Selective adsorption in ion exchange membranes: The effect of solution ion composition on ion partitioning.

Electrodialysis is a water desalination technology that enables selective separation of ions, making it a promising solution for sustainable water reuse. The selectivity of the process is mainly determined by the properties of ion exchange membranes that can vary depending on the composition of ions in water, such as water uptake and charge density. In this work, we studied selective adsorption of Na+ and K+ ions in various ion exchange membranes considering the effect of solution ion composition on membrane water volume fraction. For that purpose, we conducted membrane adsorption experiments using solutions with Na+ and K+ ions with different ion compositions including Li+, Ca2+ or Mg2+ ions at different concentrations (0.001 - 0.25 M). The experiments showed that with the total ion concentration and the amount of divalent ions in solution, the membrane water volume fraction decreases while the selective adsorption of the smaller (hydrated) K+ ions over the Na+ ions in the membrane increases. We developed a theoretical framework based on Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) theory to describe the effect of membrane water volume fraction on selective adsorption of the ions by including volumetric effects, such as size exclusion. The developed framework was used to describe ion partitioning results of the membrane adsorption experiments. In addition, the effect of solution ion composition on selective ion removal during electrodialysis operation was evaluated using experimental data and theoretical calculations. The results of this study show that considering volumetric effects can improve the ion partitioning description in ion exchange membranes for solutions with various ion compositions.

Modeling micropollutant removal by nanofiltration and reverse osmosis membranes: considerations and challenges.

Organic micropollutants (OMPs) in drinking water constitute a potential risk to human health; therefore, effective removal of these pollutants is required. Nanofiltration (NF) and reverse osmosis (RO) are promising membrane-based technologies to remove OMPs. In NF and RO, the rejection of OMPs depends on the properties and characteristics of the membrane, the solute, and the solution. In this review, we discuss how these properties can be included in models to study and predict the rejection of OMPs. Initially, an OMP classification is proposed to capture the relevant properties of 58 OMPs. Following the methodology described in this study, more and new OMPs can be easily included in this classification. The classification aims to increase the comprehension and mechanistic understanding of OMP removal. Based on the physicochemical principles used to classify the 58 OMPs, it is expected that other OMPs in the same groups will be similarly rejected. From this classification, we present an overview of the rejection mechanisms involved in the removal of specific OMP groups. For instance, we discuss the removal of OMPs classified as perfluoroalkyl substances (e.g., perfluorooctanoic acid, PFOA). These substances are highly relevant due to their human toxicity at extremely low concentration as well as their persistence and omnipresence in the environment. Finally, we discuss how the rejection of OMPs can be predicted by describing both the membrane-solution interface and calculating the transport of solutes inside the membrane. We illustrate the importance and impact of different rejection mechanisms and interfacial phenomena on OMP removal and propose an extended Nernst-Plank equation to calculate the transport of solutes across the membrane due to convection, diffusion, and electromigration. Finally, we show how the theory discussed in this review leads to improved predictions of OMP rejection by the membranes.

Role of ion exchange membranes and capacitive electrodes in membrane capacitive deionization (MCDI) for CO2 capture.

Recently we showed that membrane capacitive deionization (MCDI) can be used to capture CO2, but we found that the performance decreases with decreasing current density. In the present study, we investigate the effect of electrodes and ion exchange membranes by performing experiments with two membranes (CO2-MCDI), with one membrane (cation or anion exchange membrane), and without membranes (CO2-CDI). We find that the anion exchange membrane is essential to keep high CO2 absorption efficiencies ( [Formula: see text] /ncharge), while the absorption efficiency of the CO2-CDI cell was lower than expected (Λa≈0.5 for CO2-MCDI against Λa≈0.18 for CO2-CDI). Moreover, we theoretically investigate ion adsorption mechanisms in the electrodes by comparing experimental data of a CO2-CDI cell with theoretical results of the classic amphoteric-Donnan model developed for conventional CDI. By comparing the experimental results with the amph-D model, we find that the model overestimates the absorption efficiency in CO2-CDI experiments. To understand this discrepancy, we investigate the effects of other phenomena, i.e., (i) low ion concentration, (ii) passive CO2 absorption, and (iii) the effect of acid-base reactions on the chemical surface charge.

Selective adsorption of nitrate over chloride in microporous carbons.

Activated carbon is the most common electrode material used in electrosorption processes such as water desalination with capacitive deionization (CDI). CDI is a cyclic process to remove ions from aqueous solutions by transferring charge from one electrode to another. When multiple salts are present in a solution, the removal of each ionic species can be different, resulting in selective ion separations. This ion selectivity is the result of combined effects, such as differences in the hydrated size and valence of the ions. In the present work, we study ion selectivity from salt mixtures with two different monovalent ions, chloride and nitrate. We run adsorption experiment in microporous carbons (i.e., without applying a voltage), as well as electrosorption experiments (i.e., based on applying a voltage between two carbon electrodes). Our results show that i) during adsorption and electrosorption, activated carbon removes much more nitrate than chloride; ii) at equilibrium, ion selectivity does not depend strongly on the composition of the water, but does depend on charging voltage in CDI; and iii) during electrosorption, ion selectivity is time-dependent. We modify the amphoteric Donnan model by including an additional affinity of nitrate to carbon. We find good agreement between our experimental results and the theory. Both show very high selectivity towards nitrate over chloride, [Formula: see text] ∼10, when no voltage is applied, or when the voltage is low. The selectivity gradually decreases with increasing charging voltage to [Formula: see text] ∼6 at Vch = 1.2 V. Despite this decrease, the affinity-effect for nitrate continues to play an important role also at a high voltage. In general, we can conclude that our work provides new insights in the importance of carbon-ion interactions for electrochemical water desalination.

Energy Efficiency of Capacitive Deionization.

Capacitive deionization (CDI) as a class of electrochemical desalination has attracted fast-growing research interest in recent years. A significant part of this growing interest is arguably attributable to the premise that CDI is energy efficient and has the potential to outcompete other conventional desalination technologies. In this review, systematic evaluation of literature data reveals that while the absolute energy consumption of CDI is in general low, most existing CDI systems achieve limited energy efficiency from a thermodynamic perspective. We also analyze the causes for the relatively low energy efficiency and discuss factors that may lead to enhanced energy efficiency for CDI.

Energy consumption in capacitive deionization - Constant current versus constant voltage operation.

In the field of Capacitive Deionization (CDI), it has become a common notion that constant current (CC) operation consumes significantly less energy than constant voltage operation (CV). Arguments in support of this claim are that in CC operation the endpoint voltage is reached only at the end of the charging step, and thus the average cell voltage during charging is lower than the endpoint voltage, and that in CC operation we can recover part of the invested energy during discharge. Though these arguments are correct, in the present work based on experiments and theory, we conclude that in operation of a well-defined CDI cycle, this does not lead, for the case we analyze, to the general conclusion that CC operation is more energy efficient. Instead, we find that without energy recovery there is no difference in energy consumption between CC and CV operation. Including 50% energy recovery, we find that indeed CC is more energy efficient, but also in CV much energy can be recovered. Important in the analysis is to precisely define the desalination objective function, such as that per unit total operational time -including both the charge and discharge steps- a certain desalination quantity and water recovery must be achieved. Another point is that also in CV operation energy recovery is possible by discharge at a non-zero cell voltage. To aid the analysis we present a new method of data representation where energy consumption is plotted against desalination. In addition, we propose that one must analyze the full range of combinations of cycle times, voltages and currents, and only compare the best cycles, to be able to conclude which operational mode is optimal for a given desalination objective. We discuss three methods to make this analysis in a rigorous way, two experimental and one combining experiments and theory. We use the last method and present results of this analysis.

Theory of pH changes in water desalination by capacitive deionization.

In electrochemical water desalination, a large difference in pH can develop between feed and effluent water. These pH changes can affect the long-term stability of membranes and electrodes. Often Faradaic reactions are implicated to explain these pH changes. However, quantitative theory has not been developed yet to underpin these considerations. We develop a theory for electrochemical water desalination which includes not only Faradaic reactions but also the fact that all ions in the water have different mobilities (diffusion coefficients). We quantify the latter effect by microscopic physics-based modeling of pH changes in Membrane Capacitive Deionization (MCDI), a water desalination technology employing porous carbon electrodes and ion-exchange membranes. We derive a dynamic model and include the following phenomena: I) different mobilities of various ions, combined with acid-base equilibrium reactions; II) chemical surface charge groups in the micropores of the porous carbon electrodes, where electrical double layers are formed; and III) Faradaic reactions in the micropores. The theory predicts small pH changes during desalination cycles in MCDI if we only consider phenomena I) and II), but predicts that these pH changes can be much stronger if we consider phenomenon III) as well, which is in line with earlier statements in the literature on the relevance of Faradaic reactions to explain pH fluctuations.

Resistance identification and rational process design in Capacitive Deionization.

Capacitive Deionization (CDI) is an electrochemical method for water desalination employing porous carbon electrodes. To enhance the performance of CDI, identification of electronic and ionic resistances in the CDI cell is important. In this work, we outline a method to identify these resistances. We illustrate our method by calculating the resistances in a CDI cell with membranes (MCDI) and by using this knowledge to improve the cell design. To identify the resistances, we derive a full-scale MCDI model. This model is validated against experimental data and used to calculate the ionic resistances across the MCDI cell. We present a novel way to measure the electronic resistances in a CDI cell, as well as the spacer channel thickness and porosity after assembly of the MCDI cell. We identify that for inflow salt concentrations of 20 mM the resistance is mainly located in the spacer channel and the external electrical circuit, not in the electrodes. Based on these findings, we show that the carbon electrode thickness can be increased without significantly increasing the energy consumption per mol salt removed, which has the advantage that the desalination time can be lengthened significantly.

Enhanced charge efficiency and reduced energy use in capacitive deionization by increasing the discharge voltage.

Capacitive deionization (CDI) is an electrochemical method for water desalination using porous carbon electrodes. A key parameter in CDI is the charge efficiency, Λ, which is the ratio of salt adsorption over charge in a CDI-cycle. Values for Λ in CDI are typically around 0.5-0.8, significantly less than the theoretical maximum of unity, due to the fact that not only counterions are adsorbed into the pores of the carbon electrodes, but at the same time coions are released. To enhance Λ, ion-exchange membranes (IEMs) can be implemented. With membranes, Λ can be close to unity because the membranes only allow passage for the counterions. Enhancing the value of Λ is advantageous as this implies a lower electrical current and (at a fixed charging voltage) a reduced energy use. We demonstrate how, without the need to include IEMs, the charge efficiency can be increased to values close to the theoretical maximum of unity, by increasing the cell voltage during discharge, with only a small loss of salt adsorption capacity per cycle. In separate constant-current CDI experiments, where after some time the effluent salt concentration reaches a stable value, this value is reached earlier with increased discharge voltage. We compare the experimental results with predictions of porous electrode theory which includes an equilibrium Donnan electrical double layer model for salt adsorption in carbon micropores. Our results highlight the potential of modified operational schemes in CDI to increase charge efficiency and reduce energy use of water desalination.

Energy from CO2 using capacitive electrodes - a model for energy extraction cycles.

A model is presented for the process of harvesting electrical energy from CO2 emissions using capacitive cells. The principle consists of controlling the mixing process of a concentrated CO2 gas stream with a dilute CO2 gas stream (as, for example, exhaust gas and air), thereby converting part of the released mixing energy into electrical energy. The model describes the transient reactive transport of CO2 gas absorbed in water or in monoethanolamine (MEA) solutions, under the assumption of local chemical equilibrium. The model combines the selective transport of ions through ion-exchange membranes, the accumulation of charge in the porous carbon electrodes and the coupling between the ionic current and the produced electrical current and power. We demonstrate that the model can be used to calculate the energy that can be extracted by mixing concentrated and dilute CO2 containing gas streams. Our calculation results for the process using MEA solutions have various counterintuitive features, including: 1. When dynamic equilibrium is reached in the cyclical process, the electrical charge in the anode is negative both during charging and discharging; 2. Placing an anion-exchange membrane (AEM) in the system is not required, the energy per cycle is just as large with or without an AEM.

Theory of ion transport with fast acid-base equilibrations in bioelectrochemical systems.

Bioelectrochemical systems recover valuable components and energy in the form of hydrogen or electricity from aqueous organic streams. We derive a one-dimensional steady-state model for ion transport in a bioelectrochemical system, with the ions subject to diffusional and electrical forces. Since most of the ionic species can undergo acid-base reactions, ion transport is combined in our model with infinitely fast ion acid-base equilibrations. The model describes the current-induced ammonia evaporation and recovery at the cathode side of a bioelectrochemical system that runs on an organic stream containing ammonium ions. We identify that the rate of ammonia evaporation depends not only on the current but also on the flow rate of gas in the cathode chamber, the diffusion of ammonia from the cathode back into the anode chamber, through the ion exchange membrane placed in between, and the membrane charge density.