Floating immobilized TiO2 catalyst for the solar photocatalytic treatment of micro-pollutants within the secondary effluent of wastewater treatment plants.

Floating immobilized spherical titanium dioxide catalysts were used to degrade micro-pollutants by solar photocatalysis. The degradation of the micro-pollutants was performed in the secondary effluent of a wastewater treatment plant. During the experimental period, the continuous measurement of the solar ultraviolet (UV) radiation intensity was performed. The micro-pollutants were degraded to an average of 55% after 9 h of irradiation. A substance-specific degradation affinity was found, whereby degradation rates varied by a factor of up to 3.5. The substance-specific adsorption behavior was identified as a major limitation of the reaction performance. With an increasing influence of adsorption limitation, the degradation kinetics changed from the pseudo-first order to pseudo-zero order. A correlation between degradation rate and solar irradiance could only be found for substances with high degradation/adsorption affinity. For diclofenac, a 95% degradation rate could be achieved at a radiation dose of approximately 190 mWh/m². The investigated technology represents a promising possibility for a minimally invasive extension of wastewater treatment plants. Possibilities of implication were estimated and discussed within this work, whereby possibilities arise for large-scale as well as decentral treatment plants.

Photocatalytic ozonation in an immersion rotary body reactor for the removal of micro-pollutants from the effluent of wastewater treatment plants.

Carrier-bound titanium dioxide catalysts were used in a photocatalytic ozonation reactor for the degradation of micro-pollutants in real wastewater. A photocatalytic immersion rotary body reactor with a 36-cm disk diameter was used, and was irradiated using UV-A light-emitting diodes. The rotating disks were covered with catalysts based on stainless steel grids coated with titanium dioxide. The dosing of ozone was carried out through the liquid phase via an external enrichment and a supply system transverse to the flow direction. The influence of irradiation power and ozone dose on the degradation rate for photocatalytic ozonation was investigated. In addition, the performance of the individual processes photocatalysis and ozonation were studied. The degradation kinetics of the parent compounds were determined using liquid chromatography tandem mass spectrometry. First-order kinetics were determined for photocatalysis and photocatalytic ozonation. A maximum reaction rate of the reactor was determined, which could be achieved by both photocatalysis and photocatalytic ozonation. At a dosage of 0.4 mg O3/mg DOC, the maximum reaction rate could be achieved using 75% of the irradiation power used for sole photocatalysis, allowing increases in the energetic efficiency of photocatalytic wastewater treatment processes. The process of photocatalytic ozonation is suitable to remove a wide spectrum of micro-pollutants from wastewater.

Behavior of matrix parameters and their correlation to micro-pollutant degradation during treatment of real wastewater by carrier-bound photocatalytic ozonation.

Immobilized titanium dioxide catalysts were used within a photocatalytic immersion rotary body reactor, which was connected to a substream ozonation unit to remove micro-pollutants from wastewater. Within this work data on the behavior of cumulative parameters during treatment of wastewater by photocatalysis and photocatalytic ozonation are provided. The investigated parameters are spectral absorption coefficient at 254 nm (SAC254), total organic carbon (TOC) and chemical oxygen demand (COD). All experiments were carried out using secondary effluent from the same wastewater treatment plant. For the parameter SAC254, consistent concentration curves and dependencies to operational parameters of the experimental system could be measured. The measurements of the parameters TOC and COD showed greater uncertainties, although basic trends could nonetheless be observed. A good linear correlation (R2 < 0.85) between the reduction of SAC254 and 8 micro-pollutants for photocatalysis and photocatalytic ozonation was found. This confirms the suitability of the SAC254 as a control parameter for a large-scale application of a photocatalytic 4th treatment stage. A linear correlation between measured TOC and COD degradation rates was possible with a coefficient of determination of 0.58-0.86. The simultaneous decrease of TOC and COD is an indicator for a mineralization of the treated wastewater matrix.

Hydrogen peroxide-assisted photocatalytic water treatment for the removal of anthropogenic trace substances from the effluent of wastewater treatment plants.

Supported titanium dioxide catalysts were used in a photocatalytic flat cell reactor to remove organic micropollutants from real wastewater. Catalysts based on stainless steel mesh with a porous coating made of titanium dioxide nanoparticles with predominantly anatase modification were used. The influence of the retention time, and light output, and the effect of hydrogen peroxide on the degradation were examined. The kinetics of the degradation of the parent substances was determined by liquid chromatography-tandem mass spectrometry. As a result, first-order degradation kinetics could be confirmed for all substances. The irradiance had no linear influence on the degradation of the compounds. Hydrogen peroxides were added to the wastewater to be treated, as electron acceptors and boosters, and alone had no great oxidative effect on the parent substances. The combination of photocatalysis with the addition of hydrogen peroxide as an electron acceptor had great synergetic effects which can reduce the required energy of the process through a short retention time. The process is suitable for the removal of micropollutants from wastewater.

Investigation of the Effect of Oxide Additives on the Band Gap and Photocatalytic Efficiency of TiO2 as a Fixed Film.

The effects of various additives (Y2O3, Ga2O3, and WO3) on photocatalytic degradation efficiency under UV light-emitting diodes (LEDs) and the optical properties of TiO2 Degussa P25 were investigated using ketoprofen and diclofenac, two non-steroidal anti-inflammatory drugs commonly detected in German rivers. Experimental results demonstrated that thin films containing these additives exhibited similar photocatalytic degradation efficiencies as pure TiO2, achieving a 30% degradation of ketoprofen over 150 min. In contrast, the Y2O3/TiO2 thin film showed significantly improved performance, achieving a 46% degradation of ketoprofen in 180 min. Notably, the Y2O3/TiO2 system was three times more effective in degrading diclofenac compared to pure TiO2. Additionally, the Y2O3/TiO2 photocatalyst retained its activity over three successive cycles with only a slight decrease in efficiency. The photocatalytic degradation of both organic pollutants followed first-order kinetics with all photocatalysts. The investigation included SEM imaging to assess the surface homogeneity of the thin films and UV-vis solid-state spectroscopy to evaluate the impact of the additives on the energy band gap of TiO2.

Low-cost test rig for characterization of photocatalytic planar materials using photonically sized UV-A LED light sources.

In the presented studies, a system for the characterization of planar photocatalysts was developed and tested. In the system, reference substances can be studied online with regard to their degradability and adsorption on photocatalytic materials. In order to perform accurate calculations of the quantum and photon efficiency of the catalysts, the LED arrays used were adjusted in their spacing by simulations so that a homogeneous light field is imaged on the catalysts. The system was tested with respect to measurement accuracy and reproducibility and the photocatalytic degradation of methylene blue, methyl orange and rhodamine B was investigated. Exemplarily, the reaction kinetics, photolysis and adsorption on the tested photocatalysts were determined for these compounds and the calculation was presented in detail. The exact construction plans and circuits as well as the sensors and their programming are presented in detail and should encourage other scientists to replicate the experimental setup, since especially in the field of photocatalysis research, often the results of publications cannot be compared with each other.