Kinetics of chlorine and chloramine reactions in reverse osmosis permeate and their impact on radical formation during UV/chlorine advanced oxidation for potable reuse.

Knowledge of the speciation of chlorine and chloramines in reverse osmosis (RO) permeate is needed to estimate the performance (i.e., pollutant log reduction) of subsequent UV/chlorine advanced oxidation processes (AOPs). To accurately predict the speciation, a previously reported breakpoint chlorination kinetic model was experimentally validated for pH 5.5 and reaction times < 3 min and used to predict the kinetics of breakpoint chlorination in RO permeate. The predictions showed that eliminating chloramines by adding chlorine at a dose beyond the chlorine-to-nitrogen (Cl/N) breakpoint ratio is not practical due to the high breakpoint Cl/N ratio for RO permeate (∼3.0 molar ratio) and an estimated > 40 min reaction time. The conversion from monochloramine (NH2Cl) to dichloramine (NHCl2) is the major process involved, and either or both free chlorine and chloramines may be the major species present, depending on the Cl/N ratio. Model simulations showed that increasing the oxidant dose may not always enhance the performance of UV/chlor(am)ine in RO permeate, due to the need for a low free chlorine dose for optimal •OH exposure in RO permeate. Further UV/AOPs modelling showed that it is important to control the NH2Cl concentration to improve the UV/AOP performance in RO permeate, which may be achieved by extending the reaction time after chlorine is added or increasing the applied Cl/N ratio (e.g., increasing chlorine dose). However, these measures only enhance the pollutant percentage removal by about 5 % under the conditions modelled. A simulation tool was developed and is provided to predict the speciation of chlor(am)ine in RO permeate.

Predicting chlorine demand by peracetic acid in drinking water treatment.

Peracetic acid (PAA) may be used in drinking water treatment for pre-oxidation and mussel control at the intake. PAA may exert a downstream chlorine demand, but full details of this reaction have not been reported. There are three possible mechanisms of this demand: (1) PAA may react directly with chlorine; (2) PAA exists in equilibrium with hydrogen peroxide, which is known to react with chlorine; and (3) as H2O2 reacts with chlorine, PAA will hydrolyze to form more H2O2 to re-establish PAA/H2O2 equilibrium, thereby serving as an indirect reservoir of chlorine demand. While the H2O2 reaction with chlorine is well known, the other mechanisms of possible PAA-induced chlorine demand have not previously been investigated. The observed molar stoichiometric ratio of PAA to free chlorine (n) for the presumed direct PAA + free chlorine reaction was determined to be approximately 2, and the corresponding observed reaction rate coefficients at pH 6, 7, 8, and 9 were 2.76, 3.14, 1.61, 10.1 M-n·s-1, respectively (at 25 °C). With these estimated values, a kinetic model was built to predict the chlorine demand by PAA. The results suggest that chlorine demand from PAA is likely to be negligible over the course of several days (e.g., < 20% chlorine loss) for most conditions except for high pH (e.g., >8) and high PAA:Cl2 molar ratios (e.g., >2:1).