Search results for: advanced oxidation processes

Authors: F. Javier Benitez, Francisco J. Real, Juan Luis Acero, Francisco Casas

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Three emerging contaminants (amitriptyline hydrochloride, methyl salicylate and 2-phenoxyethanol) frequently found in waste-waters were selected to be individually degraded in ultra-pure water by the combined advanced oxidation process constituted by UV radiation and chlorine. The influence of pH, initial chlorine concentration and nature of the contaminants was firstly explored. The trend for the reactivity of the selected compounds was deduced: amitriptyline hydrochloride > methyl salicylate > 2-phenoxyethanol. A later kinetic study was carried out and focused on the specific evaluation of the first-order rate constants and the determination of the partial contribution to the global reaction of the direct photochemical pathway and the radical pathway. A comparison between the rate constant values among photochemical experiments without and with the presence of Cl₂ reveals a clear increase in the oxidation efficiency of the combined process with respect to the photochemical reaction alone. In a second stage, the simultaneous oxidation of mixtures of the selected contaminants in several types of water (ultrapure water, surface water from a reservoir, and two secondary effluents) was also performed by the same combination UV/Cl₂ under more realistic operating conditions. The efficiency of this combined system UV/Cl₂ was compared to other oxidants such as the UV/S₂O₈^2- and UV/H₂O₂ AOPs. Results confirmed that the UV/Cl₂ system provides higher elimination efficiencies among the AOPs tested.

Keywords: emerging contaminants, UV/chlorine advanced oxidation process, amitriptyline, methyl salicylate, 2-phenoxyethanol, chlorination, photolysis

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Authors: Marius Sebastian Secula, Mihaela Darie, Gabriela Carja

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Ibuprofen is a non-steroidal anti-inflammatory drug (NSAIDs) and is among the most frequently detected pharmaceuticals in environmental samples and among the most widespread drug in the world. Its concentration in the environment is reported to be between 10 and 160 ng L-1. In order to improve the abatement efficiency of this compound for water source prevention and reclamation, the development of innovative technologies is mandatory. AOPs (advanced oxidation processes) are known as highly efficient towards the oxidation of organic pollutants. Among the promising combined treatments, photo-Fenton processes using layered double hydroxides (LDHs) attracted significant consideration especially due to their composition flexibility, high surface area and tailored redox features. This work presents the self-supported Fe, Mn or Ti on ZnFeAl LDHs obtained by co-precipitation followed by reconstruction method as novel efficient photo-catalysts for Fenton-like catalysis. Fe, Mn or Ti/ZnFeAl LDHs nano-hybrids were tested for the degradation of a model pharmaceutical agent, the anti-inflammatory agent ibuprofen, by photocatalysis and photo-Fenton catalysis, respectively, by means of a lab-scale system consisting of a batch reactor equipped with an UV lamp (17 W). The present study presents comparatively the degradation of Ibuprofen in aqueous solution UV light irradiation using four different types of LDHs. The newly prepared Ti/ZnFeAl 4:1 catalyst results in the best degradation performance. After 60 minutes of light irradiation, the Ibuprofen removal efficiency reaches 95%. The slowest degradation of Ibuprofen solution occurs in case of Fe/ZnFeAl 4:1 LDH, (67% removal efficiency after 60 minutes of process). Evolution of Ibuprofen degradation during the photo Fenton process is also studied using Ti/ZnFeAl 2:1 and 4:1 LDHs in the presence and absence of H2O2. It is found that after 60 min the use of Ti/ZnFeAl 4:1 LDH in presence of 100 mg/L H2O2 leads to the fastest degradation of Ibuprofen molecule. After 120 min, both catalysts Ti/ZnFeAl 4:1 and 2:1 result in the same value of removal efficiency (98%). In the absence of H2O2, Ibuprofen degradation reaches only 73% removal efficiency after 120 min of degradation process. Acknowledgements: This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0405.

Keywords: layered double hydroxide, advanced oxidation process, micropollutant, heterogeneous Fenton

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Authors: Anurak Khrueakham, Tassanee Chanphuthin

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Indigo is a well-known natural blue dye that is used hither to even though synthetic ones are commercially available. The removal of indigo from effluents is difficult due to its resistance towards biodegradation which causes an aquatic environment effect. Fenton process is a reaction between hydrogen peroxide H2O2 and Fe2+ to generate •OH (highly reactive oxidant (E◦= 2.8 V)). Additionally, •OH is non-selective oxidant which is capable of destroying wide range of organic pollutants in water and wastewater. The aims of this research were to investigate the effect of H2O2, Fe2+ and pH on indigo wastewater oxidation by Fenton process. A liter reactor was operated in all experiments. The batch reactor was prepared by filling 1 liter of indigo wastewater. The pH was adjusted to the desired value; then, FeSO4 at predetermined amount was added. Finally, H2O2 was immediately added to start the Fenton’s reaction. The Fenton oxidation of indigo wastewater was operated for 60 minutes. Residual H2O2 was analyzed using titanium oxalate method. The Fe2+ concentration was determined by phenanthroline method. COD was determined using closed-reflux titrimetric method to indicate the removal efficiency. The results showed that at pH 2 increasing the initial ferrous concentration from 0.1 mM to 1 mM enhanced the indigo removal from 36% to 59%. Fenton reaction was rapidly due to the high generation rate of •OH. The degradation of indigo increased with increasing pH up to pH 3. This can be explained that the scavenging effect of the •OH by H+ in the condition of low pH is severe to form an oxonium ion, resulting in decrease the production of •OH and lower the decolorization efficiency of indigo. Increasing the initial H2O2 concentration from 5 mM to 20 mM could enhance the decolorization. The COD removal was increased from 35% to 65% with increasing H2O2 concentration from 5 mM to 20 mM. The generations of •OH were promoted by the increase of initial H2O2 concentration. However, the higher concentration of H2O2 resulted in the reduction of COD removal efficiency. The initial ferrous concentrations were studied in the range of 0.05-15.0 mM. The results found that the COD removals increased with increasing ferrous concentrations. The COD removals were increased from 32% to 65% when increase the ferrous concentration from 0.5 mM to 10.0 mM. However, the COD removal did not significantly change at higher 10.0 mM. This is because •OH yielding was lower level of oxidation, therefore, the COD removals were not improved. According to the studies, the Fenton’s reagents were important factors for COD removal by Fenton process. The optimum condition for COD removal of indigo dye wastewater was 10.0 mM of ferrous, 20 mM of H2O2 and at pH 3.

Keywords: indigo dye, fenton oxidation, wastewater treatment, advanced oxidation processes

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Authors: Angelo Lanzilotto, Martin Kuss-Petermann, Catherine E. Housecroft, Edwin C. Constable, Oliver S. Wenger

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We recently described the synthesis of a new tetraphenylporphyrinatozinc(II)-conjugated 2,2':6',6"-terpyridine (1) in which the tpy domain enables the molecule to act as a metalloligand. The synthetic route to 1 has been optimized, the importance of selecting a particular sequence of synthetic steps will be discussed. Three homoleptic complexes have been prepared, [Zn(1)₂]²⁺, [Fe(1)₂]²⁺ and [Ru(1)₂]²⁺, and have been isolated as the hexafluoridophosphate salts. Spectroelectrochemical measurements have been performed and the spectral changes ascribed to redox processes are partitioned on either the porphyrin or the terpyridine units. Compound 1 undergoes a reversible one-electron oxidation/reduction. The removal/gain of a second electron leads to a further irreversible chemical transformation. For the homoleptic [M(1)₂]²⁺ complexes, a suitable potential can be chosen at which both the oxidation and the reduction of the {ZnTPP} core are reversible. When the homoleptic complex contains a redox active metal such as Fe or Ru, spectroelectrochemistry has been used to investigate the metal to ligand charge transfer (MLCT) transition. The latter is sensitive to the oxidation state of the metal, and electrochemical oxidation of the metal center suppresses it. Detailed spectroelectrochemical studies will be presented.

Keywords: homoleptic complexes, spectroelectrochemistry, tetraphenylporphyrinatozinc(II), 2, 2':6', 6"-terpyridine

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Authors: Hernan Arturo Blas López, Gustavo Henndel Lopes, Antonio Carlos Silva Costa Teixeira, Carmen Elena Flores Barreda, Patricia Araujo Pantoja

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Phenols are toxic for life and the environment and may come from many sources. Uncured phenolic monomers present in phenolic resins used as binders in grinding wheels and emery paper can contaminate industrial wastewaters in abrasives manufacture plants. Furthermore, vestiges of resol and novolacs resins generated by wear and tear of abrasives are also possible sources of water contamination by phenolics in these facilities. Fortunately, advanced oxidation by dark Fenton and photo-Fenton techniques are capable of oxidizing phenols and their degradation products up to their mineralization into H₂O and CO₂. The maximal allowable concentrations for phenols in Peruvian waterbodies is very low, such that insufficiently treated effluents from the abrasives industry are a potential environmental noncompliance. The current case study highlights findings obtained during the lab-scale application of Fenton’s and photo-assisted Fenton’s chemistries to real industrial wastewater samples from an abrasives manufacture plant in Peru. The goal was to reduce the phenolic content and sample toxicity. For this purpose, two independent variables-reaction time and effect of ultraviolet radiation–were studied as for their impacts on the concentration of total phenols, total organic carbon (TOC), biological oxygen demand (BOD) and chemical oxygen demand (COD). In this study, diluted samples (1 L) of the industrial effluent were treated with Fenton’s reagent (H₂O₂ and Fe²⁺ from FeSO₄.H₂O) during 10 min in a photochemical batch reactor (Alphatec RFS-500, Brazil) at pH 2.92. In the case of photo-Fenton tests with ultraviolet lamps of 9 W, UV-A, UV-B and UV-C lamps were evaluated. All process conditions achieved 100% of phenols degraded within 5 minutes. TOC, BOD and COD decreased by 49%, 52% and 86% respectively (all processes together). However, Fenton treatment was not capable of reducing BOD, COD and TOC below a certain value even after 10 minutes, contrarily to photo-Fenton. It was also possible to conclude that the processes here studied degrade other compounds in addition to phenols, what is an advantage. In all cases, elevated effluent dilution factors and high amounts of oxidant agent impact negatively the overall economy of the processes here investigated.

Keywords: fenton oxidation, wastewater treatment, phenols, abrasives industry

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Authors: Zineb Benouahmane, Zhang Lifeng

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Experimental oxidation tests at high temperature (1300°C-1500°C) on α-SiC samples have been performed with different holding times and atmosphere (air, argon). Oxidized samples were then analyzed using X-ray photoelectron spectroscopy coupled to SEM and DAKTEK surface profiler verification. The oxidation rate and the mas gain were found to increase with temperature and holding times, corresponding to a passive oxidation regime which lead to the formation of SiO2 layer. The sessile drop method is employed in order to measure the wetting angles between Si/SiC system at high temperature (1430°C-1550°C). Contact angle can be varied between 44 °C to 85°C, by controlling the oxygen content in α-SiC. Increasing the temperature occurred the infiltration of liquid silicon and deoxidation of the coating.

Keywords: oxidation, wettability, silicon, SiC

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Authors: Krasimir Ivanov, Dimitar Dimitrov, Tatyana Tabakova, Stefka Kirkova, Anna Stoilova, Violina Angelova

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It has been suggested that nicotine, CO and tar in mainstream smoke are the most important substances and have been judged as the most harmful compounds, responsible for the health hazards of smoking. As nicotine is extremely important for smoking qualities of cigarettes and the tar yield in the tobacco smoke is significantly reduced due to the use of filters with various content and design, the main efforts of cigarettes researchers and manufacturers are related to the search of opportunities for CO content reduction. Highly active ceria supported gold catalyst was prepared by the deposition-precipitation method, and the possibilities for CO oxidation in the synthetic gaseous mixture were evaluated using continuous flow equipment with fixed bed glass reactor at atmospheric pressure. The efficiently of the catalyst in CO oxidation in the real cigarette smoke was examined by a single port, puf-by-puff smoking machine. Quality assessment of smoking using cigarette holder containing catalyst was carried out. It was established that the catalytic activity toward CO oxidation in cigarette smoke rapidly decreases from 70% for the first cigarette to nearly zero for the twentieth cigarette. The present study shows that there are two critical factors which do not permit the successful use of catalysts to reduce the CO content in the mainstream cigarette smoke: (i) significant influence of the processes of adsorption and oxidation on the main characteristics of tobacco products and (ii) rapid deactivation of the catalyst due to the covering of the catalyst’s grains with condensate.

Keywords: cigarette smoke, CO oxidation, gold catalyst, mainstream

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Authors: Yalçın Kılıç, İbrahim Kani

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The conversion of hydrocarbons to carbonyl compounds by oxidation reaction is one of the most important reactions in the synthesis of fine chemicals. As a result of the oxidation of hydrocarbons containing aliphatic sp3-CH groups in their structures, aldehydes, ketones or carboxylic acids can be obtained. In this study, OSSO-type 2,2'-[1,4-butanedylbis(thio)]bis-benzoic acid (tsabutH2) ligand and [Zn(µ-tsabut)(phen)]n complex (where phen = 1,10-phenantroline) were synthesized and their structures were characterized by single crystal x-ray diffraction method. The catalytic efficiency of the complex in the catalytic oxidation studies of organic compounds such as cyclohexane, ethylbenzene, diphenylmethane, and p-xylene containing sp3-C-H in its structure was investigated.

Keywords: metal complex, OSSO-type ligand, catalysis, oxidation

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Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov, Petya Petrova, Tatyana Tabakova

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This work studies the effect of chemical composition on the activity and selectivity of γ–alumina supported CuO/ MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether (DME) and methanol. The catalysts were prepared by impregnation of the support with an aqueous solution of copper nitrate, manganese nitrate and CrO3 under different conditions. Thermal, XRD and TPR analysis were performed. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor. Flow-line equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions that mimic closely the industrial ones was used. The reactant and product gases were analyzed by means of on-line gas chromatographs. On the basis of XRD analysis it can be concluded that the active component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4, Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio. Chemical composition strongly influences catalytic properties, this influence being quite variable with regards to the different processes. The rate of CO oxidation rapidly decrease with increasing of chromium content in the active component while for the DME was observed the reverse trend. It was concluded that the best compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and Mn/Cr molar ratio from 1:3 to 1:4.

Keywords: Cu-Mn-Cr oxide catalysts, volatile organic compounds, deep oxidation, dimethyl ether (DME)

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Authors: Lin-Lin Liu, Song-Qi Hu, Yin Wang

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Paraffin-based fuels are regarded to be a promising fuel of hybrid rocked motor because of the high regression rate, low price, and environmental friendliness. Graphene Oxide (GO) is an attractive energetic material which is expected to be widely used in propellants, explosives, and some high energy fuels. Paraffin-based fuels with paraffin and GO as raw materials were prepared, and the oxidation process of the samples was investigated by thermogravimetric analysis differential scanning calorimetry (TG/DSC) under oxygen (O₂) and nitrous oxide (N₂O) atmospheres. The oxidation reaction kinetics of the fuels was estimated through the non-isothermal measurements and model-free isoconversional methods based on the experimental results of TGA. The results show that paraffin-based fuels are easier oxidized under O₂ rather than N₂O with atmospheres due to the lower activation energy; GO plays a catalytic role for the oxidation of paraffin-based fuels under the both atmospheres, and the activation energy of the oxidation process decreases with the increase of GO; catalytic effect of GO on the oxidation of paraffin-based fuels are more obvious under O₂ atmospheres than under N₂O atmospheres.

Keywords: graphene oxide, paraffin-based fuels, oxidation, activation energy, TGA

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Authors: Muna K. Abbass, Laith A. Mohammed, Muntaha K. Abbas

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The oxidation of Al-Li base alloy containing small amounts of rare earth (RE) oxides such as 0.2 wt% Y2O3 and 0.2wt% Nd2O3 particles have been studied at temperatures: 400ºC, 500ºC and 550°C for 60hr in a dry air. Alloys used in this study were prepared by melting and casting in a permanent steel mould under controlled atmosphere. Identification of oxidation kinetics was carried out by using weight gain/surface area (∆W/A) measurements while scanning electron microscopy (SEM) and x-ray diffraction analysis were used for micro structural morphologies and phase identification of the oxide scales. It was observed that the oxidation kinetic for all studied alloys follows the parabolic law in most experimental tests under the different oxidation temperatures. It was also found that the alloy containing 0.2 wt %Y 2O3 particles possess the lowest oxidation rate and shows great improvements in oxidation resistance compared to the alloy containing 0.2 wt % Nd2O3 particles and Al-Li base alloy. In this work, Taguchi method is performed to estimate the optimum weight gain /area (∆W/A) parameter in oxidation process of Al-Li base alloys to obtain a minimum thickness of oxidation layer. Taguchi method is used to formulate the experimental layout, to analyses the effect of each parameter (time, temperature and alloy type) on the oxidation generation and to predict the optimal choice for each parameter and analyzed the effect of these parameters on the weight gain /area (∆W/A) parameter. The analysis shows that, the temperature significantly affects on the (∆W/A) parameter.

Keywords: Al-Li base alloy, oxidation, Taguchi method, temperature

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Authors: Hang Zhou, Limin Zhu

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This paper investigates the fabrication of microstructures on Si surfaces by using electrochemical anodic oxidation with agarose stamps. The fabricating process is based on a selective anodic oxidation reaction that occurs in the contact area between a stamp and a Si substrate. The stamp which is soaked in electrolyte previously acts as a current flow channel. After forming the oxide patterns as an etching mask, a KOH aqueous is used for the wet etching of Si. A complicated microstructure array of 1 cm2 was fabricated by the method with high accuracy.

Keywords: microstructures, anodic oxidation, silicon, agarose stamps

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Authors: Krittiya Pornmai, Sumaeth Chavadej

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The increasing in global energy demand has affected the climate change caused by the generation of greenhouse gases. Therefore, the objective of this work was to investigate a direct production of synthesis gas from a CO₂-containing natural gas by using gliding arc discharge plasma technology. In this research, the effects of steam reforming, combined steam reforming and partial oxidation, and using multistage gliding arc discharge system on the process performance have been discussed. The simulated natural gas used in this study contains 70% methane, 5% ethane, 5% propane, and 20% carbon dioxide. In comparison with different plasma reforming processes (under their optimum conditions), the steam reforming provides the highest H₂ selectivity resulting from the cracking reaction of steam. In addition, the combined steam reforming and partial oxidation process gives a very high CO production implying that the addition of both oxygen and steam can offer the acceptably highest synthesis gas production. The stage number of plasma reactor plays an important role in the improvement of CO₂ conversion. Moreover, 3 stage number of plasma reactor is considered as an optimum stage number for the reforming of CO₂-containing natural gas with steam and partial oxidation in term of providing low energy consumption as compared with other plasma reforming processes.

Keywords: natural gas, reforming process, gliding arc discharge, plasma technology

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Authors: Chaoqun Tan, Naiyun Gao, Xiaoyan Xin

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Perxymonosulfate (PMS)-based oxidation processes, as an alternative of hydrogen peroxide-based oxidation processes, are more and more popular because of reactive radical species (SO4-•, OH•) produced in systems. Magnetic nano-scaled particles Fe3O4 and ferrous anion (Fe2+) were studied for the activation of PMS for degradation of acetaminophen (APAP) in water. The Fe3O4 MNPs were found to effectively catalyze PMS for APAP and the reactions well followed a pseudo-first-order kinetics pattern (R2>0.95). While the degradation of APAP in PMS-Fe2+ system proceeds through two stages: a fast stage and a much slower stage. Within 5 min, approximately 7% and 18% of 10 ppm APAP was accomplished by 0.2 mM PMS in Fe3O4 (0.8g/L) and Fe2+ (0.1mM) activation process. However, as reaction proceed to 120 min, approximately 75% and 35% of APAP was removed in Fe3O4 activation process and Fe2+ activation process, respectively. Within 120 min, the mineralization of APAP was about 7.5% and 5.0% (initial APAP of 10 ppm and [PMS]0 of 0.2 mM) in Fe3O4-PMS and Fe2+-PMS system, while the mineralization could be greatly increased to about 31% and 40% as [PMS]0 increased to 2.0 mM in in Fe3O4-PMS and Fe2+-PMS system, respectively. At last, the production of reactive radical species were validated directly from Electron Paramagnetic Resonance (ESR) tests with 0.1 M 5,5-Dimethyl-1-pyrrolidine N-oxide (DMPO). Plausible mechanisms on the radical generation from Fe3O4 and Fe2+ activation of PMS are proposed on the results of radial identification tests. The results demonstrated that Fe3O4 MNPs activated PMS and Fe2+ anion activated PMS systems are promising technologies for water pollution caused by contaminants such as pharmaceutical. Fe3O4-PMS system is more suitable for slowly remediation, while Fe2+-PMS system is more suitable for fast remediation.

Keywords: acetaminophen, peroxymonosulfate, radicals, Electron Paramagnetic Resonance (ESR)

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Authors: Sherif Ismail

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Degradation of phenol-contaminated wastewater using Photocatalytic oxidation process was investigated in batch experiments using Fe doped TiO₂. Moreover, the effect of oxygen aeration on the performance of photocatalytic oxidation process by iron (Fe⁺²) doped titanium dioxide (TiO₂) was assessed. Photocatalytic oxidation using Fe doped TiO₂ effectively reduce the phenol concentration in wastewater with optimum condition of light intensity, pH, catalyst-dosing and initial concentration of phenol were 50 W/m2, 5.3, 600 mg/l and 10 mg/l respectively. The results obtained that removal efficiency of phenol was 88% after 180 min in case of N₂ addition. However, aeration by oxygen resulted in a 99% removal efficiency in 120 min. The results of photo-catalysis oxidation experiments fitted the pseudo-first-order kinetic equation with high correlation. Costs estimation of 30 m3/d full-scale photo-catalysis oxidation plant was assessed.

Keywords: phenol degradation, Fe-doped TiO2, AOPs, cost analysis

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Authors: Xiping Guo, Jing Li

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The microstructure of an Si-Al-Y co-deposition coating prepared on an Nb-Si based ultra high temperature alloy by pack cementation process at 1250°C for eight hours was studied. The results showed that the coating was composed of a (Nb,X)Si₂ (X represents Ti, Cr and Hf elements) outer layer, a (Ti,Nb)₅Si₄ middle layer and an Al, Cr-rich inner layer. For comparison, the oxidation behaviors of the coating at 800, 1050 and 1350°C were investigated respectively. Linear oxidation kinetics was found with the parabolic rate constants of 5.29×10⁻², 9×10⁻²and 5.81 mg² cm⁻⁴ h⁻¹, respectively. Catastrophic pesting oxidation has not been found at 800°C even for 100 h. The surface of the scale was covered by compact glassy SiO₂ film. The coating was able to effectively protect the Nb-Si based alloy from oxidation at 1350°C for at least 100 h. The formation process of the scale was testified following an epitaxial growth mechanism. The mechanism responsible for the oxidation behavior of the Si-Al-Y co-deposition coating at 800, 1050 and 1350°C was proposed.

Keywords: Nb-Si based ultra high temperature alloy, oxidation resistance, pack cementation, silicide coating, Al and Y modified

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Vasko Idakiev, Tatyana Tabakova, Krasimir Ivanov

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Formaldehyde production by selective oxidation of methanol is an important industrial process. The main by-products in the waste gas are CO and dimethyl ether (DME). The idea of this study is to combine the advantages of both Cu-Mn and Cu-Co catalytic systems by obtaining a new mixed Cu-Mn-Co catalyst with high activity and selectivity at the simultaneous oxidation of CO, methanol, and DME. Two basic Cu-Mn samples with high activity were selected for further investigation: (i) manganese-rich Cu-Mn/γ–Al2O3 catalyst with Cu/Mn molar ratio 1:5 and (ii) copper-rich Cu-Mn/γ-Al2O3 catalyst with Cu/Mn molar ratio 2:1. Manganese in these samples was replaced by cobalt in the whole concentration region, and catalytic properties were determined. The results show a general trend of decreasing the activity toward DME oxidation and increasing the activity toward CO and methanol oxidation with the increase of cobalt up to 60% for both groups of catalyst. This general trend, however, contains specific features, depending on the composition of the catalyst and the nature of the oxidized gas. The catalytic activity of the sample with Cu/(Mn+Co) molar ratio of 2:1 is gradually changed with increasing the cobalt content. The activity of the sample with Cu/(Mn+Co) molar ratio of 1: 5 passes through a maximum at 60% manganese replacement by cobalt, probably due to the formation of highly dispersed Co-based spinel structures (Co3O4 and/or MnCo2O4). In conclusion, the present study demonstrates that the Cu-Mn-Co/γ–alumina supported catalysts have enhanced activity toward CO, methanol and DME oxidation. Cu/(Mn+Co) molar ratio 1:5 and Co/Mn molar ratio 1.5 in the active component can ensure successful oxidation of CO, CH3OH and DME. The active component of the mixed Cu-Mn-Co/γ–alumina catalysts consists of at least six compounds - CuO, Co3O4, MnO2, Cu1.5Mn1.5O4, MnCo2O4 and CuCo2O4, depending on the Cu/Mn/Co molar ratio. Chemical composition strongly influences catalytic properties, this effect being quite variable with regards to the different processes.

Keywords: Cu-Mn-Co catalysts, oxidation, carbon oxide, VOCs

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Authors: Yosra M. Badiei, Evelyn Ortiz, Marisa Portenti, David Szalda

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Water-oxidation half-reaction is a critical reaction that can be driven by a sustainable energy source (e.g., solar or wind) and be coupled with a chemical fuel making reaction which stores the released electrons and protons from water (e.g., H₂ or methanol). The use of molecular water-oxidation catalysts (WOC) allow the rationale design of redox active metal centers and provides a better understanding of their structure-activity-relationship. Herein, the structure of a Ru(III) complex bearing a doubly deprotonated N,N'-bis(aryl)pyridine-2,6-dicarboxamide ligand which contains a water molecule in its primary coordination sphere was elucidated by single-crystal X-ray diffraction. Further spectroscopic experimental data and pH-dependent electrochemical studies reveal its water-oxidation reactivity. Emphasis on mechanistic details for O₂ formation of this complex will be addressed.

Keywords: water-oxidation, catalysis, ruthenium, artificial photosynthesis

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Authors: Rayenne Djemil

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The mechanism of oxidation reaction of linoleic acid C18: 2 (9 cis12) by singlet oxygen 1O2 were theoretically investigated via using quantum chemical methods. We explored the four reaction pathways at PM3, Hartree-Fock HF and, B3LYP functional associated with the base 6-31G (d) level. The results are in favor of the first and the last reaction ways. The transition states were found by QST3 method. Thus the pathways between the transition state structures and their corresponding minima have been identified by the IRC calculations. The thermodynamic study showed that the four ways of oxidation of linoleic acid are spontaneous, exothermic and, the enthalpy values confirm that conjugate hydroperoxydes are the most favorable products.

Keywords: echanism, quantum mechanics, oxidation, linoleic acid H

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Authors: Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Petya Cv. Petrova, Georgi V. Avdeev, Diana D. Nihtianova, Krasimir I. Ivanov, Tatyana T. Tabakova

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Recently, copper and manganese-containing systems are recognized as active and selective catalysts in many oxidation reactions. The main idea of this study is to obtain more information about γ-Al₂O₃ supported Cu-La catalysts and to evaluate their activity to simultaneous oxidation of CO, CH₃OH and dimethyl ether (DME). The catalysts were synthesized by impregnation of support with a mixed aqueous solution of nitrates of copper, manganese and lanthanum under different conditions. XRD, HRTEM/EDS, TPR and thermal analysis were performed to investigate catalysts’ bulk and surface properties. The texture characteristics were determined by Quantachrome Instruments NOVA 1200e specific surface area and pore analyzer. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor in a wide temperature range. On the basis of XRD analysis and HRTEM/EDS, it was concluded that the active component of the mixed Cu-Mn-La/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio and consisted of at least four compounds – CuO, La₂O₃, MnO₂ and Cu_1.5Mn_1.5O₄. A homogeneous distribution of the active component on the carrier surface was found. The chemical composition strongly influenced catalytic properties. This influence was quite variable with regards to the different processes.

Keywords: Cu-Mn-La oxide catalysts, carbon oxide, VOCs, deep oxidation

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Authors: Ana M. T. Mata, Alexiane Ligneul

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Textile effluents are usually heavily loaded with organic carbon and color compounds, the latter being azo dyes in an estimated 70% of the case effluent posing a major challenge in environmental protection. In this study, the ecotoxicity of simulated textile effluent after biological treatment with anaerobic and aerobic phase (aerobic granular sludge, AGS) and after advanced oxidation processes (AOP) namely ozonation and UV irradiation as post-treatment, were tested to evaluate the fitness of this treatments for ecotoxicity abatement. AGS treatment achieved an 80% removal in both COD and color. AOP was applied with the intention to mineralize the metabolites resulting from biodecolorization of the azo dye Acid Red 14, especially the stable aromatic amine (4-amino-1-naphthalenesulfonic acid, 4A1NS). The ecotoxicity evaluation was based on growth inhibition of the algae Pseudokirchneriella subcapitata following OECD TG 201 except regarding the medium, MBL medium was used instead. Five replicate control cultures and samples were performed with an average STD of 2.7% regarding specific algae growth rate determination. It was found that untreated textile effluent holds an inhibition of specific growth rate of 82%. AGS treatment by itself is able to lower ecotoxicity to 53%. This is probably due to the high color removal of the treatment. AOP post-treatment with Ozone and UV irradiation improves the ecotoxicity abatment to 49 and 43% inhibition respectively, less significantly than previously thought. Since over 85% of 4A1NS was removed by either of the AOP (followed by HPLC), an individual ecotoxicity test of 4A1NS was performed showing that 4A1NS does not inhibit algae growth (0% inhibition). It was concluded that AGS treatment is able by itself to achieve a significant ecotoxicity abatement of textile effluent. The cost-benefit of AOP as a post-treatment have to be better accessed since their application resulted in an improvement of only 10% regarding ecotoxicity effluent removal. It was also found that the 4A1NS amine had no apparent effect on ecotoxicity. Further studies will be conducted to study where ecotoxicity is coming from after AGS biological treatment and how to eliminate it.

Keywords: textile wastewate, ecotoxicity, aerobic granular sludge, AOP

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Authors: Ali Gharib, Leila Vojdanifard, Nader Noroozi Pesyan, Mina Roshani

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We describe an efficient method for oxidation of alcohols to related aldehydes and ketones by hydrogen peroxide as oxidizing agent, under reflux conditions. Nano-graphene oxide (NGO) as a heterogeneous catalyst was used and had their activity compared with other various catalysts. This catalyst was found to be an excellent catalyst for oxidation of alcohols. The effects of various parameters, including catalyst type, nature of the substituent in the alcohols and temperature, on the yield of the carboxylic acids were studied. Nano-graphene oxide was synthesized by the oxidation of graphite powders. This nanocatalyst was found to be highly efficient in this reaction and products were obtained in good to excellent yields. The recovered nano-catalyst was successfully reused for several runs without significant loss in its catalytic activity.

Keywords: nano-graphene oxide, oxidation, aldehyde, ketone, catalyst

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Authors: Mairaj Ahmad, L. Paglia, F. Marra, V. Genova, G. Pulci

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This study employed Rene N4 and FSX 414 superalloys, which are used in numerous turbine engine components due of their high strength, outstanding fatigue, creep, thermal, and corrosion-resistant properties. An in-depth examination of corrosion mechanisms with vapor present at high temperature is necessary given the industrial trend toward introducing increasing amounts of hydrogen into combustion chambers in order to boost power generation and minimize pollution in contrast to conventional fuels. These superalloys were oxidized in recent tests for 500, 1000, 2000, 3000 and 4000 hours at 982±5°C temperatures with a steady airflow at a flow rate of 10L/min and 1.5 bar pressure. These superalloys were also examined for wet corrosion for 500, 1000, 2000, 3000, and 4000 hours in a combination of air and water vapor flowing at a 10L/min rate. Weight gain, X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray spectroscopy (EDS) were used to assess the oxidation and heat corrosion resistance capabilities of these alloys before and after 500, 1000, and 2000 hours. The oxidation/corrosion processes that accompany the formation of these oxide scales are shown in the graph of mass gain vs time. In both dry and wet oxidation, oxides like Al2O3, TiO2, NiCo2O4, Ni3Al, Ni3Ti, Cr2O3, MnCr2O4, CoCr2O4, and certain volatile compounds notably CrO2(OH)2, Cr(OH)3, Fe(OH)2, and Si(OH)4 are formed.

Keywords: hot corrosion, oxidation, turbine materials, high temperature corrosion, super alloys

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Authors: Seong-Ho Ha, Young-Ok Yoon, Shae K. Kim

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Oxide layer of normal Al-Mg alloy can be characterized by upper MgO and lower MgAl2O4 spinel. The formation of the MgO outmost layer occurs by the surface segregation of Mg in the initial oxidation. After then, the oxidation is proceeded with the formation of MgA12O4 spinel beneath the MgO. Growth of the oxide layer is accelerated by constant formation of MgA12O4 spinel. On the other hand, the oxidation resistance of Al-Mg alloys can be significantly improved simply by Mg+Al2Ca master alloy use as the Mg alloying element and such an improvement is attributed to the CaO/MgO mixed layer. Al-Mg alloy containing Al2Ca shows CaO as the upper layer and MgO as the lower one without MgA12O4 spinel. Such a dense oxide film acts as a protective layer. However, the CaO/MgO scale has the outmost MgO, partly, after a long time exposure to a harsh oxidation condition. The aim of this study is to investigate the inter-filling behaviour of CaO and MgO mixed layer in oxidation resistance mechanism of Al-Mg alloys containing Al2Ca. The process of outmost MgO layer formation will be clarified.

Keywords: Al-Mg alloy, Al2Ca, oxidation, MgO

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Authors: O. Çomaklı, M. Yazıcı, T. Yetim, A. F. Yetim, A. Çelik

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In this work, TiO₂ films were deposited on Cp-Ti substrates by thermal oxidation, DC plasma oxidation, and by the sol-gel method. Microstructures of uncoated and TiO₂ film coated samples were examined by X-ray diffraction and SEM. Thin oxide film consisting of anatase (A) and rutile (R) TiO₂ structures was observed on the surface of CP-Ti by under three different treatments. Also, the more intense anatase and rutile peaks appeared at samples plasma oxidized at 700˚C. The thicknesses of films were about 1.8 μm at the TiO₂ film coated samples by sol-gel and about 2.7 μm at thermal oxidated samples, while it was measured as 3.9 μm at the plasma oxidated samples. Electrochemical corrosion behaviour of uncoated and coated specimens was mainly carried out by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in simulated body fluid (SBF) solution. Results showed that at the plasma oxidated samples exhibited a better resistance property to corrosion than that of other treatments.

Keywords: TiO₂, CP-Ti, corrosion properties, thermal oxidation, plasma oxidation, sol-gel

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Authors: Meriem Abid, Erika Oliveria-Jardim, Andres Fullana, Joaquin Silvestre-Albero

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The rapid industrial development associated with the increase of volatile organic compounds (VOCs) has seriously impacted the environment. Among VOCs, hydrogen sulfide (H₂S) is known as a highly toxic, malodorous, flammable, and corrosive gas, which is emitted from diverse chemical processes, including industrial waste-gas streams, natural gas processing, and biogas purification. The high toxicity, corrosively, and very characteristic odor threshold of H2S call for urgent development of efficient desulfurization processes from the viewpoint of environmental protection and resource regeneration. In order to reduce H₂S emissions, effective technologies for have been performed. The general method of H₂S removal included amine aqueous solution, adsorption process, biological methods, and fixed-bed solid catalytic oxidation processes. Ecologically and economically, low-temperature direct oxidation of H₂S to elemental sulfur using catalytic oxidation is the preferred approach for removing H₂S-containing gas streams. A large number of catalysts made from carbon, metal oxides, clay, and others, have been studied extensively for this application. In this sense, activated carbon (AC) is an attractive catalyst for H₂S removal because it features a high specific surface area, diverse functional groups, low cost, durability, and high efficiency. It is interesting to stand out that AC is modified using metal oxides to promote the efficiency of H₂S removal and to enhance the catalytic performance. Based on these premises, the main goal of the present study is the evaluation of the H₂S adsorption performance in carbon-encapsulated iron nanoparticles obtained from an olive mill, thermally treated at 600, 800 and 1000 ºC temperatures under anaerobic conditions. These results anticipate that carbon-encapsulated iron nanoparticles exhibit a promising performance for the H₂S removal up to 360 mg/g.

Keywords: H₂S removal, catalytic oxidation, carbon encapsulated iron, olive mill wastewater

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Authors: Natalina, Hwai Chyuan Onga, W. T. Chonga

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Oxidation stability of biodiesel is very important in fuel handling especially for remote location of biodiesel application. Variety of feedstocks and biodiesel production process resulted many variation of biodiesel oxidation stability. The current study relates to investigation of the impact of fatty acid composition that caused by natural and production process of calophyllum inophyllum palm oil methyl ester that correlated with improvement of biodiesel oxidation stability. Firstly, biodiesel was produced from crude oil of palm oil, calophyllum inophyllum and mixing of calophyllum inophyllum and palm oil. The production process of calophyllum inophyllum palm oil methyl ester (CIPOME) was divided by including washing process and without washing. Secondly, the oxidation stability was measured from the palm oil methyl ester (POME), calophyllum inophyllum methyl ester (CIME), CIPOME with washing process and CIPOME without washing process. Then, in order to find the differences of fatty acid compositions all of the biodiesels were measured by gas chromatography analysis. It was found that mixing calophyllum inophyllum into palm oil increased the oxidation stability. Washing process influenced the CIPOME fatty acid composition, and reduction of washing process during the production process gave significant oxidation stability number of CIPOME (38 h to 114 h).

Keywords: biodiesel, oxidation stability, calophyllum inophyllum, water content

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Authors: Abhishek Kumar, Mohamed Awadein, Georg Gramse, Luyang Song, He Sun, Wolfgang Schofberger, Stefan Müllegger

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Electron transfer is a crucial part of chemical reactions which drive everyday processes. With the help of an electro-chemical radio frequency scanning tunneling microscopy (EC-RF-STM) setup, we are observing single electron mediated oxidation-reduction processes in molecules like ferrocene and transition metal corroles. Combining the techniques of scanning microwave microscopy and cyclic voltammetry allows us to monitor such processes with attoampere sensitivity. A systematic study of such phenomena would be critical to understanding the nano-scale behavior of catalysts, molecular sensors, and batteries relevant to the development of novel material and energy applications.

Keywords: radiofrequency, STM, cyclic voltammetry, ferrocene

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Authors: Lifar M. S., Tereshchenko A. A., Bulgakov A. N., Guda S. A., Guda A. A., Soldatov A. V.

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Metal nanoparticles are widely used as heterogeneous catalysts to activate adsorbed molecules and reduce the energy barrier of the reaction. Reaction product yield depends on the interplay between elementary processes - adsorption, activation, reaction, and desorption. These processes, in turn, depend on the inlet feed concentrations, temperature, and pressure. At stationary conditions, the active surface sites may be poisoned by reaction byproducts or blocked by thermodynamically adsorbed gaseous reagents. Thus, the yield of reaction products can significantly drop. On the contrary, the dynamic control accounts for the changes in the surface properties and adjusts reaction parameters accordingly. Therefore dynamic control may be more efficient than stationary control. In this work, a reinforcement learning algorithm has been applied to control the simulation of CO oxidation on a catalyst. The policy gradient algorithm is learned to maximize the CO₂ production rate based on the CO and O₂ flows at a given time step. Nonstationary solutions were found for the regime with surface deactivation. The maximal product yield was achieved for periodic variations of the gas flows, ensuring a balance between available adsorption sites and the concentration of activated intermediates. This methodology opens a perspective for the optimization of catalytic reactions under nonstationary conditions.

Keywords: artificial intelligence, catalyst, co oxidation, reinforcement learning, dynamic control

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Authors: Sneha Samal, Iva Petrikova, Bohdana Marvalova

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Influence of grain size, shape and grain boundary diffusion at high temperature oxidation of pure metal is investigated as the function of microstructure evolution in this article. The oxidized scale depends on the geometrical parameter of the metal-scale system and grain shape, size, diffusion through boundary layers and influence of the contamination. The creation of the inner layer and the morphological structure develops from the internal stress generated during the growth of the scale. The oxidation rate depends on the cation and anion mobile transport of the metal in the inward and outward direction of the diffusion layer. Oxidation rate decreases with decreasing the grain size of the pure metal, whereas zinc deviates from this principle. A strong correlation between the surface roughness evolution, grain size, crystalline properties and oxidation mechanism of the oxidized metal was established.

Keywords: high temperature oxidation, pure metals, grain size, shape and grain boundary

Procedia PDF Downloads 465