Visible Light Driven Degradation of Terephthalic Acid: Optimization of Energy Demand by Light Modulation Techniques

Aims: The aim of this work was to investigate the impact of light modulation parameters on the degradation of terephthalic acid, an organic model pollutant, within a heterogeneous photocatalytic system under visible light. For this purpose, a fixed bed photocatalytic reactor, irradiated by white-light LEDs matrix controlled by a system for light dimming, was used. The bed consisted of a nitrogen-doped titania photocatalyst deposited on polystyrene pellets. Background: Wastewater containing TPA can be treated into conventional aerobic biological units. However, the mineralization of TPA is slow and inefficient and its presence negatively influences the biodegradation efficiency because this pollutant inhibits microbial growth. Nowadays, innovative technologies named advanced oxidation processes (AOPs), such as heterogeneous photocatalysis with UV and visible light, ozonation, and Fenton oxidation, have gained popularity for effective organic destruction of TPA from wastewater. The heterogeneous photocatalytic oxidation process of the TPA under visible light is the most advantageous process in terms of both fixed and operating costs. Objective: In this work, the successful application of light modulation techniques for degradation of TPA using a photocatalytic system with supported visible active photocatalysts (N-doped TiO2) immobilized on polystyrene pellets is reported. In particular, sinusoidal lighting has been used analyzing the influence of the period of oscillation and the amplitude of light modulation on the reaction kinetics, in such a way as to minimize the times and energy costs for the process. Methods: To evaluate the influence of light modulation on the efficiency of the TPA removal, a discontinuous system composed of a Recirculating Photocatalytic Fixed Bed Reactor (RPFBR) irradiated by a matrix of white light LEDs was used. The flat geometry of the photoreactor guarantees the efficient excitation of the photocatalyst. An amount of 250 mL of aqueous solution with the initial TPA concentration of 12.5 ppm was applied in the photocatalytic tests lasting 180 min of irradiation fixed or sinusoidal modulated. Results: The results show that the variation of the oscillation period of the sinusoidal modulation has a pertinent influence on the photodegradation of TPA and a maximum value of the apparent kinetic constant, 0.0045 min-1 is found when the period of oscillation is 0.24 s. The sinusoidal modulation with optimal amplitude occurs with current between 50-200 mA, that shows the highest value of the apparent kinetic constant equal to 0.0046 min-1. The optimal sinusoidal modulation, as a consequence is with current between 50-200 mA and period of 0.24 s. From the data collected from the tests, it is possible to evaluate the energy cost necessary to obtain the reduction of 90% of the terephthalic acid in 1 m3 of polluted water for each modulation (E E/O), and compare these values with other tests for TPA degradation reported in the literature. The internal comparison with the three systems of literature shows that the optima sinusoidal modulation of LEDs matrix permits a strong reduction in the electrical energy consumption. Conclusion: Photocatalytic tests have demonstrated the improvement of the process energy efficiency using the light modulation technique. A further confirmation of the advantage of light modulation was obtained by comparing the energy costs required for the abatement of 90% of the terephthalic acid in 1m 3 of the photocatalytic system. Finally, a mathematical model for photocatalytic degradation of terephthalic acid within the recirculating fixed bed photocatalytic reactor, irradiated by white-light LEDs was developed.