Recovery of ammonium sulfate solution by regeneration of loaded clinoptilolite

Abstract

The zeolite clinoptilolite (CLI) is known to be a very good ion exchanger, as it consists of a three-dimensional structure formed of AlO4- and SiO4 tetrahedral, which are connected by a common oxygen atom. The micropores formed by this structure (with free diameters in the range of 0.40 nm and 0.72 nm) are fine enough to allow cations and water molecules to enter and be exchanged. CLI is a suitable, inexpensive, and globally available material for removing ammonium from highly-concentrated wastewater and is proven to be selective in ammonium uptake and regeneration since no effect of the provenance of the ammonium (matrix-free NH4Cl solution or sludge water) could be found. However, regeneration of the clinoptilolite is necessary to recover the adsorbed ammonium for further use and restore its capability for ion exchange. Within this work, the method by which clinoptilolite, loaded with ammonium (q = 8.1-16.6 mg/g) from different sludge waters and ammonium chloride solution, can be regenerated to yield a stoichiometric ammonium sulfate solution (ASS), that could be used, e.g., as a fertilizer, was investigated. A regeneration solution containing Na2SO4 (0.25 n(Na2SO4)/n(NH4+ads)) with a varying NaOH ratio (0-2.14 n(NaOH)/n(NH4+ads)) was tested. To obtain a high ammonium concentration in the eluate, a large mass fraction ω of 284 g/kg of CLI in the regeneration solution was applied. The effects of different ammonium loads, different origins of the ammonium, and residual moisture on the necessary components of the regeneration solution, in which an ASS is obtained within a contact time of 10 min at 22 °C, were studied. A stoichiometric ASS from CLI loaded up to a maximum of 13.5 mg/g was obtained with a mixture of 0.25 n(Na2SO4)/n(NH4+ads) together with 0.8-1.0 n(NaOH)/n(NH4+ads) for dry CLI, and 0.75 n(NaOH)/n(NH4+ads) for CLI with residual moisture.