Phosphorous in wastewater

Municipal wastewaters may contain from 5 to 20 mg/l of total phosphorous, of which 1-5 mg/l is organic and the rest in inorganic. The individual contribution tend to increase, because phosphorous is one of the main constituent of synthetic detergents. The individual phosphorous contribution varies between 0.65 and 4.80 g/inhabitant per day with an average of about 2.18 g. The usual forms of phosphorous found in aqueous solutions include:

• Orthophosphates: available for biological metabolism without further breakdown
• Polyphosphates: molecules with 2 or more phosphorous atoms, oxygen and in some cases hydrogen atoms combine in a complex molecule. Usually polyphosphates undergo hydrolysis and revert to the orthophosphate forms. This process is usually quite slow.

Normally secondary treatment can only remove 1-2 mg/l, so a large excess of phosphorous is discharged in the final effluent, causing eutrophication in surface waters. New legislation requires a maximum concentration of P discharges into sensitive water of 2 mg/l.

Phosphorous removal processes

The removal of phosphorous from wastewater involves the incorporation of phosphate into TSS and the subsequent removal from these solids. Phosphorous can be incorporated into either biological solids (e.g. micro organisms) or chemical precipitates.

Phosphate precipitation

Chemical precipitation is used to remove the inorganic forms of phosphate by the addition of a coagulant and a mixing of wastewater and coagulant. The multivalent metal ions most commonly used are calcium, aluminium and iron.

Calcium:

it is usually added in the form of lime Ca(OH)2. It reacts with the natural alkalinity in the wastewater to produce calcium carbonate, which is primarily responsible for enhancing SS removal.

Ca(HCO3)2 + Ca(OH)2 à 2CaCO3 ↓+ 2H2O

As the pH value of the wastewater increases beyond about 10, excess calcium ions will then react with the phosphate, to precipitate in hydroxylapatite:

10 Ca2+ + 6 PO43- + 2 OH- ↔ Ca10(PO4)*6(OH)2 ↓

Because the reaction is between the lime and the alkalinity of the wastewater, the quantity required will be, in general, independent of the amount of phosphate present. It will depend primarily on the alkalinity of the wastewater. The lime dose required can be approximated at 1.5 times the alkalinity as CaCO3. Neutralisation may be required to reduce pH before subsequent treatment or disposal. Recarbonation with carbon dioxide (CO2) is used to lower the pH value.

Aluminium and Iron:

Alum or hydrated aluminium sulphate is widely used precipitating phosphates and aluminium phosphates (AlPO4). The basic reaction is:

Al3+ + HnPO43-n ↔ AlPO4 + nH+

This reaction is deceptively simple and must be considered in light of the many competing reactions and their associated equilibrium constants and the effects of alkalinity, pH, trace elements found in wastewater. The dosage rate required is a function of the phosphorous removal required. The efficiency of coagulation falls as the concentration of phosphorous decreases. In practice, an 80-90% removal rate is achieved at coagulant dosage rates between 50 and 200 mg/l. Dosages are generally established on the basis of bench-scale tests and occasionally by full-scale tests, especially if polymers are used. Aluminium coagulants can adversely affect the microbial population in activated sludge, especially protozoa and rotifers, at dosage rates higher than 150 mg/l. However this does not affect much either BOD or TSS removal, as the clarification function of protozoa and rotifers is largely compensated by the enhanced removal of SS by chemical precipitation.

Ferric chloride or sulphate and ferrous sulphate also know as copperas, are all widely used for phosphorous removal, although the actual reactions are not fully understood. The basic reaction is:

Fe3+ + HnPO43-n ↔ FePO4 + nH+

Ferric ions combine to form ferric phosphate. They react slowly with the natural alkalinity and so a coagulant aid, such as lime, is normally add to raise the pH in order to enhance the coagulation.

Read more: https://www.lenntech.com/phosphorous-removal.htm#ixzz6jbwlGvw8

I would think that a reverse-phase column would retain the organics and allow inorganic phosphate to pass through, when eluted with pure water or a buffer. Methanol or acetonitrile would then elute the organics.

This is a good practical question and if there is a simple answer I'd like to know. The same question arises in other environmental components because the molybdate reaction is not very selective.