Removal of phosphorus from phosphonate-loaded industrial wastewaters via precipitation/flocculation

Phosphonates are to be removed from industrial wastewater before they reach municipal wastewater treatment plants or surface waters. Industrial wastewaters contaminated with the phosphonates 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethylidene-(1,1-diphosphonic acid) (HEDP), nitrilotrimethylphosphonic acid (NTMP), ethylenediamine tetra(methylene phosphonic acid) (EDTMP) and diethylenetriamine penta (methylene phosphonic acid) (DTPMP) can be subdivided into: (1) mostly clear concentrates with a high water hardness, and (2) organically polluted wastewaters, for instance from the paper and textile industries. Our own flocculation experiments with Fe-III and Al-III salts showed that, at a pH of 7.5, the adsorption affinity of polyphosphonates onto iron hydroxides and aluminum hydroxides significantly decreases with an increasing number of C-P bonds (HEDP > NTMP > EDTMP > DTPMP). In comparison to pure water spiked with phosphonates, the total P removal from concentrates occurred at similar and even lower flocculant dosage concentrations (ss = 4-8) (ss is the molar ratio of dosed metal concentration to total P concentration in the raw sample). In organically polluted industrial wastewaters, the formation of flocks, and therefore the total P decrease, only occurred after exceeding a certain flocculant concentration, which varied strongly depending on the wastewater type (ss = 0.6-86). Below that concentration, the flocculant underwent complexation, and no elimination could be observed. For most of the wastewaters, the required ss values for at least 80% total P decrease were very similar for both Fe-III and Al-III. Furthermore, Ca(OH)(2) as flocculant turned out to be an effective tool for total P removal and simultaneous softening of calcareous concentrates.