Energy Efficient Carbon Capture through Electrochemical pH Swing Regeneration of Amine Solution.

Carbon capture is widely acknowledged as a promising strategy for achieving negative emissions. Electrochemical carbon capture technologies are considered a viable alternative to conventional temperature swing processes. Among these, employing the hydrogen oxidation and hydrogen evolution reactions as a redox couple, along with an ion exchange membrane, offers an effective means of establishing a pH swing for desorbing CO2 and regenerating the alkaline solvent. However, the practical scalability of this approach is impeded by challenges such as high energy demands resulting from a high pH differential between anodic and cathodic environments and operation with solutions with a low conductivity, required to obtain an acceptable current yield. To address these limitations, this study introduces an innovative anion exchange membrane (AEM)-based electrochemical process for solvent regeneration. Our research demonstrates the advantageous utilization of amines as chemical buffers. Selecting an amine solution with a favorable pKa (∼7 to 10) helps in maintaining bicarbonate as the predominant carbon species within the system, thereby ensuring a high current yield (>80%) across various operational conditions (current, load ratio, and solution concentration). Furthermore, our analysis indicates that the use of amine solutions effectively reduces the overpotential of the hydrogen evolution reaction due to a lower local pH. This results in a minimum energy requirement of 63 kJ/mol at a current density of 20 A/m2 to regenerate the solution (MDEA) while maintaining high (>99%) product (CO2) purity.

Origin of Limiting and Overlimiting Currents in Bipolar Membranes.

Bipolar membranes (BPMs), a special class of ion exchange membranes with the unique ability to electrochemically induce either water dissociation or recombination, are of growing interest for environmental applications including eliminating chemical dosage for pH adjustment, resource recovery, valorization of brines, and carbon capture. However, ion transport within BPMs, and particularly at its junction, has remained poorly understood. This work aims to theoretically and experimentally investigate ion transport in BPMs under both reverse and forward bias operation modes, taking into account the production or recombination of H+ and OH-, as well as the transport of salt ions (e.g., Na+, Cl-) inside the membrane. We adopt a model based on the Nernst-Planck theory, that requires only three input parameters─membrane thickness, its charge density, and pK of proton adsorption─to predict the concentration profiles of four ions (H+, OH-, Na+, and Cl-) inside the membrane and the resulting current-voltage curve. The model can predict most of the experimental results measured with a commercial BPM, including the observation of limiting and overlimiting currents, which emerge due to particular concentration profiles that develop inside the BPM. This work provides new insights into the physical phenomena in BPMs and helps identify optimal operating conditions for future environmental applications.

Effects of Current on the Membrane and Boundary Layer Selectivity in Electrochemical Systems Designed for Nutrient Recovery.

During electrochemical nutrient recovery, current and ion exchange membranes (IEM) are used to extract an ionic species of interest (e.g., ion) from a mixture of multiple ions. The species of interest (ion 1) has an opposing charge to the IEM. When ion 1 is extracted from the solution, the species fractions at the membrane and the adjunct boundary layers are affected. Hence, the species transport through the electrochemical system (ES) can no longer be described as electrodialysis-like. A dynamic state is observed in the compartments, where the ionic species are recovered. When the boundary layer-membrane interface is depleted, the IEM is at maximum current. If the ES is operated at a current higher than the maximum current, the fluxes of both ion 1 and other competing ions, with the same charge (ion 2), occur. This means, for example, ion 1 will be recovered, and the concentration of ion 2 will build up in time. Therefore, a steady state is never reached. Ideally, to prevent the effect of limiting current at the boundary layer-membrane interface, ES for nutrient recovery should be operated at low currents.

Direct Air Capture Using Electrochemically Regenerated Anion Exchange Resins.

Direct air capture (DAC) aims to remove CO2 directly from the atmosphere. In this study, we have demonstrated proof-of-concept of a DAC process combining CO2 adsorption in a packed bed of amine-functionalized anion exchange resins (AERs) with a pH swing regeneration using an electrochemical cell (EC). The resin bed was regenerated using the alkaline solution produced in the cathodic compartment of the EC, while high purity CO2 (>95%) was desorbed in the acidifying compartment. After regenerating the AERs, some alkaline solution remained on the surface of the resins and provided additional CO2 capture capacity during adsorption. The highest CO2 capture capacity measured was 1.76 mmol·g-1 dry resins. Moreover, as the whole process was operated at room temperature, the resins did not show any apparent degradation after 150 cycles of adsorption-desorption. Furthermore, when the relative humidity of the air source increased from 33 to 84%, the water loss of the process decreased by 63%, while CO2 capture capacity fell 22%. Finally, although the pressure drop of the adsorption column (5 ± 1 kPa) and the energy consumption of the EC (537 ± 33 kJ·mol-1 at 20 mA·cm-2) are high, we have discussed the potential improvements toward a successful upscaling.

Donnan Dialysis for scaling mitigation during electrochemical ammonium recovery from complex wastewater.

Inorganic scaling is often an obstacle for implementing electrodialysis systems in general and for nutrient recovery from wastewater specifically. In this work, Donnan dialysis was explored, to prevent scaling and to prolong operation of an electrochemical system for TAN (total ammonia nitrogen) recovery. An electrochemical system was operated with and without an additional Donnan dialysis cell, while being supplied with synthetic influent and real digested black water. For the same Load Ratio (nitrogen load vs applied current) while treating digested black water, the system operated for a period three times longer when combined with a Donnan cell. Furthermore, the amount of nitrogen recovered was higher. System performance was evaluated in terms of both TAN recovery and energy efficiency, at different Load Ratios. At a Load Ratio 1.3 and current density of 10 A m-2, a TAN recovery of 83% was achieved while consuming 9.7 kWh kgN-1.

Minimal Bipolar Membrane Cell Configuration for Scaling Up Ammonium Recovery.

Electrochemical systems for total ammonium nitrogen (TAN) recovery are a promising alternative compared with conventional nitrogen-removal technologies. To make them competitive, we propose a new minimal stackable configuration using cell pairs with only bipolar membranes and cation-exchange membranes. The tested bipolar electrodialysis (BP-ED) stack included six cell pairs of feed and concentrate compartments. Critical operational parameters, such as current density and the ratio between applied current to nitrogen loading (load ratio), were varied to investigate the performance of the system using synthetic wastewater with a high nitrogen content as an influent (NH4 + ≈ 1.75 g L-1). High TAN removal (>70%) was achieved for a load ratio higher than 1. At current densities of 150 A m-2 and a load ratio of 1.2, a TAN transport rate of 1145.1±14.1 gN m-2 d-1 and a TAN-removal efficiency of 80% were observed. As the TAN removal was almost constant at different current densities, the BP-ED stack performed at a high TAN transport rate (819.1 gN m-2 d-1) while consuming the lowest energy (18.3 kJ gN -1) at a load ratio of 1.2 and 100 A m-2. The TAN transport rate, TAN removal, and energy input achieved by the minimal BP-ED stack demonstrated a promising new cell configuration for upscaling.

Enhanced Phototrophic Biomass Productivity through Supply of Hydrogen Gas.

Industrial production of phototrophic microorganisms is often hindered by low productivity due to limited light availability and therefore requires large land areas. This letter demonstrates that supply of hydrogen gas (H2) increases in phototrophic biomass productivity compared to a culture growing on light only. Experiments were performed growing Synechocystis sp. in batch bottles, with and without H2 in the headspace, which were exposed to light intensities of 70 and 100 µmol/m2/s. At 70 µmol/m2/s with H2, the average increase in biomass was 96 mg DW/L/d, whereas at 100 µmol/m2/s without H2, the average increase in biomass was 27 mg DW/L/d. Even at lower light intensity, the addition of H2 tripled the biomass yield compared to growth under light only. Photoreduction and photosynthesis occurred simultaneously, as both H2 consumption and O2 production were measured during biomass growth. Photoreduction used 1.85 mmol of H2 to produce 1.0 mmol of biomass, while photosynthesis produced 1.95 mmol of biomass. After transferring the culture to the dark, growth ceased, also in the presence of H2, showing that both light and H2 were needed for growth. A renewable H2 supply for higher biomass productivity is attractive since the combined efficiency of photovoltaics and electrolysis exceeds the photosynthetic efficiency.

Electrochemical Regeneration of Spent Alkaline Absorbent from Direct Air Capture.

CO2 capture from the atmosphere (or direct air capture) is widely recognized as a promising solution to reach negative emissions, and technologies using alkaline solutions as absorbent have already been demonstrated on a full scale. In the conventional temperature swing process, the subsequent regeneration of the alkaline solution is highly energy-demanding. In this study, we experimentally demonstrate simultaneous solvent regeneration and CO2 desorption in a continuous system using a H2-recycling electrochemical cell. A pH gradient is created in the electrochemical cell so that CO2 is desorbed at a low pH, while an alkaline capture solution (NaOH) is regenerated at high pH. By testing the cell under different working conditions, we experimentally achieved CO2 desorption with an energy consumption of 374 kJ·mol-1 CO2 and a CO2 purity higher than 95%. Moreover, our theoretical calculations show that a minimum energy consumption of 164 kJ·mol-1 CO2 could be achieved. Overall, the H2-recycling electrochemical cell allowed us to accomplish the simultaneous desorption of high-purity CO2 stream and regeneration of up to 59% of the CO2 capture capacity of the absorbent. These results are promising toward the upscaling of an energy-effective process for direct air capture.

Energy-Efficient Ammonia Recovery in an Up-Scaled Hydrogen Gas Recycling Electrochemical System.

Nutrient and energy recovery is becoming more important for a sustainable future. Recently, we developed a hydrogen gas recycling electrochemical system (HRES) which combines a cation exchange membrane (CEM) and a gas-permeable hydrophobic membrane for ammonia recovery. This allowed for energy-efficient ammonia recovery, since hydrogen gas produced at the cathode was oxidized at the anode. Here, we successfully up-scaled and optimized this HRES for ammonia recovery. The electrode surface area was increased to 0.04 m2 to treat up to 11.5 L/day (∼46 gN/day) of synthetic urine. The system was operated stably for 108 days at current densities of 20, 50, and 100 A/m2. Compared to our previous prototype, this new cell design reduced the anode overpotential and ionic losses, while the use of an additional membrane reduced the ion transport losses. Overall, this reduced the required energy input from 56.3 kJ/gN (15.6 kW h/kgN) at 50 A/m2 (prototype) to 23.4 kJ/gN (6.5 kW h/kgN) at 100 A/m2 (this work). At 100 A/m2, an average recovery of 58% and a TAN (total ammonia nitrogen) removal rate of 598 gN/(m2 day) were obtained across the CEM. The TAN recovery was limited by TAN transport from the feed to concentrate compartment.

(Bio)electrochemical ammonia recovery: progress and perspectives.

In recent years, (bio)electrochemical systems (B)ES have emerged as an energy efficient alternative for the recovery of TAN (total ammonia nitrogen, including ammonia and ammonium) from wastewater. In these systems, TAN is removed or concentrated from the wastewater under the influence of an electrical current and transported to the cathode. Subsequently, it can be removed or recovered through stripping, chemisorption, or forward osmosis. A crucial parameter that determines the energy required to recover TAN is the load ratio: the ratio between TAN loading and applied current. For electrochemical TAN recovery, an energy input is required, while in bioelectrochemical recovery, electric energy can be recovered together with TAN. Bioelectrochemical recovery relies on the microbial oxidation of COD for the production of electrons, which drives TAN transport. Here, the state-of-the-art of (bio)electrochemical TAN recovery is described, the performance of (B)ES for TAN recovery is analyzed, the potential of different wastewaters for BES-based TAN recovery is evaluated, the microorganisms found on bioanodes that treat wastewater high in TAN are reported, and the toxic effect of the typical conditions in such systems (e.g., high pH, TAN, and salt concentrations) are described. For future application, toxicity effects for electrochemically active bacteria need better understanding, and the technologies need to be demonstrated on larger scale.

Hydrogen Gas Recycling for Energy Efficient Ammonia Recovery in Electrochemical Systems.

Recycling of hydrogen gas (H2) produced at the cathode to the anode in an electrochemical system allows for energy efficient TAN (Total Ammonia Nitrogen) recovery. Using a H2 recycling electrochemical system (HRES) we achieved high TAN transport rates at low energy input. At a current density of 20 A m-2, TAN removal rate from the influent was 151 gN m-2 d-1 at an energy demand of 26.1 kJ gN-1. The maximum TAN transport rate of 335 gN m-2 d-1 was achieved at a current density of 50 A m-2 and an energy demand of 56.3 kJ gN-1. High TAN removal efficiency (73-82%) and recovery (60-73%) were reached in all experiments. Therefore, our HRES is a promising alternative for electrochemical and bioelectrochemical TAN recovery. Advantages are the lower energy input and lower risk of chloride oxidation compared to electrochemical technologies and high rates and independence of organic matter compared to bioelectrochemical systems.

Load ratio determines the ammonia recovery and energy input of an electrochemical system.

Complete removal and recovery of total ammonia nitrogen (TAN) from wastewaters in (bio)electrochemical systems has proven to be a challenge. The system performance depends on several factors, such as current density, TAN loading rate and pH. The interdependence among these factors is not well understood yet: insight is needed to achieve maximum ammonium recovery at minimal energy input. The aim of this study was to investigate the influence of current density and TAN loading rate on the recovery efficiency and energy input of an electrochemical cell (EC). We therefore defined the load ratio, which is the ratio between the applied current and the TAN loading rate. The system consisted of an EC coupled to a membrane unit for the recovery of ammonia. Synthetic wastewater, with TAN concentration similar to urine, was used to develop a simple model to predict the system performance based on the load ratio, and urine was later used to evaluate TAN transport in a more complex wastewater. High fluxes (up to 433 gN m-2 d-1) and recovery efficiencies (up to 100%) were obtained. The simple model presented here is also suited to predict the performance of similar systems for TAN recovery, and can be used to optimize their operation.

Salinity Gradients for Sustainable Energy: Primer, Progress, and Prospects.

Combining two solutions of different composition releases the Gibbs free energy of mixing. By using engineered processes to control the mixing, chemical energy stored in salinity gradients can be harnessed for useful work. In this critical review, we present an overview of the current progress in salinity gradient power generation, discuss the prospects and challenges of the foremost technologies - pressure retarded osmosis (PRO), reverse electrodialysis (RED), and capacitive mixing (CapMix) and provide perspectives on the outlook of salinity gradient power generation. Momentous strides have been made in technical development of salinity gradient technologies and field demonstrations with natural and anthropogenic salinity gradients (for example, seawater-river water and desalination brine-wastewater, respectively), but fouling persists to be a pivotal operational challenge that can significantly ebb away cost-competitiveness. Natural hypersaline sources (e.g., hypersaline lakes and salt domes) can achieve greater concentration difference and, thus, offer opportunities to overcome some of the limitations inherent to seawater-river water. Technological advances needed to fully exploit the larger salinity gradients are identified. While seawater desalination brine is a seemingly attractive high salinity anthropogenic stream that is otherwise wasted, actual feasibility hinges on the appropriate pairing with a suitable low salinity stream. Engineered solutions are foulant-free and can be thermally regenerative for application in low-temperature heat utilization. Alternatively, PRO, RED, and CapMix can be coupled with their analog separation process (reverse osmosis, electrodialysis, and capacitive deionization, respectively) in salinity gradient flow batteries for energy storage in chemical potential of the engineered solutions. Rigorous techno-economic assessments can more clearly identify the prospects of low-grade heat conversion and large-scale energy storage. While research attention is squarely focused on efficiency and power improvements, efforts to mitigate fouling and lower membrane and electrode cost will be equally important to reduce levelized cost of salinity gradient energy production and, thus, boost PRO, RED, and CapMix power generation to be competitive with other renewable technologies. Cognizance of the recent key developments and technical progress on the different technological fronts can help steer the strategic advancement of salinity gradient as a sustainable energy source.

Chain Elongation with Reactor Microbiomes: Open-Culture Biotechnology To Produce Biochemicals.

Chain elongation into medium-chain carboxylates, such as n-caproate and n-caprylate, with ethanol as an electron donor and with open cultures of microbial consortia (i.e., reactor microbiomes) under anaerobic conditions is being developed as a biotechnological production platform. The goal is to use the high thermodynamic efficiency of anaerobic fermentation to convert organic biomass or organic wastes into valuable biochemicals that can be extracted. Several liter-scale studies have been completed and a first pilot-plant study is underway. However, the underlying microbial pathways are not always well understood. In addition, an interdisciplinary approach with knowledge from fields ranging from microbiology and chemical separations to biochemistry and environmental engineering is required. To bring together research from different fields, we reviewed the literature starting with the microbiology and ending with the bioprocess engineering studies that already have been performed. Because understanding the microbial pathways is so important to predict and steer performance, we delved into a stoichiometric and thermodynamic model that sheds light on the effect of substrate ratios and environmental conditions on product formation. Finally, we ended with an outlook.

Fluidized capacitive bioanode as a novel reactor concept for the microbial fuel cell.

The use of granular electrodes in Microbial Fuel Cells (MFCs) is attractive because granules provide a cost-effective way to create a high electrode surface area, which is essential to achieve high current and power densities. Here, we show a novel reactor design based on capacitive granules: the fluidized capacitive bioanode. Activated carbon (AC) granules are colonized by electrochemically active microorganisms, which extract electrons from acetate and store the electrons in the granule. Electricity is harvested from the AC granules in an external discharge cell. We show a proof-of-principle of the fluidized capacitive system with a total anode volume of 2 L. After a start-up period of 100 days, the current increased from 0.56 A/m(2) with 100 g AC granules, to 0.99 A/m(2) with 150 g AC granules, to 1.3 A/m(2) with 200 g AC granules. Contact between moving AC granules and current collector was confirmed in a control experiment without biofilm. Contribution of an electro-active biofilm to the current density with recirculation of AC granules was limited. SEM images confirmed that a biofilm was present on the AC granules after operation in the fluidized capacitive system. Although current densities reported here need further improvement, the high surface area of the AC granules in combination with external discharge offers new and promising opportunities for scaling up MFCs.

Impact of wire geometry in energy extraction from salinity differences using capacitive technology.

Energy extraction based on capacitive Donnan potential (CDP) is a recently suggested technique for sustainable power generation. CDP combines the use of ion-exchange membranes and porous carbon electrodes to convert the Gibbs free energy of mixing sea and river water into electric work. The electrodes geometry has a relevant impact on internal resistance and overall performance in CDP. In this work, we present the first effort to use wire-shaped electrodes and its suitability for improving CDP. Analytical evaluation and electrical measurements confirm a strong nonlinear decrease in internal resistance for distances between electrodes smaller than 3 mm. We also demonstrated that we get more power per material invested when compared to traditional flat plate designs. These findings show the advantages of this design for further development of CDP into a mature technology.

Bioelectrochemical systems: an outlook for practical applications.

Bioelectrochemical systems (BESs) hold great promise for sustainable production of energy and chemicals. This review addresses the factors that are essential for practical application of BESs. First, we compare benefits (value of products and cleaning of wastewater) with costs (capital and operational costs). Based on this, we analyze the maximum internal resistance (in mΩ m(2) ) and current density that is required to make microbial fuel cells (MFCs) and hydrogen-producing microbial electrolysis cells (MECs) cost effective. We compare these maximum resistances to reported internal resistances and current densities with special focus on cathodic resistances. Whereas the current densities of MFCs still need to be increased considerably (i.e., internal resistance needs to be decreased), MECs are closer to application as their current densities can be increased by increasing the applied voltage. For MFCs, the production of high-value products in combination with electricity production and wastewater treatment is a promising route.

Capacitive bioanodes enable renewable energy storage in microbial fuel cells.

We developed an integrated system for storage of renewable electricity in a microbial fuel cell (MFC). The system contained a capacitive electrode that was inserted into the anodic compartment of an MFC to form a capacitive bioanode. This capacitive bioanode was compared with a noncapacitive bioanode on the basis of performance and storage capacity. The performance and storage capacity were investigated during polarization curves and charge-discharge experiments. During polarization curves the capacitive electrode reached a maximum current density of 1.02 ± 0.04 A/m(2), whereas the noncapacitive electrode reached a current density output of only 0.79 ± 0.03 A/m(2). During the charge-discharge experiment with 5 min of charging and 20 min of discharging, the capacitive electrode was able to store a total of 22,831 C/m(2), whereas the noncapacitive electrode was only able to store 12,195 C/m(2). Regarding the charge recovery of each electrode, the capacitive electrode was able to recover 52.9% more charge during each charge-discharge experiment compared with the noncapacitive electrode. The capacitive electrode outperformed the noncapacitive electrode throughout each charge-discharge experiment. With a capacitive electrode it is possible to use the MFC simultaneously for production and storage of renewable electricity.

Rhizosphere anode model explains high oxygen levels during operation of a Glyceria maxima PMFC.

In this paper, the effect of root oxygen loss on energy recovery of the plant microbial fuel cell (PMFC) is described. In this manner, advanced understanding of competing processes within the rhizosphere-anode interface was provided. A microscopic model was developed on the basis of exudation, oxygen loss, biological oxidation, and biological current generation. The model was successfully validated by comparison to oxygen concentration profiles, volatile fatty acid profiles, and chemical oxygen demand profiles measured in the anode compartment. The model predicted oxic zones around roots in the anode of the plant microbial fuel cell. Results show no direct link between current generation and photosynthesis. This was consistent with the model which predicted that current was generated via hydrolysis of root-derived organic compounds. This result means that to optimize energy recovery of a PMFC, the plant selection should focus on high root biomass production combined with low oxygen loss.

Effect of toxic components on microbial fuel cell-polarization curves and estimation of the type of toxic inhibition.

Polarization curves are of paramount importance for the detection of toxic components in microbial fuel cell (MFC) based biosensors. In this study, polarization curves were made under non-toxic conditions and under toxic conditions after the addition of various concentrations of nickel, bentazon, sodiumdodecyl sulfate and potassium ferricyanide. The experimental polarization curves show that toxic components have an effect on the electrochemically active bacteria in the cell. (Extended) Butler Volmer Monod (BVM) models were used to describe the polarization curves of the MFC under nontoxic and toxic conditions. It was possible to properly fit the (extended) BVM models using linear regression techniques to the polarization curves and to distinguish between different types of kinetic inhibitions. For each of the toxic components, the value of the kinetic inhibition constant Ki was also estimated from the experimental data. The value of Ki indicates the sensitivity of the sensor for a specific component and thus can be used for the selection of the biosensor for a toxic component.