Comparison of four advanced oxidation processes for the removal of naphthenic acids from model oil sands process water.

Four advanced oxidation processes (UV/TiO(2), UV/IO(4)(-), UV/S(2)O(8)(2-), and UV/H(2)O(2)) were tested for their ability to mineralize naphthenic acids to inorganic carbon in a model oil sands process water containing high dissolved and suspended solids at pH values ranging from 8 to 12. A medium pressure mercury (Hg) lamp was used, and a Quartz immersion well surrounded the lamp. The treatment goal of 5mg/L naphthenic acids (3.4 mg/L total organic carbon (TOC)) was achieved under four conditions: UV/S(2)O(8)(2-) (20mM) at pH 8 and 10, and UV/H(2)O(2) (50mM) at pH 8 (all with the Quartz immersion well). Values of electrical energy required to meet the treatment goal were about equal for UV/S(2)O(8)(2-) (20mM) and UV/H(2)O(2) (50mM) at pH 8, but three to four times larger for treatment by UV/S(2)O(8)(2-) (20mM) at pH 10. The treatment goal was also achieved using UV/S(2)O(8)(2-) (20mM) at pH 10 when using a Vycor filter that transmits light primarily in the mid and near UV, suggesting that that treatment of naphthenic acids by UV/S(2)O(8)(2-) using low pressure Hg lamps may be feasible.

Photocatalytic oxidation of aqueous ammonia in model gray waters.

This study investigated the TiO2 photocatalytic degradation of aqueous ammonia (NH4+/NH3) in the presence of surfactants and monosaccharides at pH approximately 10.1. Initial rates of NH4+/NH3 photocatalytic degradation decreased by approximately 50-90% in the presence of anionic, cationic, and nonionic surfactants and monosaccharides. Through correlation analysis, we concluded that scavenging of hydroxyl radical (.OH) by the products of surfactant/monosaccharide photocatalytic degradation, including carbonate and formate, could explain approximately 80% of the variance in initial rates of NH4+/NH3 removal in our system. Addition of a supplemental .OH source (H2O2) enhanced the rate of NH4+/NH3 degradation in the presence of the surfactant Brij 23 lauryl ether (Brij 35), further supporting the idea that .OH scavenging is the mechanism by which surfactants and monosaccharides decreased initial rates of NH4+/NH3 photocatalytic degradation. Despite slowed rates of NH4+/NH3 degradation, both surfactants/monosaccharides and NH4+/NH3 were removed by TiO2 photocatalysis, indicating that this process can effectively remove both carbonaceous and nitrogenous biochemical oxygen demand from gray water.

Effects of pH and catalyst concentration on photocatalytic oxidation of aqueous ammonia and nitrite in titanium dioxide suspensions.

Batch experiments were conducted to study the effects of titanium dioxide (TiO2) concentration and pH on the initial rates of photocatalytic oxidation of aqueous ammonium/ ammonia (NH4+/NH3) and nitrite (NO2-) in UV-illuminated TiO2 suspensions. While no simple kinetic model could fit the data at lower TiO2 concentrations, at TiO2 concentrations > or = 1 g/L, the experimental data were consistent with a model assuming consecutive first-order transformation of NH4+/NH3 to NO2- and NO2- to nitrate (NO3-). For TiO2 concentrations > or = 1 g/L, the rate constants for NO2 photocatalytic oxidation to NO3 were far more dependent on TiO2 concentration than were those for NH4+/NH3 oxidation to NO2-, suggesting that, without sufficient TiO2, complete oxidation of NH4+/NH3 to NO3- will not occur. Initial NH4+/NH3 photocatalytic oxidation rates were proportional to the initial concentrations of neutral NH3 and not total NH3(i.e., [NH4+] + [NH3]). Thus, the pH-dependent equilibrium between NH4+ and NH3, and not the pH-dependent electrostatic attraction between NH4+ and the TiO2 surface, is responsible for the increase in rates of NH4+/NH3 photocatalytic oxidation with increasing pH. Electrostatic adsorption, however, can partly explain the pH dependence of the initial rates of NO2- photocatalytic oxidation. Initial rates of NO2- photocatalytic oxidation were 1 order of magnitude higher for NO2- versus NH4+/NH3, indicating thatthe rate of NH4+/NH3 photocatalytic oxidation to NO3- was limited by NH4+/NH3 oxidation to NO2- under our experimental conditions.