(Invited) Next Generation Electrified Membrane Technology for Simultaneous Wastewater Treatment and Production of Nitrogen Fertilizer
Authors: Gao Jianan , Zhang Wen 
Published: September 2023

Recovery and repurposing of wastewater nitrogen such as nitrate (NO3
−) and nitrite (NO2
−) receive increasing attention as the current approaches of biological nitrogen removal or conversion into nitrogen gas (N2) renders high energy footprints. This study reported the first electrified membrane upcycling of NO3
− into NH3 that further converted into ammonia sulfate (NH4SO4), a liquid fertilizer readily for use. Paired electrolysis was used to couple simultaneous cathodic and anodic electrochemical half-reactions to enable nitrate reduction and eliminate the external acid/base consumption. Under a partial current density of 63.8±4.4 mA·cm−2 on a cathodic membrane made of a mixed-valence copper oxide and a polytetrafluoroethylene (PTFE) hydrophobic substrate, a recovery rate and energy consumption of 3100±91 g-(NH4)2SO4·m−2·d−1 and 21.8±3.8 kWh·kg−1-(NH4)2SO4 were achieved with the synthetic feed solution (150 mM NO3
−) flowing into the cathode chamber and the produced NH3 migrating across the cathodic membrane into a trap and anode chambers filled with the flowing 0.5 M Na2SO4 solution. 99.9% NO3
− was removed in the feed after 5 h operation with a NH3 recovery rate of 99.5%. This electrified membrane process was demonstrated to achieve comparable performances of synergistic nitrate decontamination and nutrient recovery using real nitrate wastewater with durable catalytic activity and stability. Specifically, the required electricity cost for converting 10 to 100 mM NO3
− to (NH4)2SO4 was $675 to $408 ton−1, respectively. The obtained (NH4)2SO4 may be sold as fertilizer at a price of 533 $·ton−1 (according to USDA) and further offset the cost of the NO3
− removal.

According to the International Fertilizer Association, in 2018 the U.S. ranked second in nitrogen production, representing 11.6% of global production. However, it still requires the importation of nitrogen fertilizer, to fully meet the national demand. The US Environmental Protection Agency reports that in 2013, ~38 kg of nitrogen per acre per year was used for fertilization, and in 2016, 94 million acres of corn were planted in the US, representing ~40% of US fertilizer demand. Roughly, this equates to ~8.9 billion kg of nitrogen per year needed to meet total US fertilization demand. The nitrogen available in drinking water sources is roughly 65 million kg per year, and the nitrogen available in wastewater sources is roughly 2.4 billion kg per year. Thus, by fully recovering the nitrogen from wastewater 34.3% of the US nitrogen fertilizer requirement could be met. This could also further mitigate the increase in nitrogen fertilizer prices due to blocked nitrogen fertilizer imports and even free the US from nitrogen fertilizer imports. According to U.S. Department of Agriculture, the average U.S. farm price of sulfate of ammonium fertilizers is $533 per ton. Even leaving aside the revenue generated by the treatment of nitrogen-containing sewage, the market size of nitrogen fertilizer produced through sewage is as high as $12.8 billion.