Photocatalytic reduction of nitrate using titanium dioxide for regeneration of ion exchange brine

Nitrate is often removed from groundwater by ion exchange (IX) before its use as drinking water. Accumulation of nitrate in IX brine reduces the efficiency of IX regeneration and the useful life of the regeneration brine. For the first time, we present a strategy to photocatalytically reduce nitrate in IX brine, thereby extending the use of the brine. Titanium dioxide (Evonik P90), acting as photocatalyst, reduced nitrate effectively in both synthetic brines and sulfate-removed IX brine when formic acid (FA) was used as the hole scavenger (i.e., electron donor) and the initial FA to nitrate molar ratio (IFNR) was 5.6. Increasing the NaCl level in the synthetic brine slowed the nitrate reduction rate without affecting by-product selectivity of ammonium and gaseous N species (e.g., N2, N2O). In a non-modified IX brine, nitrate removal was greatly inhibited owing to the presence of sulfate, which competed with nitrate for active surface sites on P90 and induced aggregation of P90 nanoparticles. After removing sulfate through barium sulfate precipitation, nitrate was effectively reduced; approximately 3.6 × 1024 photons were required to reduce each mole of nitrate to 83% N Gases and 17% NH4+. To make optimum use of FA and control the residual FA level in treated brine, the IFNR was varied. High IFNRs (e.g., 4, 5.6) were found to be more efficient for nitrate reduction but left higher residual FA in brine. IX column tests were performed to investigate the impact of residual FA for brine reuse. The residual FA in the brine did not significantly affect the nitrate removal capacity of IX resins, and formate contamination of treated water could be eliminated by rinsing with one bed volume of fresh brine.

Graphical abstractDownload high-res image (118KB)Download full-size imageHighlights► Photocatalytic reduction using titanium dioxide is able to remove nitrate from sulfate-removed ion exchange brine. ► Presence of sulfate (6000 mg/L) in brine greatly slowed rate of nitrate reduction. ► Higher formic acid (hole scavenger) dosage is more appropriate for nitrate reduction in brine. ► The negative impact from residual formic acid in brine on ion exchange resin regeneration can be overcome.