan exclusion of hydroxyl ions (in the KU-2-8 resin) or protons (in the AV-17-8, AV-17-2P, and EDE-10P resins). The most significant pH shift is observed for the EDE-10P resin, which has the highest ion-exchange capacity causing the highest Donnan exclusion. Due to the pH shift, the electric charge of anthocyanin inside an ion-exchange resin differs from its charge in the external solution. At pH 6, the external solution contains uncharged anthocyanin molecules. However, in the AV-17-8 and AV-17-2P resins, the anthocyanins are present as singly charged anions, while in the EDE-10P resin, they are in the form of doubly charged anions. Due to the electrostatic interactions of these anions with the positively charged fixed groups of anion-exchange resins, the adsorption capacities of AV-17-8, AV-17-2P, and EDE-10P were higher than expected. It was established that the electrostatic interactions of anthocyanins with the charged fixed groups increase the adsorption capacity of the aromatic resin by a factor of 1.8-2.5 compared to the adsorption caused by the π-π (stacking) interactions. These results provide new insights into the fouling mechanism of ion-exchange materials by polyphenols; they can help develop strategies for membrane cleaning and for extracting anthocyanins from juices and wine using ion-exchange resins and membranes.