79 resultados para advanced process oxidation
em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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This work studied the degradation of dipyrone, via electrochemical processes and via electro-Fenton reaction using a 4% CeO2/C gas diffusion electrode (GDE) prepared via modified polymeric precursor method. This material was used to electrochemically generate H2O2 through oxygen reduction. The mean crystallite sizes estimated by the Scherrer equation for 4% CeO2/C were 4 nm for CeO2-x (0 4 4) and 5 nm for CeO2 (1 1 1) while using transmission electron microscopy (TEM) the mean nanoparticle size was 5.4 nm. X-ray photoelectron spectroscopy (XPS) measurements revealed nearly equal concentrations of Ce(III) and Ce(IV) species on carbon, which contained high oxygenated acid species like CO and OCO. Electrochemical degradation using Vulcan XC 72R carbon showed that the dipyrone was not removed during the two hour electrolysis in all applied potentials by electro-degradation. Besides, when the Fenton process was employed the degradation was much similar when using cerium catalysts but the mineralization reaches just to 50% at -1.1 V. However, using the CeO2/C GDE, in 20 min all of the dipyrone was degraded with 26% mineralization at -1.3 V and when the Fenton process was employed, all of the dipyrone was removed after 5 min with 57% mineralization at -1.1 V. Relative to Vulcan XC72R, ceria acts as an oxygen buffer leading to an increase in the local oxygen concentration, facilitating H2O2 formation and consequently improving the dipyrone degradation © 2013 Elsevier B.V. All rights reserved.
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Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). PPV derivatives are highly susceptible to photo-oxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (similar to 50 nm) to allow for a more realistic comparison. Degradation was monitored with UV-vis and FTIR spectroscopies. The results indicated that cast films were completely degraded in ca. 400 min, while LB took longer time, i.e. about four times the values for the cast films. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process. (c) 2006 Elsevier Ltd. All rights reserved.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Photodegradation of the pharmaceuticals amoxicillin (AMX), bezafibrate (BZF) and paracetamol (PCT) in aqueous solutions via the photo-Fenton process was investigated under black-light and solar irradiation. The influences of iron source, initial H2O2 concentration and matrix (distilled water and sewage treatment plant effluent) on degradation efficiency were discussed in detail. The results showed that (i) the degradation of the drugs was favored in the presence of potassium ferrioxalate (FeOx) in comparison to Fe(NO3)(3): (ii) the increase of the H2O2 concentration improved the efficiency of AMX and BZF oxidation; however, the same was not observed for PCT: (iii) the influence of the matrix was observed for the degradation of BZF and PCT: (iv) under solar irradiation, the oxidation of the BZF and PCT is faster than under black-light irradiation. All these pharmaceuticals can be efficiently degraded employing the process evaluated. (C) 2008 Elsevier B.V. All rights reserved.
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The recovery of the pharmaceuticals bezafibrate and tetracycline from water was evaluated, using Solid Phase Extraction (SPE) with the aim of applying this technique to interrupt the pharmaceuticals' photodegradation by photo-Fenton process for further analysis. Sep-Pack C-18, Strata X, and Oasis HLB cartridges were evaluated. Oasis HLB showed the most satisfactory recovery and repeatability results: 98% (CV - 1%) for bezafibrate (20.0 mg L-1) and 76% (CV = 1%) for tetracycline (25.0 mg L-1). There was not a significant decrease in recovery at lower concentrations of the pharmaceuticals, and neither when present in Sewage Treatment Plant (STP) effluent matrix.
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In the present work the use of a coupled process, soil washing and photo-Fenton oxidation, was investigated for remediation of a soil contaminated with p.p'-DDT (DDT) and p.p'-DDE (DDE), and a soil artificially contaminated with diesel. In the soil washing experiments,Triton X-100(TX-100) aqueous solutions were used at different concentrations to obtain wastewaters with different compositions. Removal efficiencies of 66% (DDT). 80% (DDE) and 100% (diesel) were achieved for three sequential washings using a TX-100 solution strength equivalent to 12 times the effective critical micelle concentration of the surfactant (12 CMC(eff)). The wastewater obtained was then treated using a solar photo-Fenton process. After 6 h irradiation, 99, 95 and 100% degradation efficiencies were achieved for DDT, DDE and diesel, respectively. In all experiments, the concentration of dissolved organic carbon decreased by at least 95%, indicating that residual concentration of contaminants and/or TX-100 in the wastewater was very low. The co-extraction of metals was also evaluated. Among the metals analyzed (Pb, Cr, Ni, Cu. Cd, Mn and Co), only Cr and Mn were detected in the wastewater at concentrations above the maximum value permitted by current Brazilian legislation. The effective removal of contaminants from soil by the TX-100 washing process, together with the high degradation efficiency of the solar photo-Fenton process, suggests that this procedure could be a useful option for soil remediation. (C) 2009 Elsevier B.V. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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The influence of pH on the degradation of the herbicide tebuthiuron (TBH) was investigated using in situ generated Fe(III)-citrate complexes (Fe:cit) submitted to the photo-Fenton process under solar irradiation. Using Fe:cit in a wide pH range (2.5-7.5), 100-78% TBH oxidation was achieved respectively from a UV dose of 2.0 J cm(-2) (15 min). Moreover, the oxidation of TBH obtained in the presence of Fe:cit at pH 6.0 was higher than that obtained using Fe(NO3)3 at pH 2.5. A similar behavior is observed for the removal of total organic carbon (TOC) in TBH solutions. In the presence of Fe:cit, 20% and 85% of TOC was removed at pH 7.5 and 2.5, respectively, after 7.5 J cm-2 irradiation, while no mineralization was observed employing Fe(NO3)(3) for the same UV dose. Using Fe(NO3)(3), mineralization was observed only after 11 J cm-2 (8%). A higher mineralization rate was obtained with Fe(NO3)(3) only when a concentration three times higher was employed at pH 2.5. Besides the high efficiency of TBH degradation observed using the ferric citrate complex in the solar photo-Fenton process, it also offers the advantage of application at a pH of up to 7.5. (c) 2007 Elsevier B.V. All rights reserved.
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The red Fe2+-phenanthroline complex is the basis of a classical spectrophotometric method for determination of iron. Due to the toxicity of this complexing agent, direct disposal of the wastewaters generated in analytical laboratories is not environmentally safe. This work evaluates the use of the solar photo-Fenton process for the treatment of laboratory wastewaters containing phenanthroline. Firstly, the degradation of phenanthroline in water was evaluated at two concentration levels (0.1 and 0.01%, w/v) and the efficiencies of degradation using ferrioxalate (FeOx) and ferric nitrate were compared. The 0.01% w/v solution presented much higher mineralization, achieving 82% after 30 min of solar irradiation with both iron sources. The solar photo-Fenton treatment of laboratory wastewater containing, in addition to phenanthroline, other organic compounds such as herbicides and 4-chlorophenol, equivalent to 4500 mg L-1 total organic carbon (TOC) resulted in total degradation of phenanthroline and 25% TOC removal after 150 min, in the presence of either FeOx or ferric nitrate. A ratio of 1: 10 dilution of the residue increased mineralization in the presence of ferrioxalate, achieving 38% TOC removal after 120 min, while use of ferric nitrate resulted in only 6% mineralization over the same period. (c) 2007 Elsevier B.V. All rights reserved.
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The degradation of the antibiotic tetracycline (TC) by the photo-Fenton process was evaluated under black-light and solar irradiation. The influences of iron source (Fe(NO3)(3) or ferrioxalate), hydrogen peroxide and matrix (pure water, surface water and a sewage treatment plant effluent-STP) were evaluated. Under black-light irradiation, TC degradation was favored in the presence of Fe(NO3)(3), achieving total degradation after 1 min irradiation, while under solar light the use of ferrioxalate favors the degradation. Nevertheless, no significant difference in total organic carbon removal was observed between these two iron sources, achieving a residual concentration of around 5 mg L-1 under black-light and 2 mg L-1 under solar light irradiation. No decrease of the degradation efficiency relative to pure water was observed when TC was irradiated in a sample of surface water, under either black-light or solar irradiation. However, lower efficiency was obtained under black-light when TC was present in a sample of STP effluent, indicating the interference of the constituents of this sample on the overall efficiency of the process. on the other hand, under solar irradiation in the presence of ferrioxalate, no influence of the matrix was observed, even in the sample of STP effluent, achieving total degradation of TC in 1.5 min. (c) 2006 Elsevier B.V. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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The photo-Fenton process using potassium ferrioxalate as a mediator was investigated for the photodegradation of dichloracetic acid (DCA) and 2,4-dichlorophenol (DCP) in aqueous medium using solar light as source of irradiation. The influence of the solution depth, the light intensity and the effect of stirring the solution during irradiation process were evaluated using DCA as a model compound. A negligible influence of stirring the solution was observed when the concentration of ferrioxalate (FeOx) was 0.8 mM and solution depth was 4.5 or 14 cm. The optimum FeOx concentration determined for solution depths between 4.5 and 14 cm was 0.8 mM considering total organic carbon (TOC) removal during DCA irradiation. The high efficiency of the photo-Fenton process was demonstrated on summer days, when only 10 min of exposition (around noon) were sufficient to completely destroy the organic carbon of a 1.0 mM DCA solution in the presence of 0.8 mM FeOx and 6.0 mM H2O2 using a solution depth of 4.5 cm. It was observed that the photodegradation efficiency increases linearly with the solar light intensity up to values around 15 Wm-2 but this linear relationship does not hold above this value showing a square root dependence. The photodegradation of a solution of DCP/FeOx showed a lower TOC removal rate than that observed for DCA/FeOx, achieving ∼90% after 35 min irradiation under 19 Wm-2, while under this light intensity, the same TOC removal of DCA/FeOx was achieved in only 10 min irradiation. © 2002 Elsevier Science Ltd. All rights reserved.
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Automotive parts manufacture by machining process using silicon nitride-based ceramic tool development in Brazil already is a reality. Si 3N4-based ceramic cutting tools offer a high productivity due to their excellent hot hardness, which allows high cutting speeds. Under such conditions the cutting tool must be resistant to a combination of mechanical, thermal and chemical attacks. Silicon nitride based ceramic materials constitute a mature technology with a very broad base of current and potential applications. The best opportunities for Si3N 4-based ceramics include ballistic armor, composite automotive brakes, diesel particulate filters, joint replacement products and others. The goal of this work was to show latter advance in silicon nitride manufacture and its recent evolution on machining process of gray cast iron, compacted graphite iron and Ti-6Al-4V. Materials characterization and machining tests were analyzed by X-Ray Diffraction, Scanning Electron Microscopy, Vickers hardness and toughness fracture and technical norm. In recent works the authors has been proved to advance in microstructural, mechanical and physic properties control. These facts prove that silicon nitride-based ceramic has enough resistance to withstand the impacts inherent to the machining of gray cast iron (CI), compacted graphite iron (CGI) and Ti-6Al-4V (6-4). Copyright © 2008 SAE International.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)