Degradation of nitrilotris-methylenephosphonic acid (NTMP) antiscalant via persulfate photolysis: Implications on desalination concentrate treatment

Nitrilotris-methylenephosphonic acid (NTMP) has been widely used as an antiscalant in reverse osmosis (RO) desalination and other industrial processes to inhibit scaling from calcium and other hardness ions. Removal of NTMP from RO concentrate can induce the precipitation of oversaturated scale-forming substances, enable additional water recovery from RO concentrate, and reduce the risk of eutrophication after brine disposal. This study investigated the kinetics and mechanisms of oxidative degradation of NTMP by UV photolysis of persulfate at 254 nm. Results showed that NTMP was effectively degraded by persulfate photolysis and the reaction followed pseudo first-order kinetics. The degradation of NTMP was favorable at circumneutral pHs but significantly inhibited in highly alkaline conditions (e.g., pH of 11.5), mainly due to the reduced concentration of SO4•−. Using a competition reaction kinetics approach, the second-order rate constants of NTMP with SO4•− and HO• were determined to be (2.9 ± 0.6) × 107 M−1s−1 and (1.1 ± 0.1) × 108 M−1s−1, respectively. SO4•− had a predominant contribution to NTMP degradation (62%–95%), because the steady-state concentration of SO4•− was 11–54 times higher than that of HO• at pHs between 4 and 11.5. NTMP degradation rate increased with an increase in persulfate dosage and a decrease in NTMP concentration. In the real RO concentrate, NTMP degradation rate was impacted by the presence of chloride and bicarbonate. The degradation of NTMP started with the cleavage of C–N bonds, and then generated intermediates including iminodi(methylene)phosphonate, hydroxymethylphosphonic acid and aminotris(methylenephosphonic acid), which were eventually mineralized into ammonia, phosphate and carbon dioxide. This study demonstrated that UV/persulfate is a promising technology to remove phosphonate antiscalants from RO concentrate.