The integration of up-concentration processes to increase the efficiency of primary sedimentation, as a solution to achieve energy neutral wastewater treatment plants, requires further post-treatment due to the missing ammonium removal stage. This study evaluated the use of zeolites as a post-treatment step, an alternative to the biological removal process. A natural granular clinoptilolite zeolite was evaluated as a sorbent media to remove low levels (up to 100mg-N/L) of ammonium from treated wastewater using batch and fixed bed columns. After being activated to the Na-form (Z-Na), the granular zeolite shown an ammonium exchange capacity of 29±0.8mgN-NH4+/g in single ammonium solutions and 23±0.8mgN-NH4+/g in treated wastewater simulating up-concentration effluent at pH=8. The equilibrium removal data were well described by the Langmuir isotherm. The ammonium adsorption into zeolites is a very fast process when compared with polymeric materials (zeolite particle diffusion coefficient around 3×10-12m2/s). Column experiments with solutions containing 100mgN-NH4+/L provide effective sorption and elution rates with concentration factors between 20 and 30 in consecutive operation cycles. The loaded zeolite was regenerated using 2g NaOH/L solution and the rich ammonium/ammonia concentrates 2-3g/L in NaOH were used in a liquid-liquid membrane contactor system in a closed-loop configuration with nitric and phosphoric acid as stripping solutions. The ammonia recovery ratio exceeded 98%. Ammonia nitrate and di-ammonium phosphate concentrated solutions reached up to 2-5% wt. of N.
Keywords: Ammonia valorization; Ion-exchange; Liquid fertilizers; Liquid-liquid membrane contactor; Natural clinoptilolite; Nitric acid; Phosphoric acid.
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