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Membrane filtration has been widely used in water and wastewater treatment. However, this process is not very effective for the removal of refractory organic compounds (e.g., of pharmaceutical origin). Coupling membrane filtration with ozonation (or other Advanced Oxidation Methods) can enhance the degradation of these compounds and, subsequently, the incidence of membrane fouling (i.e., the major problem of membrane uses) would be also limited. Ozonation is an efficient oxidative process, although ozone is considered to be a rather selective oxidant agent and sometimes it presents quite low mineralization rates. An improvement of this advanced oxidation process is catalytic ozonation, which can decrease the by-product formation via the acceleration of hydroxyl radicals production. The hydroxyl radicals are unselective oxidative species, presenting high reaction constants with organic compounds. An efficient way to couple membrane filtration with catalytic ozonation is the deposition of an appropriate solid catalyst onto the membrane surface. However, it must be noted that only metal oxides have been used as catalysts in this process, while the membrane material can be of either polymeric or ceramic origin. The relevant studies regarding the application of polymeric membranes are rather scarce, because only a few polymeric materials can be ozone-resistant and the deposition of metal oxides on their surface presents several difficulties (e.g., affinity etc.). The respective literature about catalytic membrane ozonation is quite limited; however, some studies have been performed concerning membrane fouling and the degradation of micropollutants, which will be presented in this review. From the relevant results it seems that this hybrid process can be an efficient technology both for the reduction of fouling occurrence as well as of enhancement of micropollutant removal, when compared to the application of single filtration or ozonation.

In order to enhance the efficiency of heterogeneous catalytic ozonation, the effect of thermal treatment on three commonly used and inexpensive minerals, i.e., zeolite, talc and kaolin (clay), which present different physicochemical properties as potential catalysts, has been examined for the removal of para-chlorobenzoic acid (p-CBA). p-CBA is considered a typical micro-pollutant, usually serving as an indicator (model compound) to evaluate the production of hydroxyl radicals in ozonation systems. The catalytic activity of selected solid catalysts was studied for different pH values (6, 7 and 8) and different temperatures (15 °C, 25 °C and 35 °C). The mechanism of radicals’ production was also verified by the addition of tert-butyl alcohol (TBA). The respective thermal behavior study showed that the point of zero charge (PZC) of these minerals increased with the increase of applied treatment temperature, as it removed crystalline water and hydroxyls, thus improving their hydrophobicity. Circa-neutral surface charge and the presence of hydrophobicity were found to favor the affinity of ozone with solid/catalytic surfaces and the subsequent production of hydroxyl radicals. Therefore, zeolite and talc, presenting PZC 7.2 and 6.5 respectively, showed higher catalytic activity after thermal treatment, while kaolin with PZC equal to 3.1 showed zero to moderate catalytic efficiency. The degradation level of p-CBA by oxidation was favored at 25 °C, while the pH value exerted positive effects when it was increased up to 8.

Catalytic ozonation is an Advanced Oxidation Process (AOPs) based on the production of hydroxyl radicals, which are very reactive oxidative species. The aim of this study is to evaluate the catalytic activity of calcite on the ozonation of four different typical micropollutants (atrazine, benzotriazole, carbamazepine, and p-CBA) at pH 7 and for low initial concentrations (4 μΜ) by performing batch mode experiments. These compounds have different physico-chemical characteristics, as well as different rate constants, when reacting with ozone and hydroxyl radicals (•OH), being in the range of <0.15 − 3 × 105 M−1s−1 and 2.4 − 8.8 × 109 M−1s−1, respectively. It was found that most of these micropollutants can be sufficiently removed by the application of heterogeneous catalytic ozonation, using calcite as the catalyst, except for the case of atrazine, which was the compound that was most difficult to degrade, when compared to the application of single ozonation. Carbamazepine with kO3 = 3 × 105 M−1s−1 can be easily removed even by single ozonation after the first minute of the reaction time, and the addition of the catalyst eliminated the oxidation/reaction time. The application of catalytic ozonation resulted in 50% and 68.2% higher removals of benzotriazole and p-CBA, respectively, in comparison with single ozonation, even during the first 3 min of the reaction/oxidation time, due to the higher production of hydroxyl radicals, caused by the catalytic ozonation. For the case of atrazine, the addition of calcite did not enhance the micropollutant degradation, and its removal reached 83% after a 30 min application of catalytic ozonation, whereas during the single ozonation, the removal under the same reaction time was 90%.