Ammonia recovery from wastewater has positive environmental benefits, avoiding eutrophication and reducing production energy consumption, which is one of the most effective ways to manage nutrients in wastewater. Specifically, ammonia recovery by membrane distillation has been gradually adopted due to its excellent separation properties for volatile substances. However, the global optimization of direct contact membrane distillation (DCMD) operating parameters to maximize ammonia recovery efficiency (ARE) has not been attempted. In this work, three key operating factors affecting ammonia recovery, i.e., feed ammonia concentration, feed pH, and DCMD running time, were identified from eight factors, by a two-level Plackett-Burman Design (PBD). Subsequently, Box-Behnken design (BBD) under the response surface methodology (RSM) was used to model and optimize the significant operating parameters affecting the recovery of ammonia though DCMD identified by PBD and statistically verified by analysis of variance (ANOVA). Results showed that the model had a high coefficient of determination value (R2 = 0.99), and the interaction between NH4Cl concentration and feed pH had a significant effect on ARE. The optimal operating parameters of DCMD as follows: NH4Cl concentration of 0.46 g/L, feed pH of 10.6, DCMD running time of 11.3 h, and the maximum value of ARE was 98.46%. Under the optimized conditions, ARE reached up to 98.72%, which matched the predicted value and verified the validity and reliability of the model for the optimization of ammonia recovery by DCMD process.

Membrane contactors are among the available technologies that allow a reduction in the amount of ammoniacal nitrogen released into the environment through a process called transmembrane chemical absorption (TMCA). This process can be operated with different substances acting as trapping solutions; however, strong inorganic acids have been studied the most. The purpose of this study was to demonstrate, at laboratory scale, the performance of citric acid as a capturing solution in TMCA processes for recovering ammonia as an organic fertilizer from anaerobic digestor reject water using membrane contactors in a liquid-liquid configuration and to compare it with the most studied solution, sulfuric acid. The experiments were carried out at 22 °C and 40 °C and with a feed water pH of 10 and 10.5. When the system was operated at pH 10, the rates of recovered ammonia from the feed solution obtained with citric acid were 10.7-16.5 percentage points (pp) lower compared to sulfuric acid, and at pH 10.5, the difference decreased to 5-10 pp. Under all tested conditions, the water vapor transport in the system was lower when using citric acid as the trapping solution, and at pH 10 and 40 °C, it was 5.7 times lower. When estimating the operational costs for scaling up the system, citric acid appears to be a better option than sulfuric acid as a trapping solution, but in both cases, the process was not profitable under the studied conditions.

The electrochemical nitrate reduction reaction (NO3RR) is able to convert nitrate (NO3 -) into reusable ammonia (NH3), offering a green treatment and resource utilization strategy of nitrate wastewater and ammonia synthesis. The conversion of NO3 - to NH3 undergoes water dissociation to generate active hydrogen atoms and nitrogen-containing intermediates hydrogenation tandemly. The two relay processes compete for the same active sites, especially under pH-neutral condition, resulting in the suboptimal efficiency and selectivity in the electrosynthesis of NH3 from NO3 -. Herein, we constructed a Cu1-Fe dual-site catalyst by anchoring Cu single atoms on amorphous iron oxide shell of nanoscale zero-valent iron (nZVI) for the electrochemical NO3RR, achieving an impressive NO3 - removal efficiency of 94.8 % and NH3 selectivity of 99.2 % under neutral pH and nitrate concentration of 50 mg L-1 NO3 --N conditions, greatly surpassing the performance of nZVI counterpart. This superior performance can be attributed to the synergistic effect of enhanced NO3 - adsorption on Fe sites and strengthened water activation on single-atom Cu sites, decreasing the energy barrier for the rate-determining step of *NO-to-*NOH. This work develops a novel strategy of fabricating dual-site catalysts to enhance the electrosynthesis of NH3 from NO3 -, and presents an environmentally sustainable approach for neutral nitrate wastewater treatment.

Ammonia recovery from wastewater is of great significance for aquatic ecology safety, human health and carbon emissions reduction. Electrochemical methods have gained increasing attention since the authigenic base and acid of electrochemical systems can be used as stripper and absorbent for transmembrane chemisorption of ammonia, respectively. However, the separation of electrodes and gas permeable membrane (GPM) significantly restricts the ammonia transfer-transformation process and the authigenic acid-base utilization. To break the restrictions, this study developed a gas permeable membrane electrode assembly (GPMEA), which innovatively integrated anode and cathode on each side of GPM through easy phase inversion of polyvinylidene fluoride binder, respectively. With the GPMEA assembled in a stacked transmembrane electro-chemisorption (sTMECS) system, in situ utilization of authigenic acid and base for transmembrane electro-chemisorption of ammonia was achieved to enhance the ammonia recovery from wastewater. At current density of 60 A/m2, the transmembrane ammonia flux of the GPMEA was 693.0 ± 15.0 g N/(m2·d), which was 86 % and 28 % higher than those of separate GPM and membrane cathode, respectively. The specific energy consumption of the GPMEA was 9.7∼16.1 kWh/kg N, which were about 50 % and 25 % lower than that of separate GPM and membrane cathode, respectively. Moreover, the application of GPMEA in the ammonia recovery from wastewater is easy to scale up in the sTMECS system. Accordingly, with the features of excellent performance, energy saving and easy scale-up, the GPMEA showed good prospects in electrochemical ammonia recovery from wastewater.

The ammonia recovery from wastewater via electrochemical technologies represents a promising way for wastewater treatment, resource recovery, and carbon emissions reduction. However, chemicals consumption and reactors scalability of the existing electrochemical systems have become the key challenges for their development and application. In this study, a stacked transmembrane electro-chemisorption (sTMECS) system was developed to utilize authigenic acid and base on site for enhancing ammonia recovery from wastewater. The easily scaled up system was achieved via innovatively connecting the cathode chamber in a unit with the anode chamber in the adjacent unit by a hydrophobic gas permeable membrane (GPM). Thus, authigenic base at cathodes and authigenic acid at anodes could be utilized as stripper and absorbent on site to enhance the transmembrane chemisorption of ammonia. Continuous power supply, reducing the distances of electrodes to GPM and moderate aeration of the catholyte could promote ammonia recovery. Applied to the ammonia recovery from the simulated urine, the sTMECS under the current density 62.5 A/cm2 with a catholyte aeration rate of 3.2 L/(L⋅min) for operation time 4 h showed the transmembrane ammonia flux of 26.00 g N/(m2·h) and the system energy consumption of 10.5 kWh/kg N. Accordingly, the developed sTMECS system with chemicals saving, easy scale-up and excellent performance shows good prospects in recovering ammonia from wastewater.

Electrocatalytic nitrate reduction to ammonia (NITRR) offers an attractive solution for alleviating environmental concerns, yet in neutral media, it is challenging as a result of the reliance on the atomic hydrogen (H*) supply by breaking the stubborn HO-H bond (∼492 kJ/mol) of H2O. Herein, we demonstrate that fluorine modification on a Cu electrode (F-NFs/CF) favors the formation of an O-H···F hydrogen bond at the Cu-H2O interface, remarkably stretching the O-H bond of H2O from 0.98 to 1.01 Å and lowering the energy barrier of water dissociation into H* from 0.64 to 0.35 eV at neutral pH. As a benefit from these advantages, F-NFs/CF could rapidly reduce NO3- to NH3 with a rate constant of 0.055 min-1 and a NH3 selectivity of ∼100%, far higher than those (0.004 min-1 and 9.2%) of the Cu counterpart. More importantly, we constructed a flow-through coupled device consisting of a NITRR electrolyzer and a NH3 recovery unit, realizing 98.1% of total nitrogen removal with 99.3% of NH3 recovery and reducing the denitrification cost to $5.1/kg of N. This study offers an effective strategy to manipulate the generation of H* from water dissociation for efficient NO3--to-NH3 conversion and sheds light on the importance of surface modification on a Cu electrode toward electrochemical reactions.

Due to the rapid growth of the aquaculture industry, large amounts of organic waste are released into nature and polluted the environment. Traditional organic waste treatment such as composting is a time-consuming process that retains the ammonia (NH3) in the compost, and the compost produced has little economic value as organic fertilizer. Illegal direct discharge into the environment is therefore widespread. This study investigates the recovery of NH3 through thermophilic composting of shrimp aquaculture sludge (SAS) and its application as a soil conditioner for the growth of mango plants. A maximum composting temperature of 57.10 °C was achieved through self-heating in a 200 L bench-scale reactor, resulting in NH3 recovery of 224.04 mol/ton-ds after 14 days. The addition of calcium hydroxide and increased aeration have been shown to increase NH3 volatilization. The recovered NH3 up to 3 kg-N can be used as a source of clean nitrogen for high-value microalgae cultivation, with a theoretical yield of up to 34.85 kg-algae of microalgae biomass from 1 ton-ds of SAS composting. Despite the high salinity, SAS compost improved mango plant growth and disease resistance. These results highlight the potential of SAS compost as a sustainable source of clean nitrogen for microalgae cultivation and soil conditioner, contributing to a waste-free circular economy through nutrient recycling and sustainable agriculture.

Gas-permeable membrane (GPM) technology is gaining interest to recover nitrogen from residual effluents due to its effectiveness, simple operation and capacity of producing a nutrient rich product with fertilising value. In this study, a GPM contactor was used at 25 °C to recover total ammoniacal nitrogen (TAN) from swine slurry as a concentrated (NH4)2SO4 solution. Firstly, a synthetic solution was tested on a wide pH range (6-12). Results showed that the ammonia mass transfer constants (Km) increased from 7.9·10-9 to 1.2·10-6 m/s as the pH increased. The reagent consumption to control the pH per mole nitrogen recovered had a minimum at pH 9, which showed a Km value of 3.0·10-7 m/s. Secondly, various pH control strategies were tested using swine slurry, including (i) no pH control, (ii) pH control at 8.5, 9.0 and 10.0, and (iii) an initial spike of the NaOH equivalent to the required to control the pH at 9. The test without pH control reached a TAN recovery of around 60%, which could be an interesting strategy when high nitrogen recoveries or short operating times are not required. The pH control at 9 stood out as the most favourable operating condition due to its high Km and lower reagent consumption. Thirdly, several feed-to-trapping volume ratios ranging from 1:1 to 15:1 were tested using swine slurry at pH 9. These assays revealed that a GPM process with a high feed-to-trapping volume ratio fastens the recovery of 99% of TAN as a high purity (NH4)2SO4 solution containing 40 g N/L.

Recovering waste NH3 to be used as a source of nitrogen fertilizer or liquid fuel has recently attracted much attention. Current methods mainly utilize activated carbon or metal-organic frameworks to capture NH3, but are limited due to low NH3 adsorption capacity and high cost, respectively. In this study, novel porous materials that are low cost and easy to synthesize were prepared as NH3 adsorbents by precipitation polymerization with acid optimization. The results showed that adsorption sites (‒COOH, -OH, and lactone) which form chemical adsorption or hydrogen bonds with NH3 were successfully regulated by response surface methods. Correspondingly, the dynamic NH3 adsorption capacity increased from 5.45 mg g-1 to 129 mg g-1, which is higher than most known activated carbon and metal-organic frameworks. Separation performance tests showed that NH3 could also be separated from CO2 and CH4. The findings in this study will advance the industrialization of NH3 polymer adsorbents and provide technical support for the recycling of waste NH3.

Recovering ammonia from waste streams (e.g., urine) is highly desirable to reduce natural gas-based NH3 production and nitrogen discharge into the water environment. Electrochemical membrane stripping is an attractive alternative because it can drive NH4+ transformation to NH3 via cathodic OH- production; however, the conventional configurations suffer from relatively low ammonia recovery (<80 %) and significant acid/material usage for ammonia adsorption. To this end, we develop a novel stack system that simply uses an oxygen evolution reaction to in-situ produce acid from water, enabling chemical-free ammonia recovery from synthetic urine. In batch mode, the percentage removal and recovery increased respectively from 74.5 % to 97.9 % and 81.8 % to 92.7 % when the electrode pairs increased from 2 to 4 in the stack system. To address the gas-sparging issue that deteriorated ammonia recovery in continuous operation, pulsed electric field (PEF) mode was applied, resulting in ∼100 % recovery under optimized conditions. At an ammonia removal rate of 35.1 g-N m-2 h-1 and electrical energy consumption of 28.9 kWh kg-N-1, our chemical-free system in PEF mode has achieved significantly higher ammonia recovery (>90 %) from synthetic urine. The total cost to recover 1 kg of NH3-N from real human urine was $15.9 in the proposed system. Results of this study demonstrate that this novel approach holds great promise for high ammonia recovery from waste streams, opening a new pathway toward sustainable nitrogen management.