Search results for: advanced oxidation potential

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: Yu-Jen Shih, Juan-Zhang Lou

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Nitrogenous compounds, such as NH4+/NH3 and NO3-, have become important contaminants in water resources. Excessive concentration of NH3 leads to eutrophication, which poses a threat to aquatic organisms in the environment. Electrochemical oxidation emerged as a promising water treatment technology, offering advantages such as simplicity, small-scale operation, and minimal reliance on additional chemicals. In this study, a nickel-based metal-organic framework (Ni-MOF) was synthesized using 2-amino terephthalic acid (BDC-NH2) and nickel nitrate. The Ni-MOF was further carbonized as derived nickel oxide and nitrogen-carbon composite, Ni/NiOx/NC. The nickel oxide within the 2D porous carbon texture served as active sites for ammonia oxidation. Results of characterization showed that the Ni-MOF was a hexagonal and flaky nanoparticle. With increasing carbonization temperature, the nickel ions in the organic framework re-crystallized as NiO clusters on the surfaces of the 2D carbon. The electrochemical surface area of Ni/NiOx/NC significantly increased as to improve the efficiency of ammonia oxidation. The phase transition of Ni(OH)2⇌NiOOH at around +0.8 V was the primary mediator of electron transfer. Batch electrolysis was conducted under constant current and constant potential modes. The electrolysis parameters included pyrolysis temperatures, pH, current density, initial feed concentration, and electrode potential. The constant current batch experiments indicated that via carbonization at 800 °C, Ni/NiOx/NC(800) was able to decrease the ammonium nitrogen of 50 mg-N/L to below 1 ppm within 4 hours at a current density of 3 mA/cm2 and pH 11 with negligible oxygenated nitrogen formation. The constant potential experiments confirmed that N2 nitrogen selectivity was enhanced up to 90% at +0.8 V.

Keywords: electrochemical oxidation, nickel oxyhydroxide, metal-organic framework, ammonium, nitrate

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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: 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: A. R. Abdul Syukor, A. W. Zularisam, Z. Ideris, M. S. Mohd Ismid, H. M. Nakmal, S. Sulaiman, A. H. Hasmanie, M. R. Siti Norsita, M. Nasrullah

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In this study, the effectiveness of integrated aquatic plants in phytogreen zone was studied and statistical analysis for the promotional integrated phytogreen system approached was discussed. It was found that the effectiveness of using aquatic plant such as Typha angustifolia sp., Lepironia articulata sp., Limnocharis flava sp., Monochoria vaginalis sp., Pistia stratiotes sp., and Eichhornia crassipes sp. in the conventional oxidation pond process in order to comply the standard A according to Malaysia Environmental Quality Act 1974 (Act 127); Environmental Quality (Sewage) Regulation 2009 for effluent discharge into inland water near the residential area was successfully shown. It was concluded that the integrated phytogreen system developed in this study has great potential for refurbishment wastewater in conventional oxidation pond.

Keywords: phytoremediation, integrated phytogreen system, sewage treatment plant, oxidation pond, aquatic plants

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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: Yalçın Kılıç, İbrahim Kani

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In recent years, interest in the synthesis of coordination compounds has greatly increased due to various application areas (such as catalysis, gas storage, luminescence). Dicarboxylic acids are often used in the synthesis of metal complexes. Bis-thiosalicylate derivative ligands contribute to the synthesis of structures of crystal engineering interest, as they can have both rigid and flexible properties. In addition, these ligands have great potential in terms of catalytic applications with the sulfur and oxygen donor atoms in their structures. In this study, we synthesized a Cu(II) complex [Cu(tsaxyl)(phen)2]•CH3OH (where tsaxyl = 2,2'-(1,2-phylenebis(methylene))bis(sulfanedyl)dibenzoate, phen = 1,10-phenantroline) and characterized through X-ray crystallography. The catalytic activities of Cu(II) complex on oxidation of ethylbenzene, cyclohexane, diphenylmethane, p-xylene were performed in acetonitrile with t-BuOOH as the source of oxygen.

Keywords: complex, crystallography, catalysis, oxidation

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Authors: Abayneh Getachew Demesa

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Interest in renewable feedstock for the chemical industry has increased considerably over the last decades, mainly due to environmental concerns and foreseeable shortage of fossil raw materials. Lignocellulosic biomass is an abundant source of bio-based raw material that is readily available and can be utilized as an alternative source for chemical production. Lignin accrues in enormous amounts as a by-product of the pulping process in the pulp and paper industry. It is estimated that 70 million tons of lignin are annually processed worldwide from the pulp and paper industry alone. Despite its attractive chemical composition, lignin is still insufficiently exploited and mainly regarded as bio-waste. Therefore, an environmentally benign process that can completely and competitively convert lignin into different value-added chemicals is needed to launch its commercial success on industrial scale. Partial wet oxidation by molecular oxygen has received increased attention as a potential process for production of chemicals from biomass wastes. In this paper, the production of chemicals by oxidation of lignin is investigated. The factors influencing the different types of products formed during the oxidation of lignin and their yields and compositions are discussed.

Keywords: biomass, lignin, waste, chemicals

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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: Ivan P. Pozdnyakov, Alexey A. Melnikov, Nikolai V. Tkachenko

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Photochemical reactions with participation of iron (III) carboxylates are important for environmental photochemistry and have a great potential of application in water purification (Advanced Oxidation Processes, photo-Fenton and Fenton-like processes). In spite of this information about excited states and primary intermediates in photochemistry of Fe(III) complexes with carboxylic acids is scarce. This talk presents and discusses the results of several recent authors' publications in a field of ultra fast spectroscopy of natural Fe(III) carboxylates.

Keywords: carboxylates, iron complexes, photochemistry, radical complexes, ultrafast processes

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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: Stefan Andersson, Balram Panjwani, Bernd Wittgens, Jan Erik Olsen

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Polycyclic Aromatic hydrocarbons are organic compounds consisting of only hydrogen and carbon aromatic rings. PAH are neutral, non-polar molecules that are produced due to incomplete combustion of organic matter. These compounds are carcinogenic and interact with biological nucleophiles to inhibit the normal metabolic functions of the cells. Norways, the most important sources of PAH pollution is considered to be aluminum plants, the metallurgical industry, offshore oil activity, transport, and wood burning. Stricter governmental regulations regarding emissions to the outer and internal environment combined with increased awareness of the potential health effects have motivated Norwegian metal industries to increase their efforts to reduce emissions considerably. One of the objective of the ongoing industry and Norwegian research council supported "SCORE" project is to reduce potential PAH emissions from an off gas stream of a ferroalloy furnace through controlled combustion. In a dedicated combustion chamber. The sizing and configuration of the combustion chamber depends on the combined properties of the bulk gas stream and the properties of the PAH itself. In order to achieve efficient and complete combustion the residence time and minimum temperature need to be optimized. For this design approach reliable kinetic data of the individual PAH-species and/or groups thereof are necessary. However, kinetic data on the combustion of PAH are difficult to obtain and there is only a limited number of studies. The paper presents an evaluation of the kinetic data for some of the PAH obtained from literature. In the present study, the oxidation is modelled for pure PAH and also for PAH mixed with process gas. Using a perfectly stirred reactor modelling approach the oxidation is modelled including advanced reaction kinetics to study influence of residence time and temperature on the conversion of PAH to CO2 and water. A Chemical Reactor Network (CRN) approach is developed to understand the oxidation of PAH inside the combustion chamber. Chemical reactor network modeling has been found to be a valuable tool in the evaluation of oxidation behavior of PAH under various conditions.

Keywords: PAH, PSR, energy recovery, ferro alloy furnace

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Authors: Nabi Ullah

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The energy crisis of the current society has attracted research attention for alternative energy sources. Methanol oxidation is the source of energy but needs efficient electrocatalysts like Pt. However, their practical ability is hindered due to cost and poisoning effects. In this regard, an efficient catalyst is required for methanol oxidation. Herein, high temperature, pressure, and diethylenetryamine (DETA) as reaction medium/structure directing agent during the solvothermal method are used for nanobelt Cu₃Se₂/Cu₁.₈Se (mostly hexagonal appearance) formation. The electrocatalyst shows optimized methanol electrooxidation reaction (MOR) response in 1 M KOH and 0.5 M methanol at a scan rate of 50 mV/s and delivers a current density of 7.12 mA/mg at a potential of 0.65 V (vs Ag/AgCl). The catalyst exhibits high electrochemical active surface area (ECSA) (0.088 mF/cm²) and low Rct with good stability for 3600 s, which favors its high MOR performance. This high response is due to its 2D hexagonal nanobelt morphology, which provides a large surface area for reaction. The space among nanobelts reduces diffusion kinetics, and the rough/irregular edge increases the reaction site to improve the methanol oxidation reaction overall.

Keywords: energy application, electrocatalysis, MOR, nanobelt

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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: 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: 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: 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

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Authors: A. Kistaubayeva, I. Savitskaya, D. Ibrayeva, M. Abdulzhanova, N. Voronova

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36 strains of sulfur-oxidizing bacteria were isolated in Southern Kazakhstan soda-saline soils and identified. Screening of strains according bio-oxidation (destruction thiosulfate to sulfate) and enzymatic (Thiosulfate dehydrogenises and thiosulfate reductase) activity was conducted. There were selected modes of aeration and culture conditions (pH, temperature), which provide optimum harvest cells. These strains can be used in bio-melioration technology.

Keywords: elemental sulfur, oxidation activity, Тhiobacilli, fertilizers, heterotrophic S-oxidizers

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Authors: Supriyono, Sumardiyono, Rendy J. Pramono

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Biodiesel is one of the alternative fuels promising for substituting petrodiesel as energy source which has an advantage as it is sustainable and eco-friendly. Due to the raw material that tends to decompose during storage, biodiesel also has the same characteristic that tends to decompose during storage. Biodiesel decomposition will form higher acid value as the result of oxidation to double bond on a fatty acid compound on biodiesel. Thus, free fatty acid value could be used to evaluate degradation of biodiesel due to the oxidation process. High free fatty acid on biodiesel could impact on the engine performance. Decomposition of biodiesel due to oxidation reaction could prevent by introducing a small amount of antioxidant. The origin of raw materials and the process for producing biodiesel will determine the effectiveness of antioxidant. Biodiesel made from high free fatty acid (FFA) crude palm oil (CPO) by using two steps esterification is vulnerable to oxidation process which is resulted in increasing on the FFA value. Tocopherol also known as vitamin E is one of the antioxidant that could improve the stability of biodiesel due to decomposition by the oxidation process. Tocopherol 0.5% concentration on palm oil biodiesel could reduce 13% of increasing FFA under temperature 80 °C and exposing time 180 minute.

Keywords: antioxidant, palm oil biodiesel, decomposition, oxidation, tocopherol

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Authors: Minoo Tavakoli, Alireza Kiani Rashid, Abbas Afrasiabi

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An aluminum coating deposited on mild steel substrate by electric arc spray and diffused to the base steel material by diffusion treatment at 800 and 900°C for 1 and 3 hours in a static air. Alloy layers formed by diffusion at both temperatures were investigated, and their features were compared with those of pack cementation aluminized steel. High-temperature oxidation tests were carried out in air at 600 °C for 145 hours. Results indicated that the aluminide coatings obtained from this process have significantly improved the high-temperature oxidation resistance in both methods due to the Al2O3 scale formation. Furthermore, it showed that the isothermal oxidation resistance of arc spray technique is better than pack cementation method. This can be attributed to voids that formed at the intermetallic layer /Al layer interface which is increased in the pack cementation method.

Keywords: electric arc spray, pack cementation, oxidation resistance, aluminized steel

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Authors: Afrouz Yousefi, Mohtada Sadrzadeh

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The widespread presence of poly- and perfluoroalkyl substances (PFAS) poses a significant concern due to their ability to accumulate in living organisms and their persistence in the environment, thanks to their robust carbon-fluorine (C-F) bonds, which require substantial energy to break (485 kJ/mol). The prevalence of toxic PFAS compounds can be highly detrimental to ecosystems, wildlife, and human health. Ongoing efforts are dedicated to investigating methods for fully breaking down and eliminating PFAS from the environment. Among the various techniques employed, advanced oxidation processes have shown promise in completely breaking down emerging contaminants in wastewater. However, the drawback lies in the relatively slow reaction rates of these processes and the substantial energy input required, which currently impedes their widespread commercial adoption. We developed a hybrid process, comprising electro-Fenton as an advanced oxidation process and membrane distillation, to simultaneously degrade organic PFAS pollutants and extract pure water from the mixture. In this study, environmentally persistent perfluorooctanoic acid (PFOA), as an emerging contaminant, was used to study the effectiveness of the electro-Fenton/membrane distillation hybrid system. The PFOA degradation studies were conducted in two modes: electro-Fenton and electro-Fenton coupled with membrane distillation. High-performance liquid chromatography with ultraviolet detection (HPLC-UV), ion-chromatography (measuring fluoride ion concentration), total organic carbon (TOC) decay, mineralization current efficiency (MCE), and specific energy consumption (SEC) were evaluated for a single EF and hybrid EF-MD processes. In contrast to a single EF reaction, TOC decay improved significantly in the EF-MD process. Overall, the MCE of hybrid processes surpassed 100% while it remained under 50% for a single EF reaction. Calculations of specific energy consumption (SEC) demonstrated a substantial decrease of nearly one-third in energy usage when integrating the EF reaction with the MD process.

Keywords: water treatment, PFAS, membrane distillation, electro-Fenton, advanced oxidation

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Authors: Alan N. A. Heberle, Salatiel W. Da Silva, Valentin Perez-Herranz, Andrea M. Bernardes

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Contaminants of emerging concern are substances widely used, such as pharmaceutical products. These compounds represent risk for both wild and human life since they are not completely removed from wastewater by conventional wastewater treatment plants. In the environment, they can be harm even in low concentration (µ or ng/L), causing bacterial resistance, endocrine disruption, cancer, among other harmful effects. One of the most common taken medicine to treat cardiocirculatory diseases is the Atenolol (ATL), a β-Blocker, which is toxic to aquatic life. In this way, it is necessary to implement a methodology, which is capable to promote the degradation of the ATL, to avoid the environmental detriment. A very promising technology is the advanced electrochemical oxidation (AEO), which mechanisms are based on the electrogeneration of reactive radicals (mediated oxidation) and/or on the direct substance discharge by electron transfer from contaminant to electrode surface (direct oxidation). The hydroxyl (HO•) and sulfate (SO₄•⁻) radicals can be generated, depending on the reactional medium. Besides that, at some condition, the peroxydisulfate (S₂O₈²⁻) ion is also generated from the SO₄• reaction in pairs. Both radicals, ion, and the direct contaminant discharge can break down the molecule, resulting in the degradation and/or mineralization. However, ATL molecule and byproducts can still remain in the treated solution. On this wise, some efforts can be done to implement the AEO process, being one of them the use of a cationic membrane to separate the cathodic (reduction) from the anodic (oxidation) reactor compartment. The aim of this study is investigate the influence of the implementation of a cationic membrane (Nafion®-117) to separate both cathodic and anodic, AEO reactor compartments. The studied reactor was a filter-press, with bath recirculation mode, flow 60 L/h. The anode was an Nb/BDD2500 and the cathode a stainless steel, both bidimensional, geometric surface area 100 cm². The solution feeding the anodic compartment was prepared with ATL 100 mg/L using Na₂SO₄ 4 g/L as support electrolyte. In the cathodic compartment, it was used a solution containing Na₂SO₄ 71 g/L. Between both solutions was placed the membrane. The applied currents densities (iₐₚₚ) of 5, 20 and 40 mA/cm² were studied over 240 minutes treatment time. Besides that, the ATL decay was analyzed by ultraviolet spectroscopy (UV/Vis). The mineralization was determined performing total organic carbon (TOC) in TOC-L CPH Shimadzu. In the cases without membrane, the iₐₚₚ 5, 20 and 40 mA/cm² resulted in 55, 87 and 98 % ATL degradation at the end of treatment time, respectively. However, with membrane, the degradation, for the same iₐₚₚ, was 90, 100 and 100 %, spending 240, 120, 40 min for the maximum degradation, respectively. The mineralization, without membrane, for the same studied iₐₚₚ, was 40, 55 and 72 %, respectively at 240 min, but with membrane, all tested iₐₚₚ reached 80 % of mineralization, differing only in the time spent, 240, 150 and 120 min, for the maximum mineralization, respectively. The membrane increased the ATL oxidation, probably due to avoid oxidant ions (S₂O₈²⁻) reduction on the cathode surface.

Keywords: contaminants of emerging concern, advanced electrochemical oxidation, atenolol, cationic membrane, double compartment reactor

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Authors: Mohd Salim Mahtab, Izharul Haq Farooqi, Anwar Khursheed

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Advanced oxidation processes (AOPs) based on Fenton are versatile options for treating complex wastewaters containing refractory compounds. However, the classical Fenton process (CFP) has limitations, such as high sludge production and reagent dosage, which limit its broad use and result in secondary contamination. As a result, long-term solutions are required for process intensification and the removal of these impediments. This study shows that Fenton sludge could serve as a catalyst in the Fe³⁺/Fe²⁺ reductive pathway, allowing non-regenerated sludge to be reused for complex wastewater treatment, such as landfill leachate treatment, even in the absence of Fenton's reagents. Experiments with and without pH adjustments in stages I and II demonstrated that an acidic pH is desirable. Humic compounds in leachate could improve the cycle of Fe³⁺/Fe²⁺ under optimal conditions, and the chemical oxygen demand (COD) removal efficiency was 22±2% and 62±2%% in stages I and II, respectively. Furthermore, excellent total suspended solids (TSS) removal (> 95%) and color removal (> 80%) were obtained in stage II. The processes underlying synergistic (oxidation/coagulation/adsorption) effects were addressed. The design of the experiment (DOE) is growing increasingly popular and has thus been implemented in the chemical, water, and environmental domains. The relevance of the statistical model for the desired response was validated using the explicitly stated optimal conditions. The operational factors, characteristics of reused sludge, toxicity analysis, cost calculation, and future research objectives were also discussed. Reusing non-regenerated Fenton sludge, according to the study's findings, can minimize hazardous solid toxic emissions and total treatment costs.

Keywords: advanced oxidation processes, catalysis, Fe³⁺/Fe²⁺ cycle, fenton sludge

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Authors: Abdullah Alhajoj, Bassam Alowaiesh

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This work aims to reduce the risks of discharging olive mill waste directly to the environment without treatment in Sakaka City, KSA. The organic loads expressed by chemical oxygen demand (COD) and biological oxygen demand (BOD) of the produced wastewater (OMWW) as well as the solid waste (OMW) were evaluated. The wastes emitted from the three-phase centrifuge decanters was found to be higher than that emitted from the two-phase centrifuge decanters. The olive mill wastewater (OMWW) was treated using advanced oxidation combined with filtration treatment. The results indicated that the concentration of COD, BOD, TSS, oil and grease and phenol was reduced by using complex sand filtration from 72150, 21660 10256, 36430, and 1470 mg/l to 980, 421, 58, 68, and 0.35 mg/l for three-phase OMWW and from 150562, 17955, 15325, 19658 and 2153 mg/l to 1050, 501, 29, 0.75, and 0.29 mg/l, respectively. While, by using modified trickling filter (packed with the neck of waste plastic bottles the concentration of the previously mentioned parameters was reduced to 1190, 570, 55, 0.85, and 0.3 mg/l, respectively. This work supports the application of such treatment technique for reducing the environmental threats of olive mill waste effluents in Saudi Arabia.

Keywords: two-phase, three-phase, olive mill, olive oil, waste treatment, filtration, advanced oxidation, waste plastic bottles

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Authors: Ruchi Jain, Chinnakonda S. Gopinath

Abstract:

The CO oxidation is a primary reaction in heterogeneous catalysis due to its potential to overcome the air pollution caused by various reasons. Indeed, in the study of sustainable catalysis, the role played by water is very important. The present work is focused on studying the effect of moisture on the sustainability of Co3O4 NR catalyst for CO oxidation reaction at ambient temperature. The catalytic activity, electronic structure and the mechanistic aspects of spinel Co3O4 nanorod surfaces have been explored in dry and wet atmosphere by near-ambient pressure photoelectron spectroscopic techniques (NAP-PES) with conventional x-ray (Al kα) and ultraviolet sources (He-I).Comparative NAPPES studies have been employed to understand the elucidation of the catalytic reaction pathway and the evolution of various surface species. The presence of water with CO+O2 plummet the catalytic activity due to the change in electronic nature from predominantly oxidic (without water in the feed) to few intermediates covered Co3O4 surface. However, ≥ 375 K Co3O4 surface recovers and regain oxidation activity, at least partially, even in the presence of water. Above mentioned observations are fully supported by the changes observed in the work function of Co3O4 in the presence of wet (H2O+CO+O2) compared to dry (CO+O2) conditions. Various type of surface species, such as CO(ads), carbonate, formate, are found to be on the catalyst surface depending on the reaction conditions. Under dry condition, CO couples with labile O atoms to form CO2, however under wet conditions it also interacts with surface OH groups results in the formation carbonate and formate intermediate. The carbonate acts at reaction inhibitor at room temperature, however proves as active intermediate at temperature 375 K or above. On the other hand, formate has proved to be reaction spectator due to its high stability. The intrinsic role of these species to suppress the oxidation has been demonstrated through a possible reaction mechanism under different reaction conditions.

Keywords: heterogeneous catalysis, surface chemistry, photoelectron spectroscopy, ambient oxidation

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Authors: Saba Didarataee, Abbas Ali Khodadadi, Yadollah Mortazavi, Fatemeh Mousavi

Abstract:

Photocatalytic water splitting is one of the most attractive alternative methods for hydrogen evolution. A variety of nanoparticle engineering techniques were introduced to improve the activity of semiconductor photocatalysts. Among these methods, heterojunction formation is an appealing method due to its ability to effectively preventing electron-hole recombination and improving photocatalytic activity. Reaching an optimal ratio of the two target semiconductors for the formation of heterojunctions is still an open question. Considering environmental issues as well as the cost and availability, ZnS and ZnO are frequently studied as potential choices. In this study, first, the ZnS nanoparticle was synthesized in a hydrothermal process; the formation of ZnS nanorods with a diameter of 14-30 nm was confirmed by field emission scanning electron microscope (FESEM). Then two different methods, partial oxidation and chemical precipitation were employed to construct ZnS/ZnO core-shell heterojunction. X-ray diffraction (XRD), BET, and diffuse reflectance spectroscopy (DRS) analysis were carried out to determine crystallite phase, surface area, and bandgap of photocatalysts. Furthermore, the temperature of oxidation was specified by a temperature programmed oxidation (TPO) and was fixed at 510℃, at which mild oxidation occurred. The bandgap was calculated by the Kubelka-Munk method and decreased by increasing oxide content from 3.53 (pure ZnS) to 3.18 (pure ZnO). The optimal samples were determined by testing the photocatalytic activity of hydrogen evolution in a quartz photoreactor with side irradiation of UVC lamps with a wavelength of 254 nm. In both procedures, it was observed that the photocatalytic activity of the ZnS/ZnO composite was sensibly higher than the pure ZnS and ZnO, which is attributed to forming a type-II heterostructure. The best ratio of oxide to sulfide was 0.24 and 0.37 in partial oxidation and chemical precipitation, respectively. The highest hydrogen evolution was 1081 µmol/gr.h, gained from partial oxidizing of ZnS nanoparticles at 510℃ for 30 minutes.

Keywords: heterostructure, hydrogen, partial oxidation, photocatalyst, water splitting, ZnS

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Authors: Pisut Painmanakul, Thawatchai Chintateerachai, Supanid Lertlapwasin, Nusara Rojvilavan, Tanun Chalermsinsuwan, Nattawin Chawaloesphonsiya, Onanong Larpparisudthi

Abstract:

Conventional coagulation, advance oxidation process (AOPs), and the combined process were evaluated and compared for its suitability to treat the stabilized cutting-oil wastewater. The 90% efficiency was obtained from the coagulation at Al2(SO4)3 dosage of 150 mg/L and pH 7. On the other hands, efficiencies of AOPs for 30 minutes oxidation time were 10% for acoustic oxidation, 12% for acoustic oxidation with hydrogen peroxide, 76% for Fenton, and 92% sono-Fenton processes. The highest efficiency for effective oil removal of AOPs required large amount of chemical. Therefore, AOPs were studied as a post-treatment after conventional separation process. The efficiency was considerable as the effluent COD can pass the standard required for industrial wastewater discharge with less chemical and energy consumption.

Keywords: cutting oily-wastewater, advance oxidation process, sono-fenton, combined process

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Authors: Sewon Kim, Changyeop Lee

Abstract:

A new concept of in-furnace partial oxidation combustion is successfully applied in this research. The burner is designed such that liquid fuel is prevaporized in the furnace then injected into a fuel rich combustion zone so that a partial oxidation reaction occurs. The effects of equivalence ratio, thermal load, injection distance and fuel distribution ratio on the NOx and CO are experimentally investigated. This newly developed burner showed very low NOx emission level, about 15 ppm when light oil is used as a fuel.

Keywords: burner, low NOx, liquid fuel, partial oxidation

Procedia PDF Downloads 319