Energy Efficiency of Electro-Driven Brackish Water Desalination: Electrodialysis Significantly Outperforms Membrane Capacitive Deionization

Electro-driven technologies are viewed as a potential alternative to the current state-of-the-art technology, reverse osmosis, for the desalination of brackish waters. Capacitive deionization (CDI), based on the principle of electrosorption, has been intensively researched under the premise of being energy efficient. However, electrodialysis (ED), despite being a more mature electro-driven technology, has yet to be extensively compared to CDI in terms of energetic performance. In this study, we utilize Nernst-Planck based models for continuous flow ED and constant-current membrane capacitive deionization (MCDI) to systematically evaluate the energy consumption of the two processes. By ensuring equivalently sized ED and MCDI systems-in addition to using the same feed salinity, salt removal, water recovery, and productivity across the two technologies-energy consumption is appropriately compared. We find that ED consumes less energy (has higher energy efficiency) than MCDI for all investigated conditions. Notably, our results indicate that the performance gap between ED and MCDI is substantial for typical brackish water desalination conditions (e.g., 3 g L-1 feed salinity, 0.5 g L-1 product water, 80% water recovery, and 15 L m-2 h-1 productivity), with the energy efficiency of ED often exceeding 30% and being nearly an order of magnitude greater than MCDI. We provide further insights into the inherent limitations of each technology by comparing their respective components of energy consumption, and explain why MCDI is unable to attain the performance of ED, even with ideal and optimized operation.

Climate change, population growth, and increased industrial activities are exacerbating freshwater scarcity and leading to increased interest in desalination of saline water. Brackish water is an attractive alternative to freshwater due to its low salinity and widespread availability in many water-scarce areas. However, partial or total desalination of brackish water is essential to reach the water quality requirements for a variety of applications. Selection of appropriate technology requires knowledge and understanding of the operational principles, capabilities, and limitations of the available desalination processes. Proper combination of feedwater technology improves the energy efficiency of desalination. In this article, we focus on pressure-driven and electro-driven membrane desalination processes. We review the principles, as well as challenges and recent improvements for reverse osmosis (RO), nanofiltration (NF), electrodialysis (ED), and membrane capacitive deionization (MCDI). RO is the dominant membrane process for large-scale desalination of brackish water with higher salinity, while ED and MCDI are energy-efficient for lower salinity ranges. Selective removal of multivalent components makes NF an excellent option for water softening. Brackish water desalination with membrane processes faces a series of challenges. Membrane fouling and scaling are the common issues associated with these processes, resulting in a reduction in their water recovery and energy efficiency. To overcome such adverse effects, many efforts have been dedicated toward development of pre-treatment steps, surface modification of membranes, use of anti-scalant, and modification of operational conditions. However, the effectiveness of these approaches depends on the fouling propensity of the feed water. In addition to the fouling and scaling, each process may face other challenges depending on their state of development and maturity. This review provides recent advances in the material, architecture, and operation of these processes that can assist in the selection and design of technologies for particular applications. The active research directions to improve the performance of these processes are also identified. The review shows that technologies that are tunable and particularly efficient for partial desalination such as ED and MCDI are increasingly competitive with traditional RO processes. Development of cost-effective ion exchange membranes with high chemical and mechanical stability can further improve the economy of desalination with electro-membrane processes and advance their future applications.

Though electrodialysis (ED) and reverse osmosis (RO) are both mature, proven technologies for brackish water desalination, RO is currently utilized to desalinate over an order of magnitude more brackish water than ED. This large discrepancy in the adoption of each technology has yet to be thoroughly justified in the literature, particularly from the perspective of energy consumption. Hence, in this study, we performed a direct and systematic comparison of the energy consumption of RO and ED for brackish water desalination, precisely mapping out the ideal operational space of each technology for the first time. Using rigorous system-scale models for RO and ED, we determine the specific energy consumption and energy efficiency of each process over a wide range of brackish water conditions. Specifically, we investigate the effects of varying feed salinity, extent of salt removal, water recovery, and productivity to ultimately identify the operational sweet spots of each technology. By maintaining the same separation parameters (i.e., feed salinity, salt removal, water recovery) and productivity between RO and ED throughout the study, we ensure that our comparison of the technologies is valid and fair. Our results indicate that both RO and ED are capable of operating with high energy efficiency (>30%) for brackish water desalination, though for differing conditions. Particularly, we show that whereas ED excels for low feed salinities (<3 g L–1) and extents of salt removal, RO operates optimally for high salinity feeds (>5 g L–1), which require more extensive desalination. Through our in-depth energetic analysis, we provide guidance for future applications of RO and ED, emphasizing that increased implementation of ED will require significant reduction in the cost of ion-exchange membranes.

The energy-water nexus, a 21st century challenge, represents a symbiotic relationship as it takes a lot of energy to purify water and a significant amount of water is needed to produce energy. Prudent manage of these precious resources is paramount for a sustainable planet. Today, numerous industrial processes, such as thermal electric power plants, consume 40% of fresh water withdrawals within the United States.1 Industry demand is often met by treating brackish water streams, which are about 5,000 ppm in total dissolved salts (TDS), and the current annual energy consumption in the U.S. amounts to 2.7x1011 kWh annually. Based on thermodynamic analysis constrained to a 50% minimal water recovery, today’s state-of-the-art for water desalination of brackish water streams is 20% efficient. Improving the efficiency from 20% to 30% could amount to a savings of $4 billion dollars worth of electricity annually in the U.S. and a reduction of energy needs by 20 GW. One technology capable of providing low energy water desalination of brackish water streams with over 30% thermodynamic efficiency is membrane capacitive deionization (MCDI). MCDI, an electrochemical technology, offers the enticing prospect of low energy water desalination as it can recover energy (demonstrated up to 83%)2 when discharging the saturated electrodes as a supercapacitor. Most research today has focused on porous carbon electrodes to increase MCDI capacity. However, material innovation with regard to the ion-exchange membranes used in MCDI has been neglected. Today’s MCDI currently uses electrodialysis (ED) membranes – not originally designed for MCDI. The ion-exchange membranes for ED tend to be thick as they serve as a separator in addition to an ion-conducting electrolyte in electrodialysis. In MCDI, the ion-exchange membranes do not serve as separator and they are employed to prevent co-ion adsorption to the porous carbon electrodes. This talk will demonstrate how thinner ion-exchange membranes with higher ionic conductivity substantially reduces the energy footprint for MCDI - approximately 35 kT per ion removed with ED membranes to 15 kT per ion removed with new ion-exchange membranes. Additionally, the new ion-exchange membranes displayed a significantly higher Coulombic efficiency. The talk will showcase how ex-situ properties of ion-exchange membranes, such as ionic conductivity, thickness, and permselectivity, are instrumental for lowering the energy footprint of MCDI. Note: Figure represents single-cell MCDI operation under constant current with newly prepared ion-exchange membranes. Green line corresponds to cell voltage, while the purple line corresponds to the salt effluent stream.

Water and energy shortages came due to rapid population growth, living standards and rapid development in the agriculture and industrial sectors. Desalination tends to be one of the most promising water solutions; however, it is a process of intense energy. Membrane Capacitive Deionization (MCDI) has received considerable interest as a promising desalination technology, and MCDI research has increased significantly over the last 10 years. In addition, there are no guidelines for the design of Capacitive Deionization (CDI) implementation strategies for individual applications. This study, therefore; provides an alternative of CDI’s recent application developments, with emphasis placed on hybrid systems to address the technological needs of different relevant fields. The MCDI’s energy consumption is compared with the reverse osmosis literature data based on experimental data from laboratory-scale system. The study demonstrates that MCDI technology is a promising technology in the next few years with an extreme competition in water recovery, energy consumption and salt removal for reverse osmosis.

Membrane capacitive deionization-reverse electrodialysis hybrid system for improving energy efficiency of reverse osmosis seawater desalination

Modeling technologies for desalination of brackish water — toward a sustainable water supply

Concentrating saline water is essential for zero liquid discharge (ZLD) of wastewater. However, prevailing membrane-based technologies, such as reverse osmosis (RO) and electrodialysis (ED), can hardly handle high concentration differences (ΔC) in a single stage, where multi-stage operation is needed, which increases the operational difficulties and energy input. However, membrane capacitive deionization (MCDI) is theoretically applicable to high ΔC. This study explored the feasibility of employing an MCDI in brine concentrating and proposed several regulating measures on the electrode's porosity, electrical quantity for charging-discharging, and desorption conditions. Based on the determination of salt and water fluxes, these measures were confirmed to mitigate water transfer across the membrane, thereby facilitating salt transportation for brine concentrating. To address the mass imbalance between adsorbed and desorbed, a novel pre-charge strategy was designed, which enabled successful MCDI continuous operation over 50 cycles. A concentration difference of 161 g/L NaCl was achieved per single stage, which is the highest reported result among RO, ED, and MCDI studies. The concentrating rate was as high as 38.4 g/(m2·h) with a comparative energy consumption at RO and ED. This study demonstrated that MCDI is an optional technology for the future application of brine concentrating in ZLD facilities.

Capacitive deionization (CDI) is a class of electrochemical desalination technologies which desalinate via ion storage in electric double-layers. CDI has received renewed attention in recent years due to the ability to couple energy storage with salt separation. During galvanostatic operation, a current is applied between porous carbon electrodes until a limiting voltage is reach. The cell is then discharged by applying a reverse current, generating brine and recovering stored charge. However, CDI desalination and energy efficiency can be limited by parasitic side reactions, and selective adsorption of counter-ions (anions at the positive electrode, and cations at the negative electrode). Several material additions and electrode configurations have been proposed to overcome these limitations, with the most prominent being the addition of ion exchange membranes (IEMs) promote counter ion flux out of the desalination chamber and incorporation of carbon slurry electrodes to increase system adsorption capacity. Likewise, functionalization of carbon electrodes has been studied to improve counter-ion adsorption within EDL micropores. While the incorporation of functionalized carbon, IEMs in membrane capacitive deionization (MCDI), and the use of slurry electrodes in flow capacitive deionization (FCDI) have successfully reduced energy consumption or increased ion adsorption capacity in CDI systems, these modifications are often evaluated under limited conditions on the basis of specific performance enhancements. Additional clarity is necessary to evaluate the associated performance and cost tradeoffs across the design space. In this study, an equivalent circuit (M)CDI model, with porous electrode sub-models, was used to measure the sensitivity of CDI performance to material selection, design, and operating choices. In order to investigate the performance of FCDI, pulse-flowed electrodes of high capacity and electronic resistances were incorporated into the existing model. Similarly, fixed charge in the anodic and cathodic micropores was studied to investigate functionalized carbon. Constrained system parameters were randomly selected via latin hypercube sampling (LHS) across multiple electrode geometries and influent salt concentrations. The resultant model outputs were then correlated with input values to quantify parameter sensitivity. Our sensitivity analysis shows that operating current density, electrode specific capacitance, and contact resistance were the parameters which most significantly dictated (M)CDI performance. These parameters where then used to construct an operational space for CDI, MCDI, and FCDI. The results of our operational space were then used to develop a simplified, operational model for both capacitive and faradic materials in CDI. Using this model we conducted a techno-economic analysis (TEA) of proposed improvement to CDI. From the TEA we are able more directly set operating parameters under which CDI might favorably compete with the primary technology for desalination, reverse osmosis (RO). We are able to evaluate materials lifetimes and costs necessary to economically operate CDI. Lastly, goals for operating parameters highlighted in the sensitivity analysis (specific capacitance, voltage limits, charge efficiency, and cell resistance) were set. These benchmarks will provide target for the continued development of CDI towards and economic and viable alternative to RO for brackish water desalination.

Capacitive deionization (CDI) is a developing technology for water desalination applications with benefits over current methods such as reverse osmosis (RO) and distillation due to its operation at lower temperatures and pressure. CDI uses small applied potentials (<2.0 V) to selectively separate ions from feed water streams by reversibly adsorbing these ions in the electric double layer of conductive, high surface area, and porous carbon electrodes. This reversible absorption process can be used in a variety of configurations including flow-by, flow-through, and flowable electrode arrangements.1 Classic CDI systems have charge efficiency (equivalent charge of salt adsorbed per electronic charge input) values well below 100% due to parasitic discharge processes and Faradaic reactions.2,3 Therefore, ion-exchange membranes have been added into these systems to increase the effective adsorption capacity of the electrodes and limit the extent of parasitic processes. Overall, CDI systems are considered to be more efficient than RO membranes for many lower concentration salt streams (<5000 ppm) due to differences in its separation mechanism.4 Shown in Figure 1 is an energy cost comparison of CDI and RO technologies as a function of salt concentration. CDI is shown with energy recovery values of 0, 25, and 50%. As the concentration of NaCl decreases, there is a distinct region where the energy cost of this separation can best RO. The more recent addition of ion-exchange membranes in a membrane capacitive deionization (MCDI) process can further increase the charge efficiency to over 100% in certain instances and aid in further decreasing energy costs.5 The efficiency of both the CDI and MCDI process make them attractive options for many larger scale applications where energy cost becomes a dominant factor in choosing the water treatment system. In this talk, a comparison between the energy costs of RO and CDI/MCDI will be given. The use of recent surface chemistries to increase the charge efficiency will be shown to decrease the energy cost of CDI/MCDI processes further. Finally, applications will be reviewed where CDI and MCDI can be used as a standalone option as well as interface with existing membrane processes. Acknowledgements The authors are grateful to the U.S. - China Clean Energy Research Center, U.S. Department of Energy for project funding (No. DE-PI0000017).

Carbon-based electrode materials with ion exchange membranes for enhanced membrane capacitive deionization

Nitrite desorption from activated carbon fiber during capacitive deionization (CDI) and membrane capacitive deionization (MCDI)

Membrane capacitive deionization (MCDI) is an energy efficient, cost effective desalination technique for brackish water to produce water for drinking and processes found in semiconductor and pharmaceutical manufacturing, energy production, and other water related industries.[1-3] The operating principle in MCDI is a potential induced electro-sorption of salt ions that migrate across the ion-exchange membrane layers to the porous carbon electrodes. Hence, the application of electric work reduces the salt content from the feed water. Saturation of the carbon electrodes then leads to discharge of the salt from the carbon electrodes, leading to recovered energy and an increase in salt concentration of the emanating flow stream from the MCDI cell. The discharge process regenerates the electrodes so salt removal can take place again. From a materials aspect of MCDI, most research has focused on carbon-based electrodes with the aim to improve device performance.[4-6] Conversely, little innovation has been made in alternative ion-exchange membrane materials for MCDI. Most reports of MCDI leverage commercially available membranes for electrodialysis.[1,3,7] In this work, MCDI performance was correlated to ion-exchange membrane thickness. The experimental design evaluated examined: i.) commercially available ion-exchange membranes, ii.) ion-exchange layered electrodes of different thicknesses with electrode samples being prepared by drop casting followed by spray painting of ionomer layer on top of the electrode; and iii.) drop casting a mixture of electron conducting carbon with dissolved ionomer. A home-built, single-cell MCDI module was characterized with the different ion-exchange materials using a 275 ppm salt feed. MCDI performance was determined by quantifying salt removal and energy efficiency and the individual resistance contributions in the system through electrochemical impedance spectroscopy.

US Marine missions require technologies that produce potable water from various water sources that include both seawater and ground water. Reverse osmosis (RO) is the most wide-spread and economical process for desalinating water from seawater. However, it is only cost-competitive and practical when deployed in large, centralized production facilities and is not conducive for marine squad units. Membrane capacitive deionization (MCDI) is an alternative water desalination platform that is enticing to military missions as it does not require high pressure piping and it does not generate significant acoustic, thermal, or electromagnetic signals. MCDI removes ions from the liquid solution using electrical energy, and the commercialized variant, flow-by MCDI, feature two porous electrodes covered by ion-exchange membranes(1). During deionization, the positively biased electrode has an anion exchange membrane (AEM) in front of it while the negatively biased electrode contains a cation exchange membrane (CEM) in front of it.Our previous research improved the energy efficiency of MCDI by using ion-exchange membranes with lower area-specific resistance (ASR) values(2) and porous ionic conductors in the spacer channel that augment solution conductivity and curtail ohmic losses(3). Reducing these resistances enabled the MCDI to operate at higher current density – which is important for shrinking the size of the MCDI unit and lowering the overall capital costs.This talk highlights our recent work examining ionic charge transport resistance at the membrane-electrode interface in MCDI. We studied the impact of this resistance on MCDI performance metrics (salt removal and energy normalized adsorbed salt (ENAS)) by systematically changing the interfacial area of the ion-exchange membrane-electrode interface via patterning of the ion-exchange membrane surfaces using soft-lithography. This strategy has been shown to be effective in reducing charge-transfer resistances in both proton exchange membrane (PEM)(4) and AEM(5) fuel cells and reducing the water dissociation kinetics resistance in bipolar membranes(6). Micropatterned AEMs and CEMs based upon poly(arylene ether) and all-carbon poly(arylene) backbones(7) were fabricated with periodic line and cylinder topographies and lateral feature sizes that vary from 2 to 20 μm. The patterned membranes were coated with graphitic carbon electrodes. It is posited that smaller lateral feature sizes, which gives rise to larger interfacial area values, reduces interfacial resistance values in MCDI and larger ENAS values. Keywords: Desalination, Membrane capacitive deionization, Ion exchange membranes, Soft lithography, Energy normalized adsorbed salt, Membrane electrode assembly References S. Porada, L. Zhang and J. E. Dykstra, Desalination, 488, 114383 (2020).V. M. Palakkal, J. E. Rubio, Y. J. Lin and C. G. Arges, ACS Sustainable Chemistry & Engineering, 6, 13778 (2018).V. M. Palakkal, M. L. Jordan, D. Bhattacharya, Y. J. Lin and C. G. Arges, Journal of The Electrochemical Society, 168, 033503 (2021).Y. Jeon, D. J. Kim, J. K. Koh, Y. Ji, J. H. Kim and Y.-G. Shul, Scientific Reports, 5, 16394 (2015).S. Jang, M. Her, S. Kim, J.-H. Jang, J. E. Chae, J. Choi, M. Choi, S. M. Kim, H.-J. Kim, Y.-H. Cho, Y.-E. Sung and S. J. Yoo, ACS Applied Materials & Interfaces, 11, 34805 (2019).S. Kole, G. Venugopalan, D. Bhattacharya, L. Zhang, J. Cheng, B. Pivovar and C. G. Arges, Journal of Materials Chemistry A, 9, 2223 (2021).W.-H. Lee, Y. S. Kim and C. Bae, ACS Macro Letters, 4, 814 (2015).

Desalination and water reuse are the key solutions to address global water scarcity. It is important to recognize the water-energy interactions and develop energy-efficient technologies to separate ions from brackish water, seawater and reclaimed wastewater. Most recently, membrane capacitive deionization (MCDI), inspired by energy storage devices (e.g., supercapacitors), is a promising desalination technology with several advantages of energy efficiency (TDS < 4000 ppm), high water recovery, less chemical additive, and environmental friendliness. In MCDI, ions are electrostatically captured within highly porous carbon electrodes through the formation of electrical double layer during the charging step, and then released into the solution by discharging the electrodes. By incorporating ion-exchange membranes (IEMs) in front of each electrode, the desalination performance can be significantly improved, achieving high salt adsorption capacity and charge efficiency. Over the past few years, we have made efforts to scale up the MCDI stacks for commercialization purposes, which are composed of 32 pairs of 400 mm × 200 mm activated carbon electrodes. Note that a stop-flow operation is applied in the discharge process to increase the water recovery (> 75%). A pilot-scale study of an MCDI system was performed to reclaim the secondary effluents from a municipal wastewater treatment plant. In addition, MCDI prototypes offer promising engineering opportunities for water recycling in high-tech industries, including reverse osmosis reject and wet scrubbing. Furthermore, we will discuss the challenges and perspectives for the future of MCDI as a cost-efficient, low-energy approach for desalination and resource recovery.