Towards an Efficient Generalization of the Online Dosage of Hydrogen Peroxide in Photo-Fenton Process to Treat Industrial Wastewater

This work addresses the dosage of H2O2 in photo-Fenton processes and the monitoring of Dissolved oxygen (DO) that can be used to drive the dosage of H2O2. The objective of this work is to show that a smarter monitoring of a process variable such as DO (for which on-line measurement can be inexpensively obtained) enables the proposal and implementation of efficient dosage strategies. The work explores the application of a recent proposed strategy consisting of: (i) initial H2O2 addition, (ii) continuous H2O2 addition until a DO set up is reached, and (iii) automatic H2O2 addition by an on-off control system based on DO slope monitoring, and applies it to the treatment of different individual contaminants and their mixtures (paracetamol and sulfamethazine). The assays performed following this dosage strategy showed improved values of TOC removed per H2O2 consumed. For the case of sulfamethazine, this improvement increased up to 25–35% with respect to the efficiency obtained without dosage. Furthermore, a deeper analysis of the results allowed detecting and assessing the opportunity to redesign the dosage scheme and reduce its complexity and the number of control parameters. The promising results obtained are discussed in regard of future research into further increasing the simplicity and robustness of this generalized control strategy that improves the applicability of the photo-Fenton process by reducing its operating costs and increasing automation.

Photocatalytic Degradation of Azo Dyes Using Microreactors: Mechanistic Study of its Effects on H2O2 Addition

The photocatalytic reaction involved in TiO₂ photocatalysis was investigated using a microreactor coated with TiO₂ film on the glass plate attached on one side of the microreactor. It was confirmed that the effect of H₂O₂ on the photocatalytic degradation efficiency of azo dyes (acid orange 7, acid red 151, and acid yellow 23) was dependent on the polymorphs (anatase and rutile) of TiO₂ coated on the glass plate of the UV-irradiated microreactor. Scavengers of holes (KI) and electrons (p-benzoquinone) were added to the solution of azo dyes, and their effects on the degradation efficiencies of the azo dye (acid orange 7) in the microreactor system were investigated. It was found that the electron scavengers of p-benzoquinone showed much larger effects on the photocatalytic degradation efficiency than the hole scavengers of KI. Based on these results, the mechanism of the photocatalytic degradation of the azo dyes in the presence of H₂O₂ was proposed.

Fly Ash Waste Recycling by Pt/TiO2 Incorporation for Industrial Dyes Removal

New materials are obtained by transforming fly ash wastes into a valuable composite, with tandem adsorption and photodegradation properties. Mild hydrothermal synthesis, from titanium dioxide, Platinum nanoparticles and zeolite materials obtained from a waste, fly ash, as support, was involved in the composite preparation. The Platinum nanoparticles extended the photocatalytic activity of the composite in Visible range (Eg = 2.1 eV). The efficiency of tandem adsorption and photocatalytic activity of the new composite were evaluated to 80.70% for Bemacid Blau and 93.89% for Bemacid Rot, after 360 min, the irradiation time, with H2O2 addition.

NO Formation and Autoignition Dynamics during Combustion of H2O-Diluted NH3/H2O2 Mixtures with Air

NO formation, which is one of the main disadvantages of ammonia combustion, was studied during the isochoric, adiabatic autoignition of ammonia/air mixtures using the algorithm of Computational Singular Perturbation (CSP). The chemical reactions supporting the action of the mode relating the most to NO were shown to be essentially the ones of the extended Zeldovich mechanism, thus indicating that NO formation is mainly thermal and not due to fuel-bound nitrogen. Because of this, addition of water vapor reduced NO formation, because of its action as a thermal buffer, but increased ignition delay, thus exacerbating the second important caveat of ammonia combustion, which is unrealistically long ignition delay. However, it was also shown that further addition of just 2% molar of H2O2 does not only reduce the ignition delay by a factor of 30, but also reverses the way water vapor affects ignition delay. Specifically, in the ternary mixture NH3/H2O/H2O2, addition of water vapor does not prolong but rather shortens ignition delay because it increases OH radicals. At the same time, the presence of H2O2 does not affect the influence of H2O in suppressing NO generation. In this manner, we were able to show that NH3/H2O/H2O2 mixtures offer a way to use ammonia as carbon-less fuel with acceptable NOx emissions and realistic ignition delay.

Use of H2O2 to Cause Oxidative Stress, the Catalase Issue

Addition of hydrogen peroxide (H2O2) is a method commonly used to trigger cellular oxidative stress. However, the doses used (often hundreds of micromolar) are disproportionally high with regard to physiological oxygen concentration (low micromolar). In this study using polarographic measurement of oxygen concentration in cellular suspensions we show that H2O2 addition results in O2 release as expected from catalase reaction. This reaction is fast enough to, within seconds, decrease drastically H2O2 concentration and to annihilate it within a few minutes. Firstly, this is likely to explain why recording of oxidative damage requires the high concentrations found in the literature. Secondly, it illustrates the potency of intracellular antioxidant (H2O2) defense. Thirdly, it complicates the interpretation of experiments as subsequent observations might result from high/transient H2O2 exposure and/or from the diverse possible consequences of the O2 release.