Raúl Molina

Heterogeneous catalytic wet peroxide oxidation systems for the treatment of an industrial pharmaceutical wastewater.

The aim of this work was to assess the treatment of wastewater coming from a pharmaceutical plant through a continuous heterogeneous catalytic wet peroxide oxidation (CWPO) process using an Fe(2)O(3)/SBA-15 nanocomposite catalyst. This catalyst was preliminary tested in a batch stirred tank reactor (STR), to elucidate the influence of significant parameters on the oxidation system, such as temperature, initial oxidant concentration and initial pH of the reaction medium. In that case, a temperature of 80 degrees C using an initial oxidant concentration corresponding to twice the theoretical stoichiometric amount for complete carbon depletion and initial pH of ca. 3 allow TOC degradation of around 50% after 200 min of contact time. Thereafter, the powder catalyst was extruded with bentonite to prepare pellets that could be used in a fixed bed reactor (FBR). Results in the up-flow FBR indicate that the catalyst shows high activity in terms of TOC mineralization (ca. 60% under steady-state conditions), with an excellent use of the oxidant and high stability of the supported iron species. The activity of the catalyst is kept constant, at least, for 55h of reaction. Furthermore, the BOD(5)/COD ratio is increased from 0.20 to 0.30, whereas the average oxidation stage (AOS) changed from 0.70 to 2.35. These two parameters show a high oxidation degree of organic compounds in the outlet effluent, which enhances its biodegradability, and favours the possibility of a subsequent coupling with a conventional biological treatment.

Integrated heterogeneous sono-photo Fenton processes for the degradation of phenolic aqueous solutions.

The removal of organic compounds from aqueous solutions has been tackled by a novel integrated heterogeneous system. The efficacy of the different systems has been assessed using Fenton-like processes (H2O2/Fe2O3-SBA-15) and phenol as model pollutant. Sono- and photo-Fenton processes separately applied as well as combined systems were studied in order to evaluate of possible beneficial effects on the use of coupled systems. The sequential system evidences an enhancement in terms of phenol and TOC conversions compared to the ultrasound or UV-light irradiation processes. A total phenol degradation and ca. 90% TOC reduction are achieved by sequentially ultrasound followed by UV-visible light irradiation. These effects are ascribed cavitation effect of ultrasound producing a reduction of particle size that provides a higher amount of available active sites due to an increased surface area for the subsequent photo-Fenton system. These encouraging results open new paths for the existing oxidation technologies for potable water and wastewater treatment.

Heterogeneous photo-Fenton treatment for the reduction of pharmaceutical contamination in Madrid rivers and ecotoxicological evaluation by a miniaturized fern spores bioassay.

Fifty-six pharmaceuticals of various chemical groups, such as anti-inflammatory, antibacterial and cardiovascular drugs, were detected in four selected river waters receiving sewage effluents in the Community of Madrid (Spain). A promising approach for the degradation of those residues is the application of a photo-Fenton treatment. Several new bioassays using fern spores were employed for the evaluation of acute and chronic toxicity based on mitochondrial activity, DNA and chlorophyll quantifications of as-received river water and photo-Fenton-treated samples. photo-Fenton treatment provided a high degree of total organic carbon mineralization with up to 70% reduction for river water samples. In addition, the elimination of most of the studied pharmaceutical compounds was confirmed. A few compounds, however (salicylic acid, ofloxacin, caffeine, cotinine and nicotine), seemed more resistant, with after-treatment concentrations between 4 and 44ngL(-1). Nicotine showed the most refractory behaviour with concentrations ranging from 29 to 224ngL(-1) for treated samples. Photo-Fenton treatment yielded a significant decrease in acute and chronic toxicity, even though some residual toxicity remained after treatment. This fact seemed to be related to the presence of toxicants in the water matrix, probably of inorganic nature, rather than the toxic effect of the studied pharmaceutical compounds, as revealed by the effective removal of these compounds and high TOC mineralization of photo-Fenton treatments.

Effect of Ultrasound on the Properties of Heterogeneous Catalysts for Sono-Fenton Oxidation Processes

Abstract The objective of this research is to assess the effect of ultrasonic irradiation (20 KHz) on the catalytic activity and catalyst particle size of different iron-containing solids (hematite/SBA-15 nanocomposite; hematite; goethite). The catalytic activities of the different catalysts were investigated in the sono-Fenton degradation of a phenolic aqueous solution in the presence of hydrogen peroxide at pH 3. The catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversions. The concentration changes of different by-products coming from incomplete mineralization of phenol were also monitored. The stability was examined by measuring iron dissolved in the reaction medium after reaction. The degradation rate in the presence of the nanocomposite material was higher than that when SBA-15 and hematite were separately suspended and also higher than that found for the bulk and unsupported iron oxides (hematite and goethite). The particle size of the catalysts suffers serious changes during the sonication which strongly depend on their nature. Unlike nanocomposite material which presents a deep catalyst particle reduction, unsupported bulk iron oxides yield an agglomeration of the particles. The considerable enhancement of the activity achieved with the nanocomposite material is due to the catalyst particles size reduction during ultrasound irradiation as well as the high dispersion of the metallic species over the mesostructured support.

Intensified-Fenton process for the treatment of phenol aqueous solutions

An intensified-Fenton process for the treatment of phenol aqueous solutions has been studied as a continuous catalytic wet hydrogen peroxide oxidation system. This process consists of coupling the catalytic activity of a heterogeneous Fenton-like catalyst with the homogeneous contribution of its dissolved iron species. Agglomerated mesoporous SBA-15 silica-supported iron oxide (Fe₂O₃/SBA-15) material was used as heterogeneous catalyst. The influence of the reaction temperature and the initial hydrogen peroxide dosages was studied in order to minimize the operation cost of the process. The catalytic performance of the process was assessed in terms of total organic carbon (TOC) and hydrogen peroxide conversions. Likewise, the stability of the solid Fenton-like catalyst was also evaluated in terms of the dissolved iron species. The increase of the reaction temperature enhanced the TOC conversion and reduced the iron leaching from the heterogeneous catalyst. These results were related to the degradation of oxalic acid as responsible for iron extraction by formation of soluble stable iron complexes into the aqueous medium. Finally, the use of a moderate hydrogen peroxide concentration (2.6 g/L) and milder temperatures (80-120 °C) has led to remarkable results of TOC and phenol reductions as well as oxidant efficiency through the intensified-Fenton process.

Activated carbon cloth: a potential adsorbing/oxidizing catalyst for phenolic wastewater.

An investigation into the use of activated carbon cloth (ACC) as a potential adsorbent and/or catalyst for oxidation processes is reported. The extent of increase/decrease of oxidation/adsorption of phenol, as measured by total organic carbon content (%), is explained by considering the effects of the oxidants such as ozone and hydrogen peroxide on the activated carbon cloth. Results also show that acid pH enhances the catalytic decomposition of H(2)O(2) to hydroxyl radicals, increasing TOC removal from 16 to 55% as a result of oxidation of phenol in addition to adsorption on the ACC surface. Furthermore when using ACC catalysis under optimized conditions, the maximum extent of TOC elimination is approximately 70% with three 15 min doses of ozone at pH 9.

ZVI Addition in Continuous Anaerobic Digestion Systems Dramatically Decreases P Recovery Potential: Dynamic Modelling

The objective of this study is to show the preliminary results of a (dynamic) mathematical model describing the effects of zero valent iron (ZVI) addition during the anaerobic digestion of waste activated sludge from wastewater treatment systems. A modified version of the Anaerobic Digestion Model No. 1 (ADM1) upgraded with an improved physico-chemical description, ZVI corrosion, propionate uptake enhancement and multiple mineral precipitation is used as a modelling platform. The proposed approach is tested against two case studies which correspond to two lab scale anaerobic digesters (AD2, AD1), with and without adding ZVI, respectively, and running in parallel for a period of 87 days. Experimental results show that ZVI enhances methane production. However, the P recovery potential is dramatically reduced as soluble P decreased by one order of magnitude in AD2 with respect to AD1. Simulations demonstrate that the model is capable to satisfactorily reproduce the dynamics of hydrolysis, acetogenesis, acidogenesis, nutrient release, pH and methanogenesis in the control anaerobic digester (AD1). This study also evidences the enhancement of methane production by the influence of ZVI on the acidogenesis and methanogenesis processes in AD2. In addition, it also identifies saturation conditions for siderite (FeCO3) and vivianite (Fe3(PO4)2), which causes changes in the biogas composition (% CH4 versus % CO2) and P release (lower values). This is the first study analysing the decrease of P recovery potential due to the addition of ZVI into AD systems.