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Advancing wastewater sustainability: Nafion-powered ammonium recovery

Wastewater treatment plant Bern

With global population growth and the resulting increase in environmental stress, the need for sustainable wastewater treatment is becoming ever more urgent. Traditional methods focus on removing pollutants but often overlook the opportunity to recover valuable resources. One such resource is ammonium. This nitrogen-containing molecule promotes growth and is a key component of fertilizers. When mishandled, such as through over-fertilization, ammonium becomes one of the main contributors to nitrogen pollution.

A promising solution lies in bioelectrical systems. This umbrella term refers to innovative technologies that not only purify wastewater but also recover resources like ammonium. At the same time, bioelectrical systems generate clean energy such as electricity or biogas. The technology is based on galvanic cells, where the two cell chambers are often separated by a membrane. High-performance cation exchange membranes enable precise ion transport and system stability. The premium product among cation exchange membranes is Nafion, such as our Nafion 115 membrane.

At Frontis Energy, we have demonstrated that bioelectrochemical systems can remove ammonium from wastewater, offering an energy-efficient alternative to the energy-intensive Haber-Bosch process. To validate this concept, we developed microbiological electrolysis cells populated with microorganisms from oxygen-deprived marine sediments off the coast of Namibia. These sediments are naturally rich in ammonia and low in organic carbon, ideal conditions for microbes capable of anaerobic ammonium oxidation. For comparison, we also used conventional municipal wastewater to populate the electrodes.

Maintaining anoxic conditions was crucial to avoid nitrification, a process that transfers electrons directly to oxygen, bypassing the anode and resulting in energy loss and reduced hydrogen production. Instead, we regulated the anode potential between +150 mV and +550 mV, well below the redox potential required for water oxidation (+820 mV). This configuration enabled the oxidation of ammonium to nitrogen gas (N₂) at the anode, while hydrogen (H₂) or methane gas was produced at the cathode.

Central to this process is Nafion 115, a membrane made of perfluorosulfonic acid polymers (PFSA polymers). Its exceptional proton conductivity, chemical resistance, and mechanical robustness make it ideal for demanding wastewater environments. Nafion 115 acts like a selective gate, allowing ammonium ions (NH₄⁺) to migrate from the anode to the cathode while blocking competing ions and maintaining anoxic conditions. This selective transport, driven by electric field gradients and concentration differences, ensures efficient nutrient recovery and stable performance of the bioelectrical system.

A practical validation of this technology comes from our earlier report, in which researchers developed a two-chamber, anoxic bioelectrical reactor that continuously removed ammonium at a rate of about 5 g/m³/day. Their system converted over 97% of the ammonium directly into nitrogen gas. This transformation occurred without the formation of harmful byproducts like nitrite or NOx gases. Particularly impressive was the energy consumption, just 0.13 kWh per kilogram of nitrogen removed. That is a 35-fold reduction compared to conventional aeration, which typically requires around 5 kWh/kg.

These results highlight the transformative potential of bioelectrical systems. As mentioned earlier, significant energy is used to remove nitrogen from wastewater, only to make it available again via the Haber-Bosch process, accounting for 1–2% of global energy consumption. Bioelectrical systems offer a circular alternative: by coupling ammonium oxidation with hydrogen production, wastewater treatment plants could become net energy producers. The generated hydrogen and biogas can be used directly for electricity generation and ultimately to reduce greenhouse gas emissions.

With the right biofilms, well-controlled electrode potentials, and robust membranes like Nafion 115, ammonium can serve as a clean, resource-efficient alternative to water electrolysis. This underscores the potential of bioelectrical systems to build a circular water economy, where waste is treated as a resource.

This technology reflects Frontis Energy’s commitment to promoting clean, efficient, and circular solutions that turn ecological challenges into sustainable opportunities.

Image: Wastewater treatment plant Bern

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Advances in Ammonium Recovery with Bioelectrical Systems

DOI: 10.13140/RG.2.2.16014.22082

In recent decades, the focus of wastewater treatment has shifted from mere disposal to the recovery of valuable resources. This approach aims to harness energy and nutrients found in wastewater. Among emerging technologies are bioelectrical systems, which can recover not only energy and carbon but also valuable compounds like ammonium. Nitrogen bound in ammonium is a key component of fertilizers. Today, two-thirds of this resource are produced through the highly energy-intensive Haber-Bosch process using natural gas extracted from air. Fertilizer production significantly contributes to anthropogenic CO₂ emissions and, ultimately, to global warming.

Bioelectrical systems for ammonium recovery are classified into microbial fuel cells and microbial electrolysis cells. In both, electrogenic microorganisms oxidize organic matter in wastewater into carbon dioxide and protons. Exoelectrogens, also known as anode-respiring bacteria, use the anode as an electron acceptor instead of oxygen, thereby gaining energy for their metabolic processes.

By combining microbial activity with electrochemical processes, chemical reactions in wastewater treatment are catalyzed efficiently. This novel biocatalytic application still faces challenges in terms of optimization for practical use. At Frontis Energy, we have already demonstrated through a patented process that ammonium can be effectively removed from wastewater using bioelectrical systems. We are currently working on scaling this method for industrial deployment. However, a comprehensive understanding of the underlying processes and recovery mechanisms is still lacking.

A new study conducted by the Autonomous University of Barcelona investigated the development and optimization of bioelectrical systems aimed at recovering ammonium from wastewater in an energy-efficient and concentrated form. The findings were recently published in Bioelectrochemistry. Using a three-chamber configuration with a hydrophobic membrane, the researchers systematically examined the influence of different levels of electric current and ammonium concentrations on recovery efficiency. The system achieved its highest ammonium recovery rate of 55 g/m²/day at a current of 75 mA. Overall, a 97% removal of ammonium from a 0.3% solution was attained.

Notably, electrons flow from the anode to the cathode via an external circuit, where they react with an electron acceptor. In ammonium recovery systems, ammonium ions migrate from the anode to the cathode through a cation exchange membrane, driven by concentration gradients and the electric field, allowing them to accumulate in the cathode chamber.

While this ion transport mechanism supports efficient ammonium recovery, the researchers found that high-performance operation led to material wear at the cathode. This highlights the need to balance operational intensity with material durability. Consequently, the team explored different cathode materials and voltages. Stainless steel electrodes operated at 1.4 V yielded the best results, achieving a removal rate of 21 g/m²/day and a recovery rate of 17 g/m²/day, primarily due to enhanced cation migration resulting from higher current density.

Long-term experiments revealed that higher ammonium concentration in the anolyte significantly improves selective migration of ammonium ions through the cation exchange membrane, further boosting system performance. Operating at 1.4 V increased recovery efficiency and reduced energy consumption per gram of nitrogen—making the process more cost-effective and environmentally friendly.

These insights underscore the practical potential of bioelectrical systems as a pioneering solution for sustainable nitrogen recovery. By fine-tuning material selection, system design, and operational parameters, high ammonium removal and recovery rates can be achieved with minimal energy input.

From an industrial perspective, this study represents a scalable advance in resource recovery within existing wastewater treatment infrastructures. If scaled, the technology could reduce reliance on the energy-intensive Haber-Bosch process.

Since concentrated ammonium is a commercially viable product, its recovery reduces operational costs for wastewater treatment plants. If the scaled-up process maintains its long-term stability and low energy demand, these would be compelling arguments for adopting bioelectrical technologies as part of a circular economy.

At Frontis Energy, we see great potential in scaling this technology and making a meaningful contribution to sustainable wastewater treatment.

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