Effect of hydroxyl and nitrate ions on the sorption of ammonium ions by sulphonic cation exchangers

The sorption of ammonium ions and ammonia by the H+ form of sulphonic acid cation exchangers Amberlite 252, Lewatit 2629 and Relite C 360 from a solution containing NH4NO3 in the range of 0 to 0.214 equ/L and NH3 in the range of 0.353 to 0 equ/L was investigated to establish the possibility of their application for the recovery of ammonium from caustic condensate generated in nitrogen fertilizer production. Breakthrough and elution curves were obtained, determining the concentration of ammonium with Nessler’s reagent. The sorption of ammonium and ammonia depends on the concentration ratio of ammonia to ammonium nitrate [NH3]/[NH4NO3]. On decreasing [NH3]/[NH4NO3], the ! + concentration ratio of hydroxyl to nitrate ions [OH-]/[NO3 ] and the effluent pH prior to NH4 breakthrough also + decrease. This results in a decrease in the NH4 sorption because of a deficiency in the neutralization of hydrogen ions + released (ordinary cation-exchange process). Thus, adverse circumstances create an unfavorable medium for NH4 + removal from the caustic condensate. Maximum sorption of NH4 is attained at [NH3]/[NH4NO3] ~1.2. A further decrease in [NH3]/[NH4NO3] is followed by a significant decrease in the effluent pH, which leads to an increase in the concentration of protonated sulphonic acid groups (-SO3H), resulting in a decrease in the ion-exchange ability of the + cation exchangers under investigation with respect to NH4 removal. The concentration (g/L) of NH4NO3 in the eluate from the cation-exchanger regeneration, carried out using 0.7 bed volumes (BV) of 20% HNO3, amounts to 136.7 for Relite C 360, 119.5 for Lewatit K 2629 and 96.7 for Amberlite 252. The content of undamaged beads after 100 cycles (each cycle comprises saturation with caustic condensate, containing ammonia and ammonium, successive regeneration with 20% nitric acid and washing) is from 97 to 99.8%. Resistance to boiling in 20% HNO3 solution is from 97 to 99.8%. These are applicable for the recovery of NH4NO3 from the caustic condensate in the nitrogen fertilizers production, preventing economic damage and environmental contamination from nitrogen compounds.

The sorption of ammonium ions and ammonia by the H+ form of sulphonic cation exchangers (Amberlite 252, Lewatit 2629, Relite C360) from the solution containing NH3 in the range of 0.353 to 0 equ/L and NH4NO3 in the range of 0 to 0.214 equ/L and corresponding to the composition of the caustic condensate, generated in the nitrogen fertilizers production, depends on the concentration ratio of ammonia to ammonium nitrate [NH3]/[NH4NO3], as well as on the initial solution pH. When [NH3]/[NH4NO3] decreases, ! the ratio of hydroxyl to nitrate [OH-]/[NO3 ] and + pH of the effluent prior to NH4 breakthrough + (0.2 g NH4 /L) also decrease. A decrease in [OH-]/ ! [NO3 ] results in a decrease in that portion of the + NH4 sorption, which proceeds on the basis of ion exchange, accompanied by irreversible reaction (neutralization of hydrogen ions, released from the cation exchanger), and leads to an increase in + that portion of NH4 sorption, which proceeds on the basis of the conventional ion exchange. As a result, the effluent pH and, subsequently, the concentration of deprotonated functional (-SO3H) groups decrease, leading also to a decrease in the + NH4 total sorption. The maximum sorption of + NH4 corresponds to [NH3]/[NH4NO3] ~1.2. The concentration (g/L) of NH4NO3 in the eluate from the cation exchanger regeneration, carried out with 0.7 BV 20% HNO3, amounts to 136.7 for Relite C360, 119.5 for Lewatit L2629 and 96.7 for the Amberlite 252. The cation exchangers investigated are resistant to boiling in 20% HNO3 solution. Osmotic stability is 97–99.8%. The exchangers are applicable for the recovery of NH4NO3 from caustic condensate, providing a new opportunity for economic consideration and environmental issues.