The excessive nitrogen in waterbodies, often caused by the discharge of ammonia-rich wastewaters, leads to eutrophication, disrupting aquatic ecosystems. Wastewater treatment plants play an important role in the removal and recovery of nitrogen from wastewater streams, thereby preventing pollution. Air stripping in combination with acid scrubbing has emerged as a promising technology not only for removing ammonia from wastewater, but also for recovering it as a valuable fertilizer, ensuring circularity. However, factors such as continuous consumption of chemicals and the hazardous use of strong acids need to be addressed. To reduce chemical consumption, a combination of air stripping and organic acid scrubbing with bipolar membrane electrodialysis (BPMED) has been proposed.
This study focused on optimizing BPMED for the recovery of ammonia and citric acid from ammonium citrate scrubber effluents. The impact of current density, membrane configuration, feed solution characteristics (pH and initial N concentration), and temperature on recovery efficiency, current efficiency, and energy consumption of a BPMED system was evaluated. The limiting current density (LCD), a key factor in the normal operating range of the system, was determined using the Cowan and Brown method, yielding a critical value of 1.01 A/m2.
Comparative experiments conducted on three BPMED configurations, including 3-chamber BPMED (BPCA), 2-chamber base BPMED (BPC), and 2-chamber acid BPMED (BPA), revealed the superior performance of the BPC in terms of current efficiency, energy consumption, and running time. The optimal operating time of BPC was determined to be 120 minutes, achieving a recovery efficiency of 55.9%, a current efficiency of 44.2%, and an energy consumption of 8.4 kWh/kg-N.
Moreover, regression models were established using Box-Behnken design (BBD) from response surface methodology (RSM) to optimize operating conditions (pH, initial N concentration, and temperature), maximize recovery efficiency, current efficiency, and minimize energy consumption. Verified by analysis of variance, normal probability plot, and residual analysis, the model showed high accuracy and significance.
Univariate analysis elucidated that pH and initial N concentration were found to be important variables, while temperature was not. Increasing pH (3–7) enhanced recovery and current efficiency while decreasing energy consumption. Higher initial N concentrations (2–10 g/L) improved current efficiency, decreased energy consumption, but reduced recovery efficiency, emphasizing the need for a careful balance. Temperature variations (20–40°C) had no significant impact on BPMED. Critical factors limiting ammonia recovery efficiency, current efficiency, and energy consumption were identified, including solution conductivity, H+ ion leakage, water migration, and NH3 diffusion.
Furthermore, the study revealed non-significant interactions between these variables through 3D response surface plots and 2D contour plots. Adjusting operational variables proved feasible for optimizing performance indicators. The optimized conditions (pH 6.05, initial N concentration 6.67 g/L, temperature 30°C) were experimentally verified, and the predicted values were in good agreement with the actual values, confirming the reliability of the optimization model. Specifically, the recovery efficiency was 52.9%, the current efficiency was 45.4%, and the energy consumption was 7.0 kWh/kg-N.
Energy evaluation of the BPMED system in BPC configuration under optimal conditions showed significant energy efficiency. Based on the comparison with the available literature, the integration of BPMED with air stripping and organic acid scrubbing could improve energy efficiencies and lower chemical consumption while offering a closed-loop system.
Future research should explore principles to inhibit ion leakage and water migration, analyze the combined effects of various operating variables using RSM, and validate the potential for lower energy consumption in full-scale BPMED. Developing continuous BPMED processes is crucial for full-scale application, and integrating BPMED with other processes such as air stripping and acid scrubbing may enhance ammonia recovery and production efficiency.
The insights gleaned from this study provided a solid foundation for enhancing ammonia recovery processes from ammonium citrate scrubber wastewater, thereby promoting sustainable and resource-saving industrial practices.

This study evaluates the effectiveness of organic acids, specifically citric acid, lactic acid, and malic acid, as scrubbing agents for ammonia (NH3) recovery from waste air streams. The acid scrubbing process was modeled using Aspen Plus® and validated against sulfuric acid scrubbing process data available in the literature. The effects of various system variables, such as temperature, gas liquid ratio (G/L) pressure, acid and NH3 concentrations, on the scrubbing efficiency as well as outlet ammonium ion mass flow rate was investigated. Results showed that reducing temperature, acid reflux ratio, G/L ratio, and inlet NH3 concentration while increasing pressure and inlet acid concentration can improve scrubbing efficiency. Citric acid exhibited the highest ammonia removal rate, the lowest acid consumption, and the least change in scrubbing efficiency when changing inlet ammonia concentration, followed by malic acid and lactic acid. These findings suggest that citric acid is a promising alternative to sulfuric acid as a scrubbing agent for NH3 recovery in wastewater treatment plants. This study needs to further incorporate the dissociation reactions equations of organic acids to provide accurate results. Additionally, the simulation's simplification in the design of the scrubber system introduces uncertainties in the results.