Ammonium nitrate wastewater treatment by coupled membrane electrolysis and electrodialysis

Contamination from nitrogen compounds in natural water is an increasing problem. This contamination stems from a number of different agricultural and industrial activities e.g. uranium refining. These nitrogen compounds are considered salt wastewater. This particular process of salt wastewater treatment is considered an electromembrane technique. The reason the process is considered coupled is because it involves two different processes that work simultaneously. One process is the membrane electrolysis and the other electrodialysis.

MEMBRANE ELECTROLYSIS
This process of the treatment involves a three compartment cell that an electrical current is run through. The middle compartment contains the raw ammonium nitrate wastewater (NH4NO3). The other two compartments straddling the middle are separated from the middle compartment by a cation (CEM) and anion (AEM) exchange membrane. These membranes only allow their respective ion charge to pass through therefore each compartment is given its name of anolyte and catholyte. When the electrical current is run through the cell NH4+ migrates through the CEM into the catholyte compartment and NO3-migrates through the AEM into the anolyte compartment. Within the catholyte compartment water and a small amount of sodium hydroxide (to ensure current transport) is already present before the process begins. Due to water oxidation at the anode within the anolyte compartment H+ are present and combine with the NO3- to create concentrated nitric acid (HNO3). Within the catholyte compartment water is already present and is reduced to hydroxyl ions (OH-) at the cathode. These hydroxyl ions react with the NH4+ to create ammonia (NH3) (Figure 2). As this process is occurring the ammonium nitrate concentration in the middle compartment is decreasing while the nitric acid concentration increases in the anolyte compartment. The ammonia concentration remains almost constant in the catholyte compartment. The value of the fixed concentration of ammonia can be controlled by adjusting stripping conditions. These involve the solubility of ammonia under fixed temperature and pressure. These concentrations can be viewed in Figure 1. There are certain issues that arise within this process that are addressed as follows. If the ammonium nitrate wastewater contains impurities they can be transferred through the ion exchange membranes and pollute the acid or the catholyte obtained by the process. Pretreatment is necessary to mitigate these effects if desired. Another issue that arises is that ammonium ions (NH4+) are able to cross the anion exchange barrier by diffusion. Ammonium ions can therefore be found in the nitric acid as an impurity however the concentration ratio [NH4+]/[NO3-] is lower than 2 x 10-5 which can be considered negligible.

RECIRCULATION PROCESS
For long time periods the current efficiency decreases which is undesirable. This is because in the salt (NH4NO3) compartment proton (H+) concentrations increase with time (Figure 1) so a pH adjustment is required to maintain the proper current efficiency. If no pH adjustment is carried out a recirculation

process is necessary. The recirculation process takes the overflow from the catholyte solution to adjust the salt solutions pH value. (See Figure 3)

ELECTRODIALYSIS
The electrodialysis process consists of a cell that takes the salt solution and concentrates it. This salt concentrate is reintroduced into the tank that contains the raw wastewater. This process also creates a diluate that is of low concentration. This product constitutes the final rejection of the process. (See Figure 3)

CONCLUSION
The Ammonium nitrate wastewater treatment by coupled membrane electrolysis and electrodialysis is efficient for regeneration of nitric acid and ammonium. It can be proved effective and environmentally friendly in an industrial setting and is therefore a viable option for wastewater treatment. The economics of this process take into account the generation of recyclable or saleable products of high purity, the credit for disposal of salt effluent, and energy consumption.

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Figure 1

Figure 2

Figure 3