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

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

Water research (2013-01-02)
Ting Yang, Kyle Doudrick, Paul Westerhoff
ABSTRACT

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., N(2), N(2)O). 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 × 10(24) photons were required to reduce each mole of nitrate to 83% N Gases and 17% NH(4)(+). 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.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Calcium formate, BioUltra, ≥99.0% (T)
Sigma-Aldrich
Cesium formate, 98%
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Ammonium formate, BioUltra, ≥99.0% (calc. based on dry substance, NT)
Supelco
Ammonium formate, eluent additive for LC-MS, LiChropur, ≥99.0%
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Thallium(I) formate, 97%
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Formic acid, ≥95%, FCC, FG
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Formic acid, reagent grade, ≥95%
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Ammonium formate, SAJ first grade, ≥95.0%
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Calcium formate, Standard for quantitative NMR, TraceCERT®, Manufactured by: Sigma-Aldrich Production GmbH, Switzerland
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Ammonium formate, ≥99.995% trace metals basis
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Formic acid, puriss., meets analytical specifications of DAC, FCC, 98.0-100%
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Formic acid, ACS reagent, ≥96%
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Formic acid, puriss. p.a., ACS reagent, reag. Ph. Eur., ≥98%
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Formic acid, JIS special grade, ≥98.0%
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Ammonium formate, reagent grade, 97%
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Formic acid, ACS reagent, ≥88%
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Formic acid solution, BioUltra, 1.0 M in H2O
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Ammonium formate solution, 10 mM in H2O, suitable for HPLC
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Formic acid, SAJ first grade, 88.0-89.5%
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Sodium formate, BioUltra, ≥99.0% (NT)
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Potassium formate, BioUltra, ≥99.0% (NT)
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Sodium formate, 99.998% trace metals basis