Search results for: internal oxidation

Authors: I. Yordanova, H. Kolev, S. Todorova, Z. Cherkezova-Zheleva

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Catalysis plays a key role in solving many environmental problems by establishing efficient catalytic systems for environmental protection and reducing emissions of greenhouse gases from industry. Volatile organic compounds are major air pollutants. There are several ways to dispose of emissions like - adsorption, condensation, absorption, bio-filtration, thermal, catalytic, plasma and ultraviolet oxidation. The catalytic oxidation has more advantages over other methods. For example - lower energy consumption; the concentration of the organic contaminant may be low or may vary within wide limits. Catalysts for complete oxidation of VOCs can be classified into three categories: noble metal, metal oxides or supported metal oxides and mixture of noble metals and metal oxides. Most of the catalysts for the complete catalytic oxidation are based on Pt, Pd, Rh or a combination thereof. The oxides of the transition metal are one of the alternatives to noble metal catalysts for these reactions. They are less active at low temperatures, but at higher - their activity is similar. The properties of the catalyst depend on the distribution of the active phase, the medium type of the pre-treatment, the interaction between the active phase and the support and the interaction between the active phase and the reaction medium. Supported mono-component Mn and bi-component Mn-Co systems are examined in present study. The samples are prepared using co-precipitation method. SiO2 (Aerosil) is used as a support. The studied samples were precipitated by NH4OH. The synthesized samples were characterized by XRD, XPS, TPR and tested in the catalytic reaction of complete oxidation of n-hexane, propane, methanol, ethanol and propanol.

Keywords: catalytic oxidation, Co-Mn oxide, oxidation of hydrocarbons and alcohols, environmental protection

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Authors: Ghada Ben Hamad, Zohir Younsi, Fabien Salaun, Hassane Naji, Noureddine Lebaz

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The graphene oxide (GO) material has attracted much attention for solar energy applications. This paper reports the synthesis and characterization of partially oxidized graphite oxide (GTO). GTO was obtained by modified Hummers method, which is based on the chemical oxidation of natural graphite. Several samples were prepared with different oxidation degree by an adjustment of the oxidizing agent’s amount. The effect of the oxidation degree on the chemical structure and on the morphology of GTO was determined by using Fourier transform infrared (FT-IR) spectroscopy, Energy Dispersive X-ray Spectroscopy (EDS), and scanning electronic microscope (SEM). The thermal stability of GTO was evaluated by using thermogravimetric analyzer (TGA) in Nitrogen atmosphere. The results indicate high degree oxidation of graphite oxide for each sample, proving that the process is efficient. The GTO synthesized by modified Hummers method shows promising characteristics. Graphene oxide (GO) obtained by exfoliation of GTO are recognized as a good candidate for thermal energy storage, and it will be used as solid shell material in the encapsulation of phase change materials (PCM).

Keywords: modified hummers method, graphite oxide, oxidation degree, solar energy storage

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Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov

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The development of active and stable catalysts without noble metals for low temperature oxidation of exhaust gases remains a significant challenge. The purpose of this study is to determine the influence of the preparation method on the catalytic activity of the supported copper-manganese mixed oxides in terms of VOCs oxidation. The catalysts were prepared by impregnation of γ-Al2O3 with copper and manganese nitrates and acetates and the possibilities for CO, CH3OH and dimethyl ether (DME) oxidation were evaluated using continuous flow equipment with a four-channel isothermal stainless steel reactor. Effect of the support, Cu/Mn mole ratio, heat treatment of the precursor and active component loading were investigated. Highly active alumina supported Cu-Mn catalysts for CO and VOCs oxidation were synthesized. The effect of preparation conditions on the activity behavior of the catalysts was discussed. The synergetic interaction between copper and manganese species increases the activity for complete oxidation over mixed catalysts. Type of support, calcination temperature and active component loading along with catalyst composition are important factors, determining catalytic activity. Cu/Mn molar ratio of 1:5, heat treatment at 450oC and 20 % active component loading are the best compromise for production of active catalyst for simultaneous combustion of CO, CH3OH and DME.

Keywords: copper-manganese catalysts, CO, VOCs oxidation, exhaust gases

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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: 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: 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: R. Kerbachi , Y. Medkour, F. Sahnoune

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The integrated waste management is an important aspect in the implementation of sustainable development. Leachate generated by sanitary landfills is a high-strength wastewater that is likely to contain large amounts of organic and inorganic matter, with humic substances, as well as ammonia nitrogen, heavy metals, chlorinated organic and inorganic salts. Untreated leachates create a great potential for harm to the environment, they can permeate ground water or mix with surface water and contribute to the pollution of soil, ground water, and surface water. In Algeria, the treatment of landfill leachate is the weakest link in the solid waste management. This study focuses on the evaluation of the pollution load carried by leachate produced in a former sanitary landfill located to the west of Algiers and the implementation of advanced oxidation treatment (advanced oxidation process, AOP), Fenton, electro-Fenton etc. The characterization of these leachates shows that they have a high organic load, mineral and nitrogen. Measured COD reaches very high values of the order of 5000 to 20,000 mg O2 / L. On this non-biodegradable leachate, treatment tests have been carried out by the methods of coagulation-flocculation, Fenton oxidation, electrocoagulation and electro-Fenton. The removal efficiencies of pollution obtained for each of these modes of treatment are respectively 69, 80, 84 and 97%. The study shows that advanced oxidation processes are very suitable for the treatment of poorly biodegradable leachate.

Keywords: advanced oxidation processes, electrocoagulation, electro-Fenton, leachates treatment, sanitary landfill

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Authors: Amal Jmaii, Damien Rousseliere, Besma Belhadj

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We explore the relationship between internal migration and poverty in Tunisia. We present a methodology combining potential outcomes approach with multiple imputation to highlight the effect of internal migration on poverty states. We find that probability of being poor decreases when leaving the poorest regions (the west areas) to the richer regions (greater Tunis and the east regions).

Keywords: internal migration, potential outcomes approach, poverty dynamics, Tunisia

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Authors: Yuri A. Kalvachev, Totka D. Todorova

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Zeolite mordenite has been investigated as a transition metal support for the preparation of efficient catalysts in the oxidation of volatile organic compounds (VOCs). The highly crystalline mordenite samples were treated with hydrofluoric acid and ammonium fluoride to get hierarchical material with secondary porosity. The obtained supports by this method have a high active surface area, good diffusion properties and prevent the extraction of metal components during catalytic reactions. The active metal phases platinum and copper were loaded by impregnation on both mordenite materials (parent and acid treated counterparts). Monometalic Pt and Cu, and bimetallic Pt/Cu catalysts were obtained. The metal phases were fine dispersed as nanoparticles on the functional porous materials. The catalysts synthesized in this way were investigated in the reaction of complete oxidation of propane and benzene. Platinum, copper and platinum/copper were loaded and there catalytic activity was investigated and compared. All samples are characterized by X-ray diffraction analysis, nitrogen adsorption, scanning electron microscopy (SEM), X-ray photoelectron measurements (XPS) and temperature programed reduction (TPR). The catalytic activity of the samples obtained is investigated in the reaction of complete oxidation of propane and benzene by using of Gas Chromatography (GC). The oxidation of three organic molecules was investigated—methane, propane and benzene. The activity of metal loaded mordenite catalysts for methane oxidation is almost the same for parent and treated mordenite as a support. For bigger molecules as propane and benzene, the activity of catalysts based on treated mordenite is higher than those based on parent zeolite.

Keywords: metal loaded catalysts, mordenite, VOCs oxidation, zeolites

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Authors: Z. Khalifa, K. M. Hassan, M. Abdel Azzem

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Potential strategies for deriving useful forms of renewable high density energy from abundant energy stored in carbohydrates is direct conversion of glucose (GLU) to electrical power. A three novel versatile modified electrodes, synthesized by electrochemical polymerization of organic monomers on glassy carbon electrodes (GC), have been developed for biofuel cells results in stable and long-term power production. Electrocatalytic oxidation of glucose in alkaline solution on conducting polymers electrodes modified by incorporation of Ni nanoparticles (NiNPs) onto poly(1,5-aminonaphthalene) (1,5-PDAN), poly(1,8-diaminonaphthalene) (1,8-PDAN) and poly(1-amino-2-methyl-9,10-anthraquinone) (PAMAQ) was investigated. The electrocatalytic oxidation of glucose at NiNPs-modified 1,5-PDAN/GC, 1,8-PDAN/GC and PAMAQ/GC electrodes has been studied using voltammetry technique. The PDAN electrodes show a slight activity in the potential of interest. The prepared NiNPs/PAMAQ/GC catalyst showed a very interesting catalytic activity that was nicely comparable to the NiNPs/1,5-PDAN/GC, NiNPs/1,8-PDAN/GC modified electrodes. In advance, both shows a significant more catalytic activity compared to the reported data for electrodes for glucose electrocatalytic oxidation.

Keywords: biofuel cells, glucose oxidation, electrocatalysis, nanoparticles and modified electrodes

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Authors: M. J. Kim, D. B. Lee

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Centrifugal casting is a metal casting method that uses forces make by centripetal acceleration to distribute molten material in mold. Centrifugal cast parts manufactured in industry contain gas pipes and water supply lines, moreover rings, turbocharger, bushings, brake drums. Turbochargers were exposed to exhaust temperatures of 900-1050°C require a material for the corrosion resistance that will withstand such high component temperatures during the entire service life of the vehicle. Hence, the study of corrosion resistance for turbocharger is important for practical application. DIN1.4091 steels were used widely. The DIN1.4091 steels whose compositions were Fe-34.4Cr-14.5Ni-2.5Mo-0.4W-0.4Mn-0.5Si-(0.009 or 0.35)S (wt.%) were centrifugally cast, and oxidized at 900°C for 50-200 h in order to find the effect of sulfur on the high-temperature oxidation of Fe-34.4Cr-14.5Ni-2.5Mo-0.4W-0.4Mn-0.5Si-(0.009 or 0.35)S (wt.%) alloys. These alloys formed oxide scales that consisted primarily of Cr₂O₃ as the major oxide and Cr₂MnO₄ as the minor one through preferential oxidation of Cr and Mn. Cr formed a thin CrOx oxide film on the surface to prevent further oxidation, and when it is added more than 20%, the sulphide decreased corrosion rate. The high affinity of Mn with S, led to the formation of scattered MnS inclusions, particularly in the 0.35S-containing cast alloy. Sulfur was harmful to the oxidation resistance because it deteriorated the scale/alloy adherence so as to accelerate the adherence and compactness of the formed scales. Acknowledgement: This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2016R1A2B1013169).

Keywords: centrifugal casting, turbocharger, sulfur, oxidation, Fe-34.4Cr-14.5Ni alloy

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Authors: Smita Krishnan, Krittika Chandran, Chandra Mohan Sinnathambi

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Produced water and its treatment and management are growing challenges in all producing regions. This water is generally considered as a nonrevenue product, but it can have significant value in enhanced oil recovery techniques if it meets the required quality standards. There is also an interest in the beneficial uses of produced water for agricultural and industrial applications. Advanced Oxidation Process is a chemical technology that has been growing recently in the wastewater treatment industry, and it is highly recommended for non-easily removal of organic compounds. The efficiency of AOPs is compound specific, therefore, the optimization of each process should be done based on different aspects.

Keywords: advanced oxidation process, photochemical processes, degradation, organic contaminants

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Authors: Jin Lin, Shouxiang Lu, Kim Meow Liew

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In a fire accident, fire smoke often poses a serious threat to human safety especially in the enclosed space such as submarine and space-crafts environment. Efficient removal of the hazardous gas products particularly a large amount of CO and CO₂ gases from these confined space is critical for the security of the staff and necessary for the post-fire environment recovery. In this work, Cu-Mn-Ce composite oxide catalysts coupled with CO₂ sorbents were prepared using wet impregnation method, solid-state impregnation method and wet/solid-state impregnation method. The as-prepared samples were tested dynamically and isothermally for CO oxidation and CO₂ sorption and further characterized by the X-ray diffraction (XRD), nitrogen adsorption and desorption, and field emission scanning electron microscopy (FE-SEM). The results showed that all the samples were able to catalyze CO into CO₂ and capture CO₂ in situ by chemisorption. Among all the samples, the sample synthesized by the wet/solid-state impregnation method showed the highest catalytic activity toward CO oxidation and the fine ability of CO₂ sorption. The sample prepared by the solid-state impregnation method showed the second CO oxidation performance, while the coupled sample using the wet impregnation method exhibited much poor CO oxidation activity. The various CO oxidation and CO₂ sorption properties of the samples might arise from the different dispersed states of the CO₂ sorbent in the CO catalyst, owing to the different preparation methods. XRD results confirmed the high-dispersed sorbent phase in the samples prepared by the wet and solid impregnation method, while that of the sample prepared by wet/solid-state impregnation method showed the larger bulk phase as indicated by the high-intensity diffraction peaks. Nitrogen adsorption and desorption results further revealed that the latter sample had a higher surface area and pore volume, which were beneficial for the CO oxidation over the catalyst. Hence, the Cu-Mn-Ce oxide catalyst coupled with CO₂ sorbent using wet/solid-state impregnation method could be a good choice for fire smoke removal in the enclosed space.

Keywords: CO oxidation, CO₂ sorption, preparation methods, smoke removal

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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: 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: Roshan Jelal, Charles Mbohwa

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In today’s world, internal fraud remains one of the most challenging problems within companies worldwide and despite investment in controls and attention given to the problem, the instances of internal fraud has not abated. To the contrary it appears that internal fraud is on the rise especially in the wake of the economic downturn. Leadership within companies believes that the more sophisticated the controls employed the less likely it would be for employees to pilfer. This is a very antiquated view as investment in controls may not be enough to curtail internal fraud; however, ensuring that a company drives the correct culture and behaviour within the organisation is likely to yield desired results. This research aims to understand how creating a strong ethical culture and embedding the principle of good corporate governance impacts on levels of internal fraud with an organization (a South African Bank).

Keywords: internal fraud, corporate governance, ethics, reserve bank, the King Code

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Authors: Karla Lienau, Rafael Müller, René Moré, Debora Ressnig, Dan Cook, Richard Walton, Greta R. Patzke

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The increasing demand for renewable energy sources and storable fuels underscores the high potential of artificial photosynthesis. The four electron transfer process of water oxidation remains the bottleneck of water splitting, so that special emphasis is placed on the development of economic, stable and efficient water oxidation catalysts (WOCs). Our investigations introduced cobalt carbodiimide CoNCN and its transition metal analogues as WOC types, and further studies are focused on the interaction of different transition metals in the convenient all-nitrogen/carbon matrix. This provides further insights into the nature of the ‘true catalyst’ for cobalt centers in this non-oxide environment. Water oxidation activity is evaluated with complementary methods, namely photocatalytically using a Ru-dye sensitized standard setup as well as electrocatalytically, via immobilization of the WOCs on glassy carbon electrodes. To further explore the tuning potential of transition metal combinations, complementary investigations were carried out in oxidic spinel WOC matrices with more versatile host options than the carbodiimide framework. The influence of the preparative history on the WOC performance was evaluated with different synthetic methods (e.g. hydrothermally or microwave assisted). Moreover, the growth mechanism of nanoscale Co3O4-spinel as a benchmark WOC was investigated with in-situ PXRD techniques.

Keywords: carbodiimide, photocatalysis, spinels, water oxidation

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Authors: Jiazhen Liao, Xiaolan Zeng

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A series of BiOCl nanoplates with different oxygen vacancies (OVs) concentrations were successfully synthesized via a facile solvothermal method. The concentration of OVs of BiOCl can be tuned by the ratios of water/ethylene glycol. Such nanoplates containing oxygen vacancies served as an efficient visible-light-driven photocatalyst for NO oxidation. Compared with pure BiOCl, the enhanced photocatalytic performance was mainly attributed to the introduction of OVs, which greatly enhanced light absorption, promoted electron transfer, activated oxygen molecules. The present work could provide insights into the understanding of the role of OVs in photocatalysts for reference. Combined with characterization analysis, such as XRD（X-ray diffraction）, XPS（X-ray photoelectron spectroscopy), TEM（Transmission Electron Microscopy）, PL（Fluorescence Spectroscopy）, and DFT (Density Functional Theory) calculations, the effect of vacancies on photoelectrochemical properties of BiOCl photocatalysts are shown. Furthermore, the possible reaction mechanisms of photocatalytic NO oxidation were also revealed. According to the results of in situ DRIFTS （ Diffused Reflectance Infrared Fourier Transform Spectroscopy）, various intermediates were produced during different time intervals of NO photodegradation. The possible pathways are summarized below. First, visible light irradiation induces electron-hole pairs on the surface of OV-BOC (BiOCl with oxygen vacancies). Second, photogenerated electrons form superoxide radical with the contacted oxygen. Then, the NO molecules adsorbed on the surface of OV-BOC are attacked by superoxide radical and form nitrate instead of NO₂ (by-products). Oxygen vacancies greatly improve the photocatalytic oxidation activity of NO and effectively inhibit the production of harmful by-products during the oxidation of NO.

Keywords: OVs-BiOCl nanoplate, oxygen vacancies, NO oxidation, photocatalysis

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Krasimir Ivanov

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The catalytic oxidation of methanol to formaldehyde is an important industrial process in which the waste gas in addition to CO contains methanol and dimethyl ether (DME). Evaluation of the possibility of removing the harmful components from the exhaust gasses needs a more complex investigation. Our previous work indicates that supported Cu-Mn oxide catalysts are promising for effective deep oxidation of these compounds. This work relates to the catalyst, comprising copper-manganese spinel, coated on carrier γ-Al₂O₃. The effect of preparation conditions on the active component composition and activity behavior of the catalysts is discussed. Different organometallic compounds on the base of four natural amino acids (Glycine, Alanine, Valine, Leucine) as precursors were used for the preparation of catalysts with Cu/Mn molar ratio 1:5. X-Ray and TEM analysis were performed on the catalyst’s bulk, and surface composition and the specific surface area was determined by BET method. The results obtained show that the activity of the catalysts increase up to 40% although there are some specific features, depending on the nature of the amino acid and the oxidized compound.

Keywords: Cu-Mn/γ-Al₂O₃, CO and VOCs oxidation, heterogeneous catalysis, amino acids

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Authors: Jae-Ho Kim, Ryosuke Yokochi, Miho Fuzihashi, Susumu Yonezawa

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The use of silver nanoparticles in conductive inks and their printing by injecting technology has been known for years. However, the very high cost of silver limits wide industrial applications. Since copper is much cheaper but possesses a very high conductivity (only 6% less than that of Ag), Cu nanoparticles can be considered as a replacement for silver nanoparticles. However, a major problem in utilizing their copper nanoparticles is their inherent tendency to oxidize in ambient conditions. In conductive printing applications, the presence of copper oxide on the surface of nanoparticles has two negative consequences: it increases the required sintering temperature and reduces the electrical conductivity. Only a limited number of reports have attempted to address the oxidation problem, which in general is based on minimizing the exposure of the copper nanoparticles to oxygen by a protective layer composed of a second material at the surface of the particles. To form the protective layer on the surface, carbon-based materials, surfactants, metals, and so on. In this study, we tried to modify the oxide on Cu particles using fluorine gas. And the creation effects of oxyfluorides or fluorides on the oxidation resistance of Cu particles were investigated. Compared with untreated sample (a), the fluorinated samples can restrain the weight increase even at 200℃ from the TG-DTA results. It might be considered that the substantial oxyfluorides on the surface play a role in protecting metal oxidation.

Keywords: copper metal, electrical conductivity, oxidation resistance, surface fluorination

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Authors: Erica T. R. Mendonça, Caroline M. B. de Araujo, Filho, Osvaldo Chiavone, Sobrinho, Maurício A. da Motta

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Oil and gas exploration is an essential activity for modern society, although the supply of its global demand has caused enough damage to the environment, mainly due to produced water generation, which is an effluent associated with the oil and gas produced during oil extraction. It is the aim of this study to evaluate the treatment of produced water, in order to reduce its oils and greases content (OG), by using flotation as a pre-treatment, combined with oxidation for the remaining organic load degradation. Thus, there has been tested Advanced Oxidation Process (AOP) using both Fenton and photo-Fenton reactions, as well as a chemical oxidation treatment using sodium ferrate(VI), Na₂[FeO₄], as a strong oxidant. All the studies were carried out using real samples of produced water from petroleum industry. The oxidation process using ferrate(VI) ion was studied based on factorial experimental designs. The factorial design was used in order to study how the variables pH, temperature and concentration of Na₂[FeO₄] influences the O&G levels. For the treatment using ferrate(VI) ion, the results showed that the best operating point is obtained when the temperature is 28 °C, pH 3, and a 2000 mg.L^-1 solution of Na₂[FeO₄] is used. This experiment has achieved a final O&G level of 4.7 mg.L^-1, which means 94% percentage removal efficiency of oils and greases. Comparing Fenton and photo-Fenton processes, it was observed that the Fenton reaction did not provide good reduction of O&G (around 20% only). On the other hand, a degradation of approximately 80.5% of oil and grease was obtained after a period of seven hours of treatment using photo-Fenton process, which indicates that the best process combination has occurred between the flotation and the photo-Fenton reaction using solar radiation, with an overall removal efficiency of O&G of approximately 89%.

Keywords: advanced oxidation process, ferrate (VI) ion, oils and greases removal, produced water treatment

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Authors: Chupicai Manuel

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The purpose of this article is to examine the political economy and history of internal displacement, migration and human security in Zimbabwe from 1800 to present day. The article gives a timeline of major internal displacement, migration trends that took place in Zimbabwe before colonialism, through the colonial period up to the present day and examines the human security context of such periods. In view of the above, a political economy analysis will be employed to examine the different factors that promoted internal displacement and human movements from 1800 to the present day and explore the architecture of human security in Zimbabwe. The ultimate goal of this literature review is to provide a longitudinal analysis of internal displacement, migration and human security regimes that existed in Zimbabwe with the view of promoting social cohesion and nation building.

Keywords: human security, internal displacement, migration, political economy

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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: Amin Mojiri, Akiyoshi Ohashi, Tomonori Kindaichi

Abstract:

Synthetic domestic wastewater was treated via combining treatment methods, including electrochemical oxidation, adsorption, and sequencing batch reactor (SBR). In the upper part of the reactor, an anode and a cathode (Ti/RuO₂-IrO₂) were organized in parallel for the electrochemical oxidation procedure. Sodium sulfate (Na₂SO₄) with a concentration of 2.5 g/L was applied as the electrolyte. The voltage and current were fixed on 7.50 V and 0.40 A, respectively. Then, 15% working value of the reactor was filled by activated sludge, and 85% working value of the reactor was added with synthetic wastewater. Powdered cockleshell, 1.5 g/L, was added in the reactor to do ion-exchange. Response surface methodology was employed for statistical analysis. Reaction time (h) and pH were considered as independent factors. A total of 97.0% biochemical oxygen demand, 99.9% phosphorous and 88.6% cadmium were eliminated at the optimum reaction time (80.0 min) and pH (6.4).

Keywords: adsorption, electrochemical oxidation, metals, SBR

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Authors: Ruchi Jain, Chinnakonda S. Gopinath

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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: Yaling Gou, Sucai Yang, Pengwei Qiao

Abstract:

Integrated chemical-biological treatment is an attractive alternative to remove polycyclic aromatic hydrocarbons (PAHs) from contaminated soil; wherein indigenous bacteria is the key factor for the biodegradation of residual PAHs concentrations after the application of chemical oxidation. However, the systematical study on the impact of persulfate (PS) oxidation on indigenous bacteria as well as PAHs removal is still scarce. In this study, the influences of different PS dosages (1%, 3%, 6%, and 10% [w/w]), as well as various activation methods (native iron, H2O2, alkaline, ferrous iron, and heat) on PAHs removal and indigenous bacteria in highly contaminated aged soil were investigated. Apparent degradation of PAHs in the soil treated with PS oxidation was observed, and the removal efficiency of total PAHs in the soil ranged from 38.28% to 79.97%. The removal efficiency of total PAHs in the soil increased with increasing consumption of PS. However, the bacterial abundance in soil was negatively affected following oxidation for all of the treatments added with PS, with bacterial abundance in the soil decreased by 0.89~2.88 orders of magnitude compared to the untreated soil. Moreover, the number of total bacteria in the soil decreased as PS consumption increased. Different PS activation methods and PS dosages exhibited different influences on the bacterial community composition. Bacteria capable of degrading PAHs under anoxic conditions were composed predominantly by Proteobacteria and Firmicutes. The total amount of Proteobacteria and Firmicutes also decreased with increasing consumption of PS. The results of this study provide important insight into the design of PAHs contaminated soil remediation projects.

Keywords: activation method, chemical oxidation, indigenous bacteria, polycyclic aromatic hydrocarbon

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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: Baobao Li

Abstract:

Operational risk covers all operations of commercial banks and has a close relationship with the bank’s internal control. But in the commercial banks' management practice, internal control is always separated from the operational risk measurement. With the increasing of operational risk events in recent years, operational risk is paid more and more attention by regulators and banks’ managements. The paper first discussed the relationship between internal control and operational risk management and used CVaR-POT model to measure operational risk, and then put forward a modified measurement method (to use operational risk assessment results to modify the measurement results of the CVaR-POT model). The paper also analyzed the necessity and rationality of this method. The method takes into consideration the influence of internal control, improves the accuracy and effectiveness of operational risk measurement and save the economic capital for commercial banks, avoiding the drawbacks of using some mainstream models one-sidedly.

Keywords: commercial banks, internal control, operational risk, risk measurement

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Authors: Helena M. Wilhelm, Paulo O. Fernandes, Laís P. Dill, Kethlyn G. Moscon

Abstract:

The use of vegetable oil (or natural ester) as an insulating fluid in electrical transformers is a trend that aims to contribute to environmental preservation since it is biodegradable and non-toxic. Besides, vegetable oil has high flash and combustion points, being considered a fire safety fluid. However, vegetable oil is usually less stable towards oxidation than mineral oil. Both insulating fluids, mineral and vegetable oils, need to be tested periodically according to specific standards. Oxidation stability can be determined by the induction period measured by conductivity method (Rancimat) by monitoring the effectivity of oil’s antioxidant additives, a methodology already developed for food application and biodiesel but still not standardized for insulating fluids. Besides adequate oxidation stability, fluids must be compatible with transformer's construction materials under normal operating conditions to ensure that damage to the oil and parts of the transformer does not occur. ASTM standard and Brazilian normative differ in parameters evaluated, which reveals the need to regulate tests for each oil type. The aim of this study was to assess oxidation stability and compatibility of vegetable oils to suggest the best way to assure a viable performance of vegetable oil as transformer insulating fluid. The determination of the induction period for several vegetable insulating oils from the local market by using Rancimat was carried out according to BS EN 14112 standard, at different temperatures (110, 120, and 130 °C). Also, the compatibility of vegetable oil was assessed according to ASTM and ABNT NBR standards. The main results showed that the best temperature for use in the Rancimat test is 130 °C, which allows a better observation of conductivity change. The compatibility test results presented differences between vegetable and mineral oil standards that should be taken into account in oil testing since materials compatibility and oxidation stability are essential for equipment reliability.

Keywords: compatibility, Rancimat, natural ester, vegetable oil

Procedia PDF Downloads 171