Recovery of Ammonium Sulfate Solution by Regeneration of Loaded Clinoptilolite

Stephan Wasielewski; Eduard Rott; Ralf Minke; Heidrun Steinmetz

doi:10.3390/nano12030525

Recovery of Ammonium Sulfate Solution by Regeneration of Loaded Clinoptilolite

Nanomaterials (Basel). 2022 Feb 2;12(3):525. doi: 10.3390/nano12030525.

Authors

Stephan Wasielewski¹, Eduard Rott¹, Ralf Minke¹, Heidrun Steinmetz²

Affiliations

¹ Chair of Sanitary Engineering and Water Recycling, Institute for Sanitary Engineering, Water Quality and Solid Waste Management (ISWA), University of Stuttgart, Bandtaele 2, 70569 Stuttgart, Germany.
² Chair of Resource-Efficient Wastewater Technology, Faculty of Civil Engineering, University of Kaiserslautern, Paul-Ehrlich-Str. 14, 67663 Kaiserslautern, Germany.

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.

Keywords: alkalic regeneration; ammonium recovery; molecular sieve; regenerability; resource recovery; sludge liquor; sludge water; wastewater.