Search results for: Catalytic wet air oxidation

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, biodiesel, decomposition, oxidation, tocopherol.

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Authors: Supriyono, Sumardiyono, Rendy J. Pramono

Abstract:

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, biodiesel, decomposition, oxidation, tocopherol.

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Authors: S. Nouri

Abstract:

In this study, the Si-aluminide coating was prepared on gamma-TiAl [Ti-45Al-2Nb-2Mn-1B (at. %)] via liquid-phase slurry procedure. The high temperature oxidation resistance of this diffusion coating was evaluated at 1100 °C for 400 hours. The results of the isothermal oxidation showed that the formation of Si-aluminide coating can remarkably improve the high temperature oxidation of bare gamma-TiAl alloy. The identification of oxide scale microstructure showed that the formation of protective Al₂O₃+SiO₂ mixed oxide scale along with a continuous, compact and uniform layer of Ti₅Si₃ beneath the surface oxide scale can act as an oxygen diffusion barrier during the high temperature oxidation. The other possible mechanisms related to the formation of Si-aluminide coating and oxide scales were also discussed.

Keywords: Gamma-TiAl alloy, Si-aluminide coating, slurry procedure, high temperature oxidation.

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Authors: Geun-Il Park, Jae-Won Lee, Dou-Youn Lee, Jung-Won Lee, Kwang-Wook Kim, Kee-Chan Song

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Thermochemcial characteristics of powder fabricated using oxidation treatment of spent PWR fuel and SIMFUEL were evaluated for recycling of spent fuel such as DUPIC process. Especially, the influence of spent fuel burn-ups on the powder fabrication characteristics was experimentally evaluated, ranging from 27,300 to 65,000 MWd/tU. Densities of powder manufactured from an oxidation, OREOX and the milling processes at the same process conditions were compared as a function of the fuel burn-ups respectively. Also, based on chemical analysis results, homogeneity of fissile elements in oxidized powder was confirmed.

Keywords: Spent PWR fuel, DUPIC, Oxidation, OREOX, Powder, Chemical analysis

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Authors: P. Painmanakul, T. Chintateerachai, S. Lertlapwasin, N. Rojvilavan, T. Chalermsinsuwan, N. Chawaloesphonsiya, O. Larpparisudthi

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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: Nihat Hakan Akyol, Irfan Yolcubal

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In-situ chemical oxidation (ISCO) has been widely used for source zone remediation of Dense Nonaqueous Phase Liquids (DNAPLs) in subsurface environments. DNAPL source zones for karst aquifers are generally located in epikarst where the DNAPL mass is trapped either in karst soil or at the regolith contact with carbonate bedrock. This study aims to investigate the performance of oxidation of residual trichloroethylene found in such environments by potassium permanganate. Batch and flow cell experiments were conducted to determine the kinetics and the mass removal rate of TCE. pH change, Cl production, TCE and MnO4 destruction were monitored routinely during experiments. Nonreactive tracer tests were also conducted prior and after the oxidation process to determine the influence of oxidation on flow conditions. The results show that oxidant consumption rate of the calcareous epikarst soil was significant and the oxidant demand was determined to be 20 g KMnO4/kg soil. Oxidation rate of residual TCE (1.26x10-3 s-1) was faster than the oxidant consumption rate of the soil (2.54 - 2.92x10-4 s-1) at only high oxidant concentrations (> 40 mM KMnO4). Half life of TCE oxidation ranged from 7.9 to 10.7 min. Although highly significant fraction of residual TCE mass in the system was destroyed by permanganate oxidation, TCE concentration in the effluent remained above its MCL. Flow interruption tests indicate that efficiency of ISCO was limited by the rate of TCE dissolution and the rate-limited desorption of TCE. The residence time and the initial concentration of the oxidant in the source zone also controlled the efficiency of ISCO in epikarst.

Keywords: Epikarst, in-situ chemical oxidation, permanganate.

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Authors: Hsien T. Hsieh, Chao R. Chen, Li C. Chuang, Chin C. Shen

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Fenton oxidation technology is the general strategy for the treatment of organic compounds-contained wastewater. However, a considerable amount of ferric sludge was produced during the Fenton process as secondary wastes, which were needed to be further removed from the effluent and treated. In this study, heterogeneous catalysts based on ferrite oxide (Cu-Fe-Ce-O) were synthesized and characterized, and their application for Fenton-like oxidation of simulated and actual radioactive organic wastewater was investigated. The results of TOC decomposition efficiency around 54% ~ 99% were obtained when the catalyst loading, H₂O₂ loading, pH, temperature, and reaction time were controlled. In this case, no secondary wastes formed and the given catalysts were able to be separated by magnetic devices and reused again.

Keywords: Fenton, oxidation, heterogeneous catalyst, wastewater.

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Authors: Farouq Twaiq, Ishaq Al-Anbari, Mustafa Nasser

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The kinetics of palm oil catalytic cracking over aluminum containing mesoporous silica Al-MCM-41 (5% Al) was investigated in a batch autoclave reactor at the temperatures range of 573 – 673 K. The catalyst was prepared by using sol-gel technique and has been characterized by nitrogen adsorption and x-ray diffraction methods. Surface area of 1276 m2/g with average pore diameter of 2.54 nm and pore volume of 0.811 cm3/g was obtained. The experimental catalytic cracking runs were conducted using 50 g of oil and 1 g of catalyst. The reaction pressure was recorded at different time intervals and the data were analyzed using Levenberg- Marquardt (LM) algorithm using polymath software. The results show that the reaction order was found to be -1.5 and activation energy of 3200 J/gmol.

Keywords: Batch Reactor, Catalytic Cracking, Kinetics, Palm Oil.

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Authors: S. Desouky, A. Al sabagh , M. Betiha, A. Badawi, A. Ghanem, S. Khalil

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Two Amphiphilic catalysts, iron (III) dodecylbenzene sulfonate and nickel (II) dodecylbenzene sulfonate, were synthesized and used in the catalytic aquathermolysis of heavy crude oil to reduce its viscosity. The prepared catalysts exhibited good performance in the aquathermolysis and the viscosity is reduced by ~ 78.9 % for Egyptian heavy crude oil. The chemical and physical properties of heavy oil both before and after reaction were investigated by FT-IR, dynamic viscosity, molecular weight and SARA analysis. The results indicated that the content of resin, asphaltene, average molecular weight and sulfur content of heavy oil is reduced after the catalytic aquathermolysis.

Keywords: Amphiphilic catalyst, Aquathermolysis, Heavy oil, Viscosity reduction.

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Authors: Sewon Kim, Changyeop Lee, Minjun Kwon

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A noble low NOx combustion technology, based on partial oxidation combustion concept in a fuel rich combustion zone, is successfully applied in this research. The burner is designed such that a portion of fuel is heated and pre-vaporized 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, and fuel distribution ratio on the emissions of NOx and CO are experimentally investigated. This newly developed combustion technology showed very low NOx emission level, about 12 ppm, when light oil is used as a fuel.

Keywords: Burner, low NOx, liquid fuel, partial oxidation, fuel rich.

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Authors: Z. Abdolldhi, A. A. Ziaee M., A. Afshar

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In this paper the combination of thermal oxidation and electrochemical anodizing processes is used to produce titanium oxide layers. The response of titanium alloy Ti6Al4V to oxidation processes at various temperatures and electrochemical anodizing in various voltages are investigated. Scanning electron microscopy (SEM); X-Ray Diffraction (XRD) and porosity determination have been used to characterize the oxide layer thickness, surface morphology, oxide layer-substrate adhesion and porosity. In the first experiment, samples modified by thermal oxidation process then followed by electrochemical anodizing. Second experiment consists of surfaces modified by electrochemical anodizing process and then followed by thermal oxidation. The first method shows better properties than other one. In second experiment, Surfaces modified were achieved by thicker and more adherent thick oxide layers on titanium surface. The existence of an electrochemical anodized oxide layer did not improve the adhesion of thermal oxide layer. The high temperature, thermal formation of an oxide layer leads to a coarse oxide grain morphology and a complete oxidative particle. In addition, in high temperature oxidation porosity content is increased. The oxide layer of thermal oxidation and electrochemical anodizing processes; on Ti–6Al–4V substrate was covered with different colored oxide layers.

Keywords: Electrochemically anodizing, Porosity, Thermaloxidation, Ti6Al4 alloy.

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Authors: Jayesh P. Ruparelia, Bhavna D. Soni

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Electrochemical-oxidation of Reactive Black-5 (RB- 5) was conducted for degradation using DSA type Ti/RuO2-SnO2- Sb2O5 electrode. In the study, for electro-oxidation, electrode was indigenously fabricated in laboratory using titanium as substrate. This substrate was coated using different metal oxides RuO2, Sb2O5 and SnO2 by thermal decomposition method. Laboratory scale batch reactor was used for degradation and decolorization studies at pH 2, 7 and 11. Current density (50mA/cm2) and distance between electrodes (8mm) were kept constant for all experiments. Under identical conditions, removal of color, COD and TOC at initial pH 2 was 99.40%, 55% and 37% respectively for initial concentration of 100 mg/L RB-5. Surface morphology and composition of the fabricated electrode coatings were characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) respectively. Coating microstructure was analyzed by X-ray diffraction (XRD). Results of this study further revealed that almost 90% of oxidation occurred within 5-10 minutes.

Keywords: Electrochemical-oxidation, RB- dye, Decolorization.

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Authors: S. Chauhan, T.P.K. Grewal, S.K. Aggarwal, V.K. Srivastava

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Solution for the complete removal of carbon monoxide from the exhaust gases still poses a challenge to the researchers and this problem is still under development. Modeling for reduction of carbon monoxide is carried out using heterogeneous reaction using low cost non-noble metal based catalysts for the purpose of controlling emissions released to the atmosphere. A simple one-dimensional model was developed for the monolith using hopcalite catalyst. The converter is assumed to be an adiabatic monolith operating under warm-up conditions. The effect of inlet gas temperatures and catalyst loading on carbon monoxide reduction during cold start period in the converter is analysed.

Keywords: carbon monoxide, catalytic, modeling, monolith

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Authors: Noor S. Nasri, Eric C. A. Tatt, Usman D. Hamza, Jibril Mohammed, Husna M. Zain

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Catalytic combustion of methane is imperative due to stability of methane at low temperature. Methane (CH4), therefore, remains unconverted in vehicle exhausts thereby causing greenhouse gas GHG emission problem. In this study, heterogeneous catalysts of palladium with bio-char (2 wt% Pd/Bc) and Al2O3 (2wt% Pd/ Al2O3) supports were prepared by incipient wetness impregnation and then subsequently tested for catalytic combustion of CH4. Support-porous heterogeneous catalytic combustion (HCC) material were selected based on factors such as surface area, porosity, thermal stability, thermal conductivity, reactivity with reactants or products, chemical stability, catalytic activity, and catalyst life. Sustainable and renewable support-material of bio-mass char derived from palm shell waste material was compared with those from the conventional support-porous materials. Kinetic rate of reaction was determined for combustion of methane on Palladium (Pd) based catalyst with Al2O3 support and bio-char (Bc). Material characterization was done using TGA, SEM, and BET surface area. The performance test was accomplished using tubular quartz reactor with gas mixture ratio of 3% methane and 97% air. The methane porous-HCC conversion was carried out using online gas analyzer connected to the reactor that performed porous-HCC. BET surface area for prepared 2 wt% Pd/Bc is smaller than prepared 2wt% Pd/ Al2O3 due to its low porosity between particles. The order of catalyst activity based on kinetic rate on reaction of catalysts in low temperature was 2wt% Pd/Bc>calcined 2wt% Pd/ Al2O3> 2wt% Pd/ Al2O3>calcined 2wt% Pd/Bc. Hence agro waste material can successfully be utilized as an inexpensive catalyst support material for enhanced CH4 catalytic combustion.

Keywords: Catalytic-combustion, Environmental, Support-bio-char material, Sustainable, Renewable material.

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Authors: Sushil Kumar Saraswat, K. K. Pant

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Co metal supported on SiO2 and Al2O3 catalysts with a metal loading varied from 30 of 70 wt.% were evaluated for decomposition of methane to COx free hydrogen and carbon nanomaterials. The catalytic runs were carried out from 550-800oC under atmospheric pressure using fixed bed vertical flow reactor. The fresh and spent catalysts were characterized by BET surface area analyzer, XRD, SEM, TEM and TG analysis. The data showed that 50% Co/Al2O3 catalyst exhibited remarkable higher activity at 800oC with respect to H2 production compared to rest of the catalysts. However, the catalytic activity and durability was greatly declined at higher temperature. The main reason for the catalytic inhibition of Co containing SiO2 catalysts is the higher reduction temperature of Co2SiO4. TEM images illustrate that the carbon materials with various morphologies, carbon nanofibers (CNFs), helical-shaped CNFs and branched CNFs depending on the catalyst composition and reaction temperature were obtained.

Keywords: Carbon nanotubes, Cobalt, Hydrogen Production, Methane decomposition.

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Authors: Chandrashekar, R. T. Radhika, B. M. Venkatesha, S. Ananda, Shivalingegowda, T. S. Shashikumar, H. Ramachandra

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The kinetics of the oxidation of amitriptyline (AT) by sodium N-bromotoluene sulphonamide (C₆H₅SO₂NBrNa) has been studied in an acidic buffer medium of pH 1.2 at 303 K. The oxidation reaction of AT was followed spectrophotometrically at maximum wavelength, 410 nm. The reaction rate shows a first order dependence each on concentration of AT and concentration of sodium N-bromotoluene sulphonamide. The reaction also shows an inverse fractional order dependence at low or high concentration of HCl. The dielectric constant of the solvent shows negative effect on the rate of reaction. The addition of halide ions and the reduction product of BAT have no significant effect on the rate. The rate is unchanged with the variation in the ionic strength (NaClO₄) of the medium. Addition of reaction mixtures to be aqueous acrylamide solution did not initiate polymerization, indicating the absence of free radical species. The stoichiometry of the reaction was found to be 1:1 and oxidation product of AT is identified. The Michaelis-Menton type of kinetics has been proposed. The CH₃C₆H₅SO₂NHBr has been assumed to be the reactive oxidizing species. Thermodynamical parameters were computed by studying the reactions at different temperatures. A mechanism consistent with observed kinetics is presented.

Keywords: Amitriptyline, bromamine-T, kinetics, oxidation.

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Authors: M. Poveda, S. Lozecznik, J. Oleszkiewicz, Q. Yuan

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The goal of this experiment is to evaluate the effectiveness of different leachate pre-treatment options in terms of COD and ammonia removal. This research focused on the evaluation of physical-chemical methods for pre-treatment of leachate that would be effective and rapid in order to satisfy the requirements of the sewer discharge by-laws. The four pre-treatment options evaluated were: air stripping, chemical coagulation, electrocoagulation and advanced oxidation with sodium ferrate. Chemical coagulation reported the best COD removal rate at 43%, compared to 18% for both air stripping and electro-coagulation, and 20% for oxidation with sodium ferrate. On the other hand, air stripping was far superior to the other treatment options in terms of ammonia removal with 86%. Oxidation with sodium ferrate reached only 16%, while chemical coagulation and electro-coagulation removed less than 10%. When combined, air stripping and chemical coagulation removed up to 50% COD and 85% ammonia.

Keywords: Leachate pretreatment, air stripping, chemical coagulation, electro-coagulation, oxidation.

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Authors: Mohammad Rezaee, Mohammad Kazemeini, Ali Morad Rashidi, Moslem Fattahi

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Selective oxidation of H2S to elemental sulfur in a fixed bed reactor over newly synthesized alumina nanocatalysts was physio-chemically investigated and results compared with a commercial Claus catalyst. Amongst these new materials, Al2O3- supported sodium oxide prepared with wet chemical technique and Al2O3 nanocatalyst prepared with spray pyrolysis method were the most active catalysts for selective oxidation of H2S to elemental sulfur. Other prepared nanocatalysts were quickly deactivated, mainly due to the interaction with H2S and conversion into sulfides.

Keywords: H2S, Claus process, Al2O3, Spray pyrolysis method, Wet chemical technique

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Authors: Krasimir Ivanov, Dimitar Dimitrov, Boyan Boyanov

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The paper relates to a catalyst, comprising copperchromium spinel, coated on carrier γ-Al2O3. The effect of preparation conditions on the active component composition and activity behavior of the catalysts is discussed. It was found that the activity of carbon monoxide, DME, formaldehyde and methanol oxidation reaches a maximum at an active component content of 20 – 30 wt. %. Temperature calcination at 500oC seems to be optimal for the γ– alumina supported CuO-Cr2O3 catalysts for CO, DME, formaldehyde and methanol oxidation. A three months industrial experiment was carried out to elucidate the changes in the catalyst composition during industrial exploitation of the catalyst and the main reasons for catalyst deactivation. It was concluded that the CuO–Cr2O3/γ–alumina supported catalysts have enhanced activity toward CO, DME, formaldehyde and methanol oxidation and that these catalysts are suitable for industrial application. The main reason for catalyst deactivation seems to be the deposition of iron and molybdenum, coming from the main reactor, on the active component surface.

Keywords: catalyst deactivation, CuO-Cr2O3 catalysts, deep oxidation.

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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 an integrated aquatic plants in phytogreen zone was studied and statistical analysis for the promotional integrated phytogreen system approached was discussed. It was found that's 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 phtogreen 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: M. Michalska-Domańska, P. Jóźwik, Z. Bojar

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Intermetallic Ni3Al – based alloys belong to a group of advanced materials characterized by good chemical and physical properties (such as structural stability, corrosion resistance) which offer advenced technological applications. The paper presents the study of catalytic properties of Ni3Al foils (thickness approximately 50 &m) in the methanol and hexane decomposition. The egzamined material posses microcrystalline structure without any additional catalysts on the surface. The better catalytic activity of Ni3Al foils with respect to quartz plates in both methanol and hexane decomposition was confirmed. On thin Ni3Al foils the methanol conversion reaches approximately 100% above 480 oC while the hexane conversion reaches approximately 100% (98,5%) at 500 oC. Deposit formed during the methanol decomposition is built up of carbon nanofibers decorated with metal-like nanoparticles.

Keywords: hexane decomposition, methanol decomposition, Ni3Al thin foils, Ni nanoparticles

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Authors: Vishnu S. Prasad, Preeti Aghalayam

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The major harmful automobile exhausts are nitric oxide (NO) and unburned hydrocarbon (HC). Reduction of NO using unburned fuel HC as a reductant is the technique used in hydrocarbon-selective catalytic reduction (HC-SCR). In this work, we study the microkinetic modelling of NO reduction using propene as a reductant on Pt catalysts. The selectivity of NO reduction to N₂O is detected in some ranges of operating conditions, whereas the effect of inlet O₂% causes a number of changes in the feasible regimes of operation.

Keywords: Microkinetic modelling, NOx, Pt on alumina catalysts, selective catalytic reduction.

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Authors: Thitipong Auttanat, Siriporn Jongpatiwut, Thirasak Rirksomboon

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The catalytic dehydroxylation of glycerol to propylene glycol was investigated over Cu-ZnO/Al2O3 prepared by incipient wetness impregnation (IWI) method with different purity feedstocks - refined glycerol and technical grade glycerol. The main purpose is to investigate the effects of feed impurities that cause the catalyst deactivation. The prepared catalyst were tested for its catalytic activity and selectivity in a continuous flow fixed bed reactor at 523 K, 500 psig, H2/feed molar ratio of 4 and WHSV of 3 h-1. The results showed that conversion of refined glycerol and technical grade glycerol at time on stream 6 hour are 99% and 71% and selectivity to propylene glycol are 87% and 56% respectively. The ICP-EOS and TPO results indicated that the cause of catalyst deactivation was the amount of impurities in the feedstock. The higher amount of impurities (especially Na and K) the lower catalytic activity.

Keywords: Cu-ZnO/Al2O3, dehydroxylation, glycerol, propylene glycol,

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Authors: M. Amanipour, J. Towfighi, E. Ganji Babakhani, M. Heidari

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Cylindrical alumina microfiltration membrane (GMITM Corporation, inside diameter=9 mm, outside diameter=13 mm, length= 50 mm) with an average pore size of 0.5 micrometer and porosity of about 0.35 was used as the support for membrane reactor. This support was soaked in boehmite sols, and the mean particle size was adjusted in the range of 50 to 500 nm by carefully controlling hydrolysis time, and calcined at 650 °C for two hours. This process was repeated with different boehmite solutions in order to achieve an intermediate layer with an average pore size of about 50 nm. The resulting substrate was then coated with a thin and dense layer of silica by counter current chemical vapour deposition (CVD) method. A boehmite sol with 10 wt.% of nickel which was prepared by a standard procedure was used to make the catalytic layer. BET, SEM, and XRD analysis were used to characterize this layer. The catalytic membrane reactor was placed in an experimental setup to evaluate the permeation and hydrogen separation performance for a steam reforming reaction. The setup consisted of a tubular module in which the membrane was fixed, and the reforming reaction occurred at the inner side of the membrane. Methane stream, diluted with nitrogen, and deionized water with a steam to carbon (S/C) ratio of 3.0 entered the reactor after the reactor was heated up to 500 °C with a specified rate of 2 °C/ min and the catalytic layer was reduced at presence of hydrogen for 2.5 hours. Nitrogen flow was used as sweep gas through the outer side of the reactor. Any liquid produced was trapped and separated at reactor exit by a cold trap, and the produced gases were analyzed by an on-line gas chromatograph (Agilent 7890A) to measure total CH₄ conversion and H₂ permeation. BET analysis indicated uniform size distribution for catalyst with average pore size of 280 nm and average surface area of 275 m².g^-1. Single-component permeation tests were carried out for hydrogen, methane, and carbon dioxide at temperature range of 500-800 °C, and the results showed almost the same permeance and hydrogen selectivity values for hydrogen as the composite membrane without catalytic layer. Performance of the catalytic membrane was evaluated by applying membranes as a membrane reactor for methane steam reforming reaction at gas hourly space velocity (GHSV) of 10,000 h⁻¹ and 2 bar. CH₄ conversion increased from 50% to 85% with increasing reaction temperature from 600 °C to 750 °C, which is sufficiently above equilibrium curve at reaction conditions, but slightly lower than membrane reactor with packed nickel catalytic bed because of its higher surface area compared to the catalytic layer.

Keywords: Catalytic membrane, hydrogen, methane steam reforming, permeance.

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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: Zhi Zhang, Tao Tang, Guangda Lu, Cheng Qin, Huogen Huang, Shaotao Zheng

Abstract:

High purity hydrogen and the valuable by-product of carbon nanotubes (CNTs) can be produced by the methane catalytic decomposition. The methane conversion and the performance of CNTs were determined by the choices of catalysts and the condition of decomposition reaction. In this paper, Ni/MgO and Ni/O-D (oxidized diamond) catalysts were prepared by wetness impregnation method. The effects of reaction temperature and space velocity of methane on the methane conversion were investigated in a fixed-bed. The surface area, structure and micrography were characterized with BET, XPS, SEM, EDS technology. The results showed that the conversion of methane was above 8% within 150 min (T=500) for 33Ni/O-D catalyst and higher than 25% within 120 min (T=650) for 41Ni/MgO catalyst. The initial conversion increased with the increasing temperature of the decomposition reaction, but their catalytic activities decreased rapidly while at too higher temperature. To decrease the space velocity of methane was propitious to promote the methane conversion, but not favor of the hydrogen yields. The appearance of carbon resulted from the methane decomposition lied on the support type and the condition of catalytic reaction. It presented as fiber shape on the surface of Ni/O-D at the relatively lower temperature such as 500 and 550, but as grain shape stacked on and overlayed on the surface of the metal nickel while at 650. The carbon fiber can form on the Ni/MgO surface at 650 and the diameter of the carbon fiber increased with the decreasing space velocity.

Keywords: methane, catalytic decomposition, hydrogen, carbon nanofiber

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Authors: C. Pongcharoen, K. Kaiyavongand T. Satapanajaru

Abstract:

Theobjective of this study was to evaluate the optimal treatment condition of Fenton oxidation process to removal contaminant in soil slurry contaminated by petroleum hydrocarbons. This research studied somefactors that affect the removal efficiency of petroleum hydrocarbons in soil slurry including molar ratio of hydrogen peroxide (H2O2) to ferrous ion(Fe2+), pH condition and reaction time.The resultsdemonstrated that the optimum condition was that the molar ratio of H2O2:Fe3+ was 200:1,the pHwas 4.0and the rate of reaction was increasing rapidly from starting point to 7th hour and destruction kinetic rate (k) was 0.24 h-1. Approximately 96% of petroleum hydrocarbon was observed(initialtotal petroleum hydrocarbon (TPH) concentration = 70±7gkg-1)

Keywords: Contaminated soil, Fenton oxidation, Petroleumhydrocarbon, Remediation.

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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.

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Authors: A. A. Alhazza

Abstract:

The recycling process of Tungsten alloy (Swarf) by oxidation reduction technique have been investigated. The reduced powder was pressed under a pressure 20Kg/cm2 and sintered at 1150°C in dry hydrogen atmosphere. The particle size of the recycled alloy powder was 1-3 μm and the shape was regular at a reduction temperature 800°C. The chemical composition of the recycled alloy is the same as the primary Swarf.

Keywords: Recycling, Swarf, Oxidation, Reduction.

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