Calcium Carbonate Packed Electrochemical Precipitation Column: New Concept of Phosphate Removal and Recovery.

Phosphorus (P) is a vital micronutrient element for all life forms. Typically, P can be extracted from phosphate rock. Unfortunately, the phosphate rock is a nonrenewable resource with a limited reserve on the earth. High levels of P discharged to water bodies lead to eutrophication. Therefore, P needs to be removed and is preferably recovered as an additional P source. A possible way to achieve this goal is by electrochemically induced phosphate precipitation with coexisting calcium ions. Here, we report a new concept of phosphate removal and recovery, namely a CaCO3 packed electrochemical precipitation column, which achieved improved removal efficiency, shortened hydraulic retention time, and substantially enhanced stability, compared with our previous electrochemical system. The concept is based on the introduction of CaCO3 particles, which facilitates calcium phosphate precipitation by buffering the formed H+ at the anode, releases Ca2+, acts as seeds, and establishes a high pH environment in the bulk solution in addition to that in the vicinity of the cathode. It was found that the applied current, the CaCO3 particle size, and the feed rate affect the removal of phosphate. Under optimized conditions (particle size, <0.5 mm; feed rate, 0.4 L/d; current, 5 mA), in a continuous flow system, the CaCO3 packed electrochemical precipitation column achieved 90 ± 5% removal of phosphate in 40 days and >50% removal over 125 days with little maintenance. The specific energy consumptions of this system lie between 29 and 61 kWh/kg P. The experimental results demonstrate the promising potential of the CaCO3 packed electrochemical precipitation column for P removal and recovery from P-containing streams.

Is There a Precipitation Sequence in Municipal Wastewater Induced by Electrolysis?

Electrochemical wastewater treatment can induce calcium phosphate precipitation on the cathode surface. This provides a simple yet efficient way for extracting phosphorus from municipal wastewater without dosing chemicals. However, the precipitation of amorphous calcium phosphate (ACP) is accompanied by the precipitation of calcite (CaCO3) and brucite (Mg(OH)2). To increase the content of ACP in the products, it is essential to understand the precipitation sequence of ACP, calcite, and brucite in electrochemical wastewater treatment. Given the fact that calcium phosphate (i.e., hydroxyapatite) has the lowest thermodynamic solubility product and highest saturation index in the wastewater, it has the potential to precipitate first. However, this is not observed in electrochemical phosphate recovery from raw wastewater, which is probably because of the very high Ca/P molar ratio (7.5) and high bicarbonate concentration in the wastewater resulting in formation of calcite. In the case of decreased Ca/P molar ratio (1.77) by spiking external phosphate, most of the removed Ca in the wastewater was used for ACP formation instead of calcite. The formation of of brucite, however, was only affected when the current density was decreased or the size of cathode was changed. Overall, the removal of Ca and Mg is much more affected by current density than the surface area of cathode, whereas for P removal, the reverse is true. Because of these dependencies, though there is no definite precipitation sequence among ACP, calcite, and brucite, it is still possible to influence the precipitation degree of these species by relatively low current density and high surface area or by targeting phosphorus-rich wastewaters.

Electrochemical Induced Calcium Phosphate Precipitation: Importance of Local pH.

Phosphorus (P) is an essential nutrient for living organisms and cannot be replaced or substituted. In this paper, we present a simple yet efficient membrane free electrochemical system for P removal and recovery as calcium phosphate (CaP). This method relies on in situ formation of hydroxide ions by electro mediated water reduction at a titanium cathode surface. The in situ raised pH at the cathode provides a local environment where CaP will become highly supersaturated. Therefore, homogeneous and heterogeneous nucleation of CaP occurs near and at the cathode surface. Because of the local high pH, the P removal behavior is not sensitive to bulk solution pH and therefore, efficient P removal was observed in three studied bulk solutions with pH of 4.0 (56.1%), 8.2 (57.4%), and 10.0 (48.4%) after 24 h of reaction time. While P removal efficiencies are not generally affected by bulk solution pH, the chemical-physical properties of CaP solids collected on the cathode are still related to bulk solution pH, as confirmed by structure characterizations. High initial solution pH promotes the formation of more crystalline products with relatively high Ca/P molar ratio. The Ca/P molar ratio increases from 1.30 (pH 4.0) to 1.38 (pH 8.2) and further increases to 1.55 (pH 10.0). The formation of CaP precipitates was a typical crystallization process, with an amorphous phase formed at the initial stage which then transforms to the most stable crystal phase, hydroxyapatite, which is inferred from the increased Ca/P molar ratio from 1.38 (day 1) to the theoretical 1.76 (day 11) and by the formation of needle-like crystals. Finally, we demonstrated the efficiency of this system for real wastewater. This, together with the fact that the electrochemical method can work at low bulk pH, without dosing chemicals and a need for a separation process, highlights the potential application of the electrochemical method for P removal and recovery.

Prototype of a scaled-up microbial fuel cell for copper recovery.

Background: Bioelectrochemical systems (BESs) enable recovery of electrical energy through oxidation of a wide range of substrates at an anode and simultaneous recovery of metals at a cathode. Scale-up of BESs from the laboratory to pilot scale is a challenging step in the development of the process, and there are only a few successful experiences to build on. This paper presents a prototype BES for the recovery of copper. Results: The cell design presented here had removable electrodes, similar to those in electroplating baths. The anode and cathode in this design could be replaced independently. The prototype bioelectrochemical cell consisted of an 835 cm2 bioanode fed with acetate, and a 700 cm2 cathode fed with copper. A current density of 1.2 A/-2 was achieved with 48 mW m-2 of power production. The contribution of each component (anode, electrolytes, cathode and membrane) was evaluated through the analysis of the internal resistance distribution. This revealed that major losses occurred at the anode, and that the design with removable electrodes results in higher internal resistance compared with other systems. To further assess the practical applicability of BES for copper recovery, an economic evaluation was performed. Conclusion: Analysis shows that the internal resistance of several lab-scale BESs is already sufficiently low to make the system economic, while the internal resistance for scaled-up systems still needs to be improved considerably to become economically applicable.© 2017 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Gas diffusion electrodes improve hydrogen gas mass transfer for a hydrogen oxidizing bioanode.

Background: Bioelectrochemical systems (BESs) are capable of recovery of metals at a cathode through oxidation of organic substrate at an anode. Recently, also hydrogen gas was used as an electron donor for recovery of copper in BESs. Oxidation of hydrogen gas produced a current density of 0.8 A m-2 and combined with Cu2+ reduction at the cathode, produced 0.25 W m-2. The main factor limiting current production was the mass transfer of hydrogen to the biofilm due to the low solubility of hydrogen in the anolyte. Here, the mass transfer of hydrogen gas to the bioanode was improved by use of a gas diffusion electrode (GDE). Results: With the GDE, hydrogen was oxidized to produce a current density of 2.9 A m-2 at an anode potential of -0.2 V. Addition of bicarbonate to the influent led to production of acetate, in addition to current. At a bicarbonate concentration of 50 mmol L-1, current density increased to 10.7 A m-2 at an anode potential of -0.2 V. This increase in current density could be due to oxidation of formed acetate in addition to oxidation of hydrogen, or enhanced growth of hydrogen oxidizing bacteria due to the availability of acetate as carbon source. The effect of mass transfer was further assessed through enhanced mixing and in combination with the addition of bicarbonate (50 mmol L-1) current density increased further to 17.1 A m-2. Conclusion: Hydrogen gas may offer opportunities as electron donor for bioanodes, with acetate as potential intermediate, at locations where excess hydrogen and no organics are available. © 2017 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Periodic feedwater reversal and air sparging as antifouling strategies in reverse electrodialysis.

Renewable energy can be generated using natural streams of seawater and river water in reverse electrodialysis (RED). The potential for electricity production of this technology is huge, but fouling of the membranes and the membrane stack reduces the potential for large scale applications. This research shows that, without any specific antifouling strategies, the power density decreases in the first 4 h of operation to 40% of the originally obtained power density. It slowly decreases further in the remaining 67 days of operation. Using antifouling strategies, a significantly higher power density can be maintained. Periodically switching the feedwaters (i.e., changing seawater for river water and vice versa) generates the highest power density in the first hours of operation, probably due to a removal of multivalent ions and organic foulants from the membrane when the electrical current reverses. In the long term, colloidal fouling is observed in the stack without treatment and the stack with periodic feedwater switching, and preferential channeling is observed in the latter. This decreases the power density further. This decrease in power density is partly reversible. Only a stack with periodic air sparging has a minimum of colloidal fouling, resulting in a higher power density in the long term. A combination of the discussed antifouling strategies, together with the use of monovalent selective membranes, is recommended to maintain a high power density in RED in short-term and long-term operations.

Electrochemical route outperforms chemical struvite precipitation in mitigating heavy metal contamination.

Electrochemically mediated struvite precipitation (EMSP) offers a robust, chemical-free process towards phosphate and ammonium reclamation from nutrients-rich wastewater, i.e., swine wastewater. However, given the coexistence of heavy metal, struvite recovered from wastewater may suffer from heavy metal contamination. Here, we systematically investigated the fate of Cu2+, as a representative heavy metal, in the EMSP process and compared it with the chemical struvite precipitation (CSP) system. The results showed that Cu2+ was 100% transferred from solution to solid phase as a mixture of copper and struvite under pHi 9.5 with 2-20 mg/L Cu2+ in the CSP system, and varying pH would affect struvite production. In the EMSP system, the formation of struvite was not affected by bulk pH, and struvite was much less polluted by co-removed Cu2+ (24.4%) at pHi 7.5, which means we recovered a cleaner and safer product. Specifically, struvite mainly accumulates on the front side of the cathode. In contrast, the fascinating thing is that Cu2+ is ultimately deposited primarily to the back side of the cathode in the form of copper (hydro)oxides due to the distinct thickness of the local high pH layer on the two sides of the cathode. In turn, struvite and Cu (hydro)oxides can be harvested separately from the front and back sides of the cathode, respectively, facilitating the subsequent recycling of heavy metals and struvite. The contrasting fate of Cu2+ in the two systems highlights the merits of EMSP over conventional CSP in mitigating heavy metal pollution on recovered products, promoting the development of EMSP technology towards a cleaner recovery of struvite from waste streams.

Toward Redox-Free Reverse Electrodialysis with Carbon-Based Slurry Electrodes.

Clean and renewable salinity gradient energy can be harvested using reverse electrodialysis (RED). The electrode system is an essential part to convert ionic current into electrical current. In this study, a typical 0.10 × 0.10 m2 RED stack with a cross-flow configuration was used to test carbon-based slurry electrodes (CSEs) to replace the usual redox solutions, like hexacyanoferrate, to enhance the RED process' sustainability, stability, and economic value. Six different slurry compositions comprising activated carbon, carbon black, and graphite powder were tested. The CSE characteristics were systematically studied by measuring viscosity, electrode compartment pressure drop, maximum current density, stability, and performance of power density and energy efficiency. Using a single membrane configuration, the CSE ran continuously for 17 days with a stable output. The application of CSEs for RED, with artificial seawater and river water, using mixing activated carbon and carbon black at a total concentration of 20 wt %, resulted in the best performance with a net power density of 0.7 W·m-2. Moreover, higher current densities up to 350 A·m-2 were tested for ED and shown to be feasible until 150 A·m-2. CSEs show promising versatility for different application modes.

Understanding the Impact of the Three-Dimensional Junction Thickness of Electrospun Bipolar Membranes on Electrochemical Performance.

The use of electrospun bipolar membranes (BPMs) with an interfacial three-dimensional (3D) junction of entangled nano-/microfibers has been recently proposed as a promising fabrication strategy to develop high-performance BPMs. In these BPMs, the morphology and physical properties of the 3D junction are of utmost importance to maximize the membrane performance. However, a full understanding of the impact of the junction thickness on the membrane performance is still lacking. In this study, we have developed bipolar membranes with the same composition, only varying the 3D junction thicknesses, by regulating the electrospinning time used to deposit the nano-/microfibers at the junction. In total, four BPMs with 3D junction thicknesses of ∼4, 8, 17, and 35 µm were produced to examine the influence of the junction thickness on the membrane performance. Current-voltage curves for water dissociation of BPMs exhibited lower voltages for BPMs with thicker 3D junctions, as a result of a three-dimensional increase in the interfacial contact area between cation- and anion-exchange fibers and thus a larger water dissociation reaction area. Indeed, increasing the BPM thickness from 4 to 35 µm lowered the BPM water dissociation overpotential by 32%, with a current efficiency toward HCl/NaOH generation higher than 90%. Finally, comparing BPM performance during the water association operation revealed a substantial reduction in the voltage from levels of its supplied open circuit voltage (OCV), owing to excessive hydroxide ion (OH-) and proton (H+) leakage through the relevant layers. Overall, this work provides insights into the role of the junction thickness on electrospun BPM performance as a crucial step toward the development of membranes with optimal entangled junctions.

Combined Electrospinning-Electrospraying for High-Performance Bipolar Membranes with Incorporated MCM-41 as Water Dissociation Catalysts.

Electrospinning has been demonstrated as a very promising method to create bipolar membranes (BPMs), especially as it allows three-dimensional (3D) junctions of entangled anion exchange and cation exchange nanofibers. These newly developed BPMs are relevant to demanding applications, including acid and base production, fuel cells, flow batteries, ammonia removal, concentration of carbon dioxide, and hydrogen generation. However, these applications require the introduction of catalysts into the BPM to allow accelerated water dissociation, and this remains a challenge. Here, we demonstrate a versatile strategy to produce very efficient BPMs through a combined electrospinning-electrospraying approach. Moreover, this work applies the newly investigated water dissociation catalyst of nanostructured silica MCM-41. Several BPMs were produced by electrospraying MCM-41 nanoparticles into the layers directly adjacent to the main BPM 3D junction. BPMs with various loadings of MCM-41 nanoparticles and BPMs with different catalyst positions relative to the junction were investigated. The membranes were carefully characterized for their structure and performance. Interestingly, the water dissociation performance of BPMs showed a clear optimal MCM-41 loading where the performance outpaced that of a commercial BPM, recording a transmembrane voltage of approximately 1.11 V at 1000 A/m2. Such an excellent performance is very relevant to fuel cell and flow battery applications, but our results also shed light on the exact function of the catalyst in this mode of operation. Overall, we demonstrate clearly that introducing a novel BPM architecture through a novel hybrid electrospinning-electrospraying method allows the uptake of promising new catalysts (i.e., MCM-41) and the production of very relevant BPMs.

Basket anode filled with CaCO3 particles: A membrane-free electrochemical system for boosting phosphate recovery and product purity.

Phosphorus (P) is often regarded as the primary stimulant for eutrophication, while its importance as a crucial life element is also well acknowledged. Given its future scarcity, P recycling from waste streams is suggested and practiced. Electrochemically mediated precipitation (EMP) is a robust and chemical-free process for P removal and recovery, yet it requires further developments. The first generation of the CaCO3-packed electrochemical precipitation column successfully solved the problem of H+-OH- recombination, achieving enhanced P removal efficiency with less energy consumption but suffering from low Ca-phosphate purity in recovered products. Herein, a new concept of a basket-anode electrochemical system is proposed and validated to prevent direct H+-OH- recombination and enhance product purity. The CaCO3 pellets packed basket anode alleviates the OH- depletion by CaCO3-H+ interaction and provides extra Ca2+ for enhanced P removal. The novel structure of the basket anode, by its derived acidic anode region and alkaline cathode region, completely avoids the precipitation of Ca-phosphate on the packed CaCO3 and greatly facilitates the collection of high-quality Ca-phosphate product. Our results suggest that almost 100% of the removed P was in high-purity, highly crystalline Ca-phosphate on the cathode. The recovered products contained significantly more P (13.5 wt%) than in the previous study (0.1 wt%) at similar energy consumptions (29.8 kWh/kg P). The applied current density, pellets size, and influent P concentration were critical for P removal performance, product purity, and power consumption. We further demonstrated the long-term stability of this novel system and its technical and economic feasibility in treating real stored urine. Our study provides new cell architectural designs to enhance the performance of EMP systems and may inspire innovations and developments in other electrochemical water treatment processes.

Doubled power density from salinity gradients at reduced intermembrane distance.

The mixing of sea and river water can be used as a renewable energy source. The Gibbs free energy that is released when salt and fresh water mix can be captured in a process called reverse electrodialysis (RED). This research investigates the effect of the intermembrane distance and the feedwater flow rate in RED as a route to double the power density output. Intermembrane distances of 60, 100, 200, and 485 µm were experimentally investigated, using spacers to impose the intermembrane distance. The generated (gross) power densities (i.e., generated power per membrane area) are larger for smaller intermembrane distances. A maximum value of 2.2 W/m(2) is achieved, which is almost double the maximum power density reported in previous work. In addition, the energy efficiency is significantly higher for smaller intermembrane distances. New improvements need to focus on reducing the pressure drop required to pump the feedwater through the RED-device using a spacerless design. In that case power outputs of more than 4 W per m(2) of membrane area at small intermembrane distances are envisaged.

Tailoring the Surface Chemistry of Anion Exchange Membranes with Zwitterions: Toward Antifouling RED Membranes.

Fouling is a pressing issue for harvesting salinity gradient energy with reverse electrodialysis (RED). In this work, antifouling membranes were fabricated by surface modification of a commercial anion exchange membrane with zwitterionic layers. Either zwitterionic monomers or zwitterionic brushes were applied on the surface. Zwitterionic monomers were grafted to the surface by deposition of a polydopamine layer followed by an aza-Michael reaction with sulfobetaine. Zwitterionic brushes were grafted on the surface by deposition of polydopamine modified with a surface initiator for subsequent atom transfer radical polymerization to obtain polysulfobetaine. As expected, the zwitterionic layers did increase the membrane hydrophilicity. The antifouling behavior of the membranes in RED was evaluated using artificial river and seawater and sodium dodecylbenzenesulfonate as the model foulant. The zwitterionic monomers are effective in delaying the fouling onset, but the further build-up of the fouling layer is hardly affected, resulting in similar power density losses as for the unmodified membranes. Membranes modified with zwitterionic brushes show a high potential for application in RED as they not only delay the onset of fouling but they also slow down the growth of the fouling layer, thus retaining higher power density outputs.

Electrochemical Recovery of Phosphorus from Acidic Cheese Wastewater: Feasibility, Quality of Products, and Comparison with Chemical Precipitation.

The recovery of phosphorus (P) from high-strength acidic waste streams with high salinity and organic loads is challenging. Here, we addressed this challenge with a recently developed electrochemical approach and compared it with the chemical precipitation method via NaOH dosing. The electrochemical process recovers nearly 90% of P (∼820 mg/L) from cheese wastewater in 48 h at 300 mA with an energy consumption of 64.7 kWh/kg of P. With chemical precipitation, >86% of P was removed by NaOH dosing with a normalized cost of 1.34-1.80 euros/kg of P. The increase in wastewater pH caused by NaOH dosing triggered the formation of calcium phosphate sludge instead of condensed solids. However, by electrochemical precipitation, the formed calcium phosphate is attached to the electrode, allowing the subsequent collection of solids from the electrode after treatment. The collected solids are characterized as amorphous calcium phosphate (ACP) at 200 mA or a precipitation pH of ≥9. Otherwise, they are a mixture of ACP and hydroxyapatite. The products have sufficient P content (≤14%), of which up to 85% was released within 30 min in 2% citric acid and a tiny amount of heavy metals compared to phosphate rocks. This study paves the way for applying electrochemical removal and recovery of phosphorus from acidic P-rich wastewater and offers a sustainable substitute for mined phosphorus.

Electrochemical recovery of phosphorus from wastewater using tubular stainless-steel cathode for a scalable long-term operation.

Phosphorus (P) is an irreplaceable element, playing a vital role in living organisms, yet has limited earth reserves. The possibility of P recovery from wastewaters by electrochemically-induced calcium phosphate precipitation (ECaPP) was demonstrated previously. The current study presents a novel scalable prototype consisting of a column-shaped electrochemical reactor, a tubular stainless-steel cathode, and a Pt coated Ti anode. The adhesion of solids to the cathode, important for product recovery, was shown not to be negatively impacted by electrodes' vertical placement. The influence of current (density), hydraulic retention time (HRT), and initial phosphate concentration in this prototype were examined under continuous flow operation. The system accomplished the highest P removal rate (1267 mg/day) at 1.5 d HRT and 800 mA in treating undiluted cheese wastewater with 48.5 kWh/kg P. Moreover, the prototype showed high stability and efficiency (> 50%) over 173 days of continuous operation without performing maintenance. After turning off the current (0 mA), the system realized a surprising P removal jump up to 97.3%, revealing the delayed diffusion of hydroxide ions by the deposition layer. The calculation of CAPEX and OPEX of ECaPP in treating 100 m3 cheese wastewater per week indicates that the ECaPP plant can realize net-positive from the 12th year. The recovered solids have relatively high P content (> 9wt%) and insignificant contamination of heavy metals. Overall, the proven suitability of the scalable prototype can pave the way towards the actual adoption of the ECaPP process.

Entanglement-Enhanced Water Dissociation in Bipolar Membranes with 3D Electrospun Junction and Polymeric Catalyst.

With the use of bipolar membranes (BPMs) in an expanding range of applications, there is an urgent need to understand and improve the catalytic performance of BPMs for water dissociation, as well as to increase their physical and chemical stability. In this regard, electrospinning BPMs with 2D and 3D junction structures have been suggested as a promising route to produce high-performance BPMs. In this work, we investigate the effect of entangling anion and cation exchange nanofibers at the junction of bipolar membranes on the water dissociation rate. In particular, we compare the performance of different tailor-made BPMs with a laminated 2D junction and a 3D electrospun entangled junction, while using the same type of anion and cation exchange polymers in a single/dual continuous electrospinning manufacturing method. The bipolar membrane with a 3D entangled junction shows an enhanced water dissociation rate as compared to the bipolar membrane with laminated 2D junction, as measured by the decreased bipolar membrane potential. Moreover, we investigate the use of a third polymer, that is, poly(4-vinylpyrrolidine) (P4VP), as a catalyst for water dissociation. This polymer confirmed that a 3D entangled junction BPM (with incorporated P4VP) gives a higher water dissociation rate than does a 2D laminated junction BPM with P4VP as the water dissociation catalyst. This work demonstrates that the entanglement of the anion exchange polymer with P4VP as the water dissociation catalyst in a 3D junction is promising to develop bipolar membranes with enhanced performance as compared to the conventionally laminated membranes.

Electrochemically mediated precipitation of phosphate minerals for phosphorus removal and recovery: Progress and perspective.

Phosphorus (P) is an essential element for the growth and reproduction of organisms. Unfortunately, the natural P cycle has been broken by the overexploitation of P ores and the associated discharge of P into water bodies, which may trigger the eutrophication of water bodies in the short term and possible P shortage soon. Consequently, technologies emerged to recover P from wastewater to mitigate pollution and exploit secondary P resources. Electrochemically induced phosphate precipitation has the merit of achieving P recovery without dosing additional chemicals via creating a localized high pH environment near the cathode. We critically reviewed the development of electrochemically induced precipitation systems toward P removal and recovery over the past ten years. We summarized and discussed the effects of pH, current density, electrode configuration, and water matrix on the performance of electrochemical systems. Next to ortho P, we identified the potential and illustrated the mechanism of electrochemical P removal and recovery from non-ortho P compounds by combined anodic or anode-mediated oxidation and cathodic reduction (precipitation). Furthermore, we assessed the economic feasibility of electrochemical methods and concluded that they are more suitable for treating acidic P-rich waste streams. Despite promising potentials and significant progress in recent years, the application of electrochemical systems toward P recovery at a larger scale requires further research and development. Future work should focus on evaluating the system's performance under long-term operation, developing an automatic process for harvesting P deposits, and performing a detailed economic and life-cycle assessment.

Electrical power from sea and river water by reverse electrodialysis: a first step from the laboratory to a real power plant.

Electricity can be produced directly with reverse electrodialysis (RED) from the reversible mixing of two solutions of different salinity, for example, sea and river water. The literature published so far on RED was based on experiments with relatively small stacks with cell dimensions less than 10 × 10 cm(2). For the implementation of the RED technique, it is necessary to know the challenges associated with a larger system. In the present study we show the performance of a scaled-up RED stack, equipped with 50 cells, each measuring 25 × 75 cm(2). A single cell consists of an AEM (anion exchange membrane) and a CEM (cation exchange membrane) and therefore, the total active membrane area in the stack is 18.75 m(2). This is the largest dimension of a reverse electrodialysis stack published so far. By comparing the performance of this stack with a small stack (10 × 10 cm(2), 50 cells) it was found that the key performance parameter to maximal power density is the hydrodynamic design of the stack. The power densities of the different stacks depend on the residence time of the fluids in the stack. For the large stack this was negatively affected by the increased hydrodynamic losses due to the longer flow path. It was also found that the large stack generated more power when the sea and river water were flowing in co-current operation. Co-current flow has other advantages, the local pressure differences between sea and river water compartments are low, hence preventing leakage around the internal manifolds and through pinholes in the membranes. Low pressure differences also enable the use of very thin membranes (with low electrical resistance) as well as very open spacers (with low hydrodynamic losses) in the future. Moreover, we showed that the use of segmented electrodes increase the power output by 11%.

Electrochemically mediated calcium phosphate precipitation from phosphonates: Implications on phosphorus recovery from non-orthophosphate.

Phosphonates are an important type of phosphorus-containing compounds and have possible eutrophication potential. Therefore, the removal of phosphonates from waste streams is as important as orthophosphate. Herein, we achieved simultaneously removal and recovery of phosphorus from nitrilotris (methylene phosphonic acid) (NTMP) using an electrochemical cell. It was found that the C-N and C-P bonds of NTMP were cleaved at the anode, leading to the formation of orthophosphate and formic acid. Meanwhile, the converted orthophosphate reacted with coexisting calcium ions and precipitated on the cathode as recoverable calcium phosphate solids, due to an electrochemically induced high pH region near the cathode. Electrochemical removal of NTMP (30 mg/L) was more efficient when dosed to effluent of a wastewater treatment plant (89% in 24 h) than dosed to synthetic solutions of 1.0 mM Ca and 50 mM Na2SO4 (43% in 168 h) while applying a current density of 28 A/m2 and using a Pt anode and Ti cathode. The higher removal efficiency of NTMP in real waste water is due to the presence of chloride ions, which resulted in anodic formation of chlorine. This study establishes a one-step approach for simultaneously phosphorus removal and recovery of calcium phosphate from non-orthophosphates.

Electrochemical removal of phosphate in the presence of calcium at low current density: Precipitation or adsorption？.

Phosphorus removal and recovery from waste streams are crucial to prevent eutrophication and sustain fertilizer production. As has been shown in our previous papers, electrochemical treatment has the potential to achieve this goal. However, the adoption of electrochemical approach is limited by its high energy consumption. Here, we investigate the possibility of electrochemical phosphorus removal at extremely low current density using graphite felt as the cathode. We found a current density as low as 0.04 A/m2 can enhance the removal of phosphate in our electrochemical system. The removal of phosphate at extremely low current density resulted from electrochemical induced calcium phosphate precipitation and not by electrochemical adsorption. Electrochemical treatment of real domestic wastewater at 0.2 A/m2 almost eliminates the precipitation of Mg(OH)2 and limits the formation of CaCO3. The recovered precipitates are dominated by calcium phosphate (59%), followed by 35% CaCO3 and 6% Mg(OH)2. The specific energy consumption of this newly electrochemical system is between 4.4 and 26.4 kW h/kg P, which is 2 orders of magnitude lower than our previous system (110-2238 kW h/kg P). Key factors for this improvement prove to be enlarged precipitation area and hydroxide flux retardation by graphite felt. Practically, our study offers a potential way to reduce the energy consumption in electrochemical removal of phosphate by using a graphite felt cathode and at a current density below 0.2 A/m2. Fundamentally, our study contributes to the understanding of adsorption and precipitation in electrochemical removal of phosphate at an extremely low current density and with carbon-based electrodes.