Search results for: Copper-manganese-chromium oxide catalysts

Authors: Worawoot Prasitturattanachai, Kamchai Nuithitikul

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The conventional production of biodiesel from crude palm oil which contains large amounts of free fatty acids in the presence of a homogeneous base catalyst confronts the problems of soap formation and very low yield of biodiesel. To overcome these problems, free fatty acids must be esterified to their esters in the presence of an acid catalyst prior to alkaline-catalyzed transesterification. Sulfated metal oxides are a promising group of catalysts due to their very high acidity. In this research, aluminadoped sulfated tin oxide (SO4 2-/Al2O3-SnO2) catalysts were prepared and used for esterification of free fatty acids in crude palm oil in a batch reactor. The SO4 2-/Al2O3-SnO2 catalysts were prepared from different Al precursors. The results showed that different Al precursors gave different activities of the SO4 2-/Al2O3-SnO2 catalysts. The esterification of free fatty acids in crude palm oil with methanol in the presence of SO4 2-/Al2O3-SnO2 catalysts followed first-order kinetics.

Keywords: Methyl ester, Biodiesel, Esterification, Sulfated tin oxide, Fatty acid.

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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: K. Pipitthapan, S. Maksasithorn, P. Praserthdam, J. Panpranot, K. Suriye, S. Kunjara Na Ayudhya

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WO3/SiO2 catalysts were modified by an ion exchange method with sodium hydroxide or potassium hydroxide solution. The performance of the modified catalysts was tested in the metathesis of ethylene and trans-2-butene to propylene. During ion exchange, sodium and potassium ions played different roles. Sodium modified catalysts revealed constant trans-2-butene conversion and propylene selectivity when the concentrations of sodium in the solution were varied. In contrast, potassium modified catalysts showed reduction of the conversion and increase of the selectivity. From these results, potassium hydroxide may affect the transformation of tungsten oxide active species, resulting in the decrease in conversion whereas sodium hydroxide did not. Moreover, the modification of catalysts by this method improved the catalyst stability by lowering the amount of coke deposited on the catalyst surface.

Keywords: Acid sites, alkali metals, isomerization, metathesis.

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Authors: Krasimir I. Ivanov, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Georgi V. Avdeev, Tatyana T. Tabakova

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In recent research copper and manganese systems were found to be the most active in CO and organic compounds oxidation among the base catalysts. The mixed copper manganese oxide has been widely studied in oxidation reactions because of their higher activity at low temperatures in comparison with single oxide catalysts. The results showed that the formation of spinel CuxMn3−xO4 in the oxidized catalyst is responsible for the activity even at room temperature. That is why the most of the investigations are focused on the hopcalite catalyst (CuMn2O4) as the best coppermanganese catalyst. Now it’s known that this is true only for CO oxidation, but not for mixture of CO and VOCs. The purpose of this study is to investigate the alumina supported copper-manganese catalysts with different Cu/Mn molar ratio in terms of oxidation of CO, methanol and dimethyl ether. The catalysts were prepared by impregnation of γ-Al2O3 with copper and manganese nitrates and the catalytic activity measurements were carried out in two stage continuous flow equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions closest possible to the industrial. Gas mixtures on the input and output of the reactor were analyzed with a gas chromatograph, equipped with FID and TCD detectors. The texture characteristics were determined by low-temperature (- 196oС) nitrogen adsorption in a Quantachrome Instruments NOVA 1200e (USA) specific surface area & pore analyzer. Thermal, XRD and TPR analyses were performed. It was established that the active component of the mixed Cu- Mn/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio. Highly active alumina supported Cu-Mn catalysts for CO, methanol and DME oxidation were synthesized. While the hopcalite is the best catalyst for CO oxidation, the best compromise for simultaneous oxidation of all components is the catalyst with Cu/Mn molar ratio 1:5.

Keywords: Supported copper-manganese catalysts, CO and VOCs oxidation.

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Authors: Weixin Qian, Haitao Zhang, Hongfang Ma, Yongdi Liu, Weiyong Ying, Dingye Fang

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The adsorption properties of CO and H2 on iron-based catalyst with addition of Zr and Ni were investigated using temperature programmed desorption process. It was found that on the carburized iron-based catalysts, molecular state and dissociative state CO existed together. The addition of Zr was preferential for the molecular state adsorption of CO on iron-based catalyst and the presence of Ni was beneficial to the dissociative adsorption of CO. On H2 reduced catalysts, hydrogen mainly adsorbs on the surface iron sites and surface oxide sites. On CO reduced catalysts, hydrogen probably existed as the most stable CH and OH species. The addition of Zr was not benefit to the dissociative adsorption of hydrogen on iron-based catalyst and the presence of Ni was preferential for the dissociative adsorption of hydrogen.

Keywords: adsorption, Fischer-Tropsch synthesis, iron-based catalysts

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Authors: V. Rednic, N. Aldea, P. Marginean, D. Macovei, C. M. Teodorescu, E. Dorolti, F. Matei

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The supported Pd catalysts were analyzed by X-ray diffraction and X-ray absorption spectroscopy in order to determine their global and local structure. The average particle size of the supported Pd catalysts was determined by X-ray diffraction method. One of the main purposes of the present contribution is to focus on understanding the specific role of the Pd particle size determined by X-ray diffraction and that of the support oxide. Based on X-ray absorption fine structure spectroscopy analysis we consider that the whole local structure of the investigated samples are distorted concerning the atomic number but the distances between atoms are almost the same as for standard Pd sample. Due to the strong modifications of the Pd cluster local structure, the metal-support interface may influence the electronic properties of metal clusters and thus their reactivity for absorption of the reactant molecules.

Keywords: metal-support interaction, supported metal catalysts, synchrotron radiation, X-ray absorption spectroscopy, X-raydiffraction

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Authors: Tatyana T. Tabakova, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Krasimir I. Ivanov, Yordanka G. Karakirova, Petya Cv. Petrova, Georgi V. Avdeev

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The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH₃OH and (CH₃)₂O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH₃OH conversion at about 60 and 140 ^oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al₂O₃ 1:5 exhibited higher activity for CO and CH₃OH oxidation in comparison with Au on Cu-Ce/γ-Al₂O₃ 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.

Keywords: CO and VOCs oxidation, copper oxide, ceria, gold catalysts.

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Authors: Velid Demir, Mesut Akgün

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The lanthanum and zinc oxide were synthesized and then loaded with 6 wt% over γ-Al2O3 using the wet impregnation method. The samples were calcined at 900 °C to ensure a coherent structure with high catalytic performance. Characterization of the catalysts was verified by X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). The effect of catalysts on biodiesel content from jatropha oil was studied under supercritical conditions. The results showed that ZnO/γ-Al2O3 was the superior catalyst for jatropha oil with 98.05% biodiesel under reaction conditions of 7 min reaction time, 1:40 oil to methanol molar ratio, 6 wt% of catalyst loading, 90 bar of reaction pressure, and 300 °C of reaction temperature, compared to 95.50% with La2O3/γ-Al2O3 at the same parameters. For this study, ZnO/γ-Al2O3 was the most suitable catalyst due to performance and cost considerations.

Keywords: Biodiesel, heterogeneous catalyst, Jatropha oil, supercritical methanol, transesterification.

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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: N. Aldea, V. Rednic, F. Matei, Tiandou Hu, M. Neumann

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The nickel and gold nanoclusters as supported catalysts were analyzed by XAS, XRD and XPS in order to determine their local, global and electronic structure. The present study has pointed out a strong deformation of the local structure of the metal, due to its interaction with oxide supports. The average particle size, the mean squares of the microstrain, the particle size distribution and microstrain functions of the supported Ni and Au catalysts were determined by XRD method using Generalized Fermi Function for the X-ray line profiles approximation. Based on EXAFS analysis we consider that the local structure of the investigated systems is strongly distorted concerning the atomic number pairs. Metal-support interaction is confirmed by the shape changes of the probability densities of electron transitions: Ni K edge (1s → continuum and 2p), Au LIII-edge (2p3/2 → continuum, 6s, 6d5/2 and 6d3/2). XPS investigations confirm the metal-support interaction at their interface.

Keywords: local and global structure, metal-support interaction, supported metal catalysts, synchrotron radiation, X-ray absorptionspectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy.

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Authors: T. Thitiapichart, P. Praserthdama

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The effect of additional magnesium oxide (MgO) was investigated by using the tungsten oxide supported on silica catalyst (WOx/SiO2) physically mixed with MgO in a weight ratio 1:1. The both fresh and spent catalysts were characterized by FT-Raman spectrometer, UV-Vis spectrometer, X-Ray diffraction (XRD) and temperature programmed oxidation (TPO). The results indicated that the additional MgO could enhance the conversion of trans-2-butene due to isomerization reaction. However, adding MgO would increase the amount of coke deposit on the WOx/SiO2 catalyst. The TPO profile presented two peaks when the WOx/SiO2 catalyst was physically mixed with MgO. The further peak was suggested that came from coke precursor could be produced by isomerization reaction of undesired product. Then, the occurred coke precursor could deposit and form coke on the acid catalyst.

Keywords: Coke formation, metathesis, magnesium oxide, physically mix.

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Authors: Ude N. Callistus, Amulu F. Ndidi, Onukwuli D. Okechukwu, Amulu E. Patrick

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Power law approximation was used in this study to evaluate the reaction orders of calcium oxide, CaO catalyzed transesterification of refined cottonseed oil and methanol. The kinetics study was carried out at temperatures of 45, 55 and 65 ^oC. The kinetic parameters such as reaction order 2.02 and rate constant 2.8 hr^-1g^-1cat, obtained at the temperature of 65 ^oC best fitted the kinetic model. The activation energy, Ea obtained was 127.744 KJ/mol. The results indicate that the transesterification reaction of the refined cottonseed oil using calcium oxide catalyst is approximately second order reaction.

Keywords: Refined cottonseed oil, transesterification, CaO, heterogeneous catalysts, kinetic model.

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Authors: Krasimir I. Ivanov, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Petya Ts. Petrova, Tatyana T. Tabakova

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

Keywords: Copper-manganese-chromium oxide catalysts, CO, deep oxidation, volatile organic compounds.

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Authors: Phuong T. Dang, Hy G. Le, Giang T. Pham, Hong T. M. Vu, Kien T, Nguyen, Canh D. Dao, Giang H. Le, Hoa T. K. Tran, Quang K. Nguyen, Tuan A. Vu

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Nanostructured catalysts were successfully prepared by acidification of diatomite and regeneration of FCC spent catalysts. The obtained samples were characterized by IR, XRD, SEM, EDX, MAS-NMR (27Al and 29Si), NH3-TPD and tested in catalytic pyrolysis of biomass (rice straw). The results showed that the similar bio-oil yield of 41.4% can be obtained by pyrolysis with catalysts at 450oC as compared to that of the pyrolysis without catalyst at 550oC. The bio-oil yield reached a maximum of 42.55% at the pyrolysis temperature of 500oC with catalytic content of 20%. Moreover, by catalytic pyrolysis, bio-oil quality was better as reflected in higher ratio of H/C, lower ratio of O/C. This clearly indicated high application potential of these new nanostructured catalysts in the production of bio-oil with low oxygenated compounds.

Keywords: Acidified diatomite, biomass, catalytic pyrolysis, bio-oil, nanostructured catalysts, regenerated FCC catalyst.

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Authors: Chaojie Song, Lianhui Ding, Craig Fairbridge, Hansan Liu, Rob Hui, Jiujun Zhang

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Two novel hydrodesulfurization (HDS) catalysts: FeN4/C and FeN2/C, were prepared using an impregnation-pyrolysis method. The two materials were investigated as catalysts for hydrodesulfurization (HDS) and hydrodearomitization (HDA) of model compounds. The turnover frequency of the two FeN catalysts is comparable to (FeN4/C) or even higher (FeN2/C) than that of MoNi/Al2O3. The FeN4/C catalyst also exhibited catalytic activity toward HDA.

Keywords: catalyst, FeN2/C, FeN4/C, HDS, HDA

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Authors: N. Hataivichian, K. Suriye, S. Kunjara Na Ayudhya, P. Praserthdam, S. Phatanasri

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The effect of transition metal doping on Pt/Al2O3 catalyst used in propane dehydrogenation reaction at 500°C was studied. The preparation methods investigated were sequential impregnation (Pt followed by the 2nd metal or the 2nd metal followed by Pt) and co-impregnation. The metal contents of these catalysts were fixed as the weight ratio of Pt per the 2nd metal of around 0.075. These catalysts were characterized by N2-physisorption, TPR, COchemisorption and NH3-TPD. It was found that the impregnated 2nd metal had an effect upon reducibility of Pt due to its interaction with transition metal-containing structure. This was in agreement with the CO-chemisorption result that the presence of Pt metal, which is a result from Pt species reduction, was decreased. The total acidity of bimetallic catalysts is decreased but the strong acidity is slightly increased. It was found that the stability of bimetallic catalysts prepared by co-impregnation and sequential impregnation where the 2nd metal was impregnated before Pt were better than that of monometallic catalyst (undoped Pt one) due to the forming of Pt sites located on the transition metal-oxide modified surface. Among all preparation methods, the sequential impregnation method- having Pt impregnated before the 2nd metal gave the worst stability because this catalyst lacked the modified Pt sites and some fraction of Pt sites was covered by the 2nd metal.

Keywords: Alumina, dehydrogenation, platinum, transition metal.

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Authors: A.Guntida, K. Suriye, S. Kunjara Na Ayudhya, J. Panpranot, P. Praserthdam

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Propylene self-metathesis to ethylene and butene was studied over WOx/SiO2 catalysts at 450oC and atmospheric pressure. The WOx/SiO2 catalysts were prepared by incipient wetness impregnation of ammonium metatungstate aqueous solution. It was found that, adding nano-sized extra supports (SiO2 and TiO2) by physical mixing with the WOx/SiO2 enhanced propylene conversion. The UV-Vis and FT-Raman results revealed that WOx could migrate from the original silica support to the extra support, leading to a better dispersion of WOx. The ICP-OES results also indicate that WOx existed on the extra support. Coke formation was investigated on the catalysts after 10 h time-on-stream by TPO. However, adding nano-sized extra supports led to higher coke formation which may be related to acidity as characterized by NH3-TPD.

Keywords: Extra support, nanomaterial, propylene self-metathesis, tungsten oxide.

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Authors: Rana Th. A. Al-Rubaye, Arthur A. Garforth

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This work details the generation of thin films of structured zeolite catalysts (ZSM–5 and Y) onto the surface of a metal substrate (FeCrAlloy) using in-situ hydrothermal synthesis. In addition, the zeolite Y is post-synthetically modified by acidified ammonium ion exchange to generate US-Y. Finally the catalytic activity of the structured ZSM-5 catalyst films (Si/Al = 11, thickness 146 0m) and structured US–Y catalyst film (Si/Al = 8, thickness 230m) were compared with the pelleted powder form of ZSM–5 and USY catalysts of similar Si/Al ratios. The structured catalyst films have been characterised using a range of techniques, including X-ray diffraction (XRD), Electron microscopy (SEM), Energy Dispersive X–ray analysis (EDX) and Thermogravimetric Analysis (TGA). The transition from oxide-onalloy wires to hydrothermally synthesised uniformly zeolite coated surfaces was followed using SEM and XRD. In addition, the robustness of the prepared coating was confirmed by subjecting these to thermal cycling (ambient to 550oC). The cracking of n–heptane over the pellets and structured catalysts for both ZSM–5 and Y zeolite showed very similar product selectivities for similar amounts of catalyst with an apparent activation energy of around 60 kJ mol-1. This paper demonstrates that structured catalysts can be manufactured with excellent zeolite adherence and when suitably activated/modified give comparable cracking results to the pelleted powder forms. These structured catalysts will improve temperature distribution in highly exothermic and endothermic catalysed processes.

Keywords: FeCrAlloy, Structured catalyst, and Zeolite Y, Zeolite ZSM-5.

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Authors: Anmin Zhao, Weiyong Yingı , Haitao Zhang, Hongfang Ma, Dingye Fang

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The Ni/α-Al2O3 catalysts with different amounts of La as promoter from 0 to 4 wt % were prepared, characterized and their catalytic activity was investigated in syngas methanation reaction. Effects of reaction temperature and lanthanum loading on carbon oxides conversion and methane selectivity were also studied. Adding certain amount of lanthanum to 10Ni /α-Al2O3 catalysts can decrease the average NiO crystallite diameter which leads to higher activity and stability while excessive addition would cause deactivation quickly. Stability on stream towards deactivation was observed up to 800 min at 500 °C, 0.1MPa and 600000 mL·g-1·h-1.

Keywords: Methanation; Nickel catalysts; Syngas methanation

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Authors: Kanda Wongwailikhit

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Copper (I) oxide microparticles with the morphology of cubic and hollow sphere were synthesized with the assistance of surfactant as the shape controller. Both particles were then subjected to study the catalytic activity and observed the results of shape effects of catalysts on rate of catalytic reaction. The decolorizing reaction of crystal violet and sodium hydroxide was chosen and measured the decreasing of reactant with respect to times using spectrophotometer. The result revealed that morphology of crystal had no effect on the catalytic activity for crystal violet reaction but contributed to total surface area predominantly.

Keywords: Copper (I) oxide, Catalytic activity, Crystal violet.

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Authors: Anushree, Chhaya Sharma, Satish Kumar

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Catalytic wet air oxidation (CWAO) is normally carried out at elevated temperature and pressure. This work investigates the potential of NiO-CeO₂ nano-catalyst in CWAO of paper industry wastewater under milder operating conditions of 90 °C and 1 atm. The NiO-CeO₂ nano-catalysts were synthesized by a simple co-precipitation method and characterized by X-ray diffraction (XRD), before and after use, in order to study any crystallographic change during experiment. The extent of metal-leaching from the catalyst was determined using the inductively coupled plasma optical emission spectrometry (ICP-OES). The catalytic activity of nano-catalysts was studied in terms of total organic carbon (TOC), adsorbable organic halides (AOX) and chlorophenolics (CHPs) removal. Interestingly, mixed oxide catalysts exhibited higher activity than the corresponding single-metal oxides. The maximum removal efficiency was achieved with Ce₄₀Ni₆₀ catalyst. The results indicate that the CWAO process is efficient in removing the priority organic pollutants from wastewater, as it exhibited up to 59% TOC, 55% AOX, and 54 % CHPs removal.

Keywords: Nano-materials, NiO-CeO2, wastewater, wet air oxidation.

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Authors: Loai Ben Naji, Osama M. Ibrahim, Khaled J. Al-Fadhalah

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The objective of this paper is to investigate the formation and adhesion of a protective aluminum-oxide (Al₂O₃, alumina) layer on the surface of Iron-Chromium-Aluminum Alloy (Fe-Cr-Al) sintered-metal-fibers. The oxide-scale layer was developed via multi-stage thermal oxidation at 930 ^oC for 1 hour, followed by 1 hour at 960 ^oC, and finally at 990 ^oC for 2 hours. Scanning Electron Microscope (SEM) images show that the multi-stage thermal oxidation resulted in the formation of predominantly Al₂O₃ platelets-like and whiskers. SEM images also reveal non-uniform oxide-scale growth on the surface of the fibers. Furthermore, peeling/spalling of the alumina protective layer occurred after minimum handling, which indicates weak adhesion forces between the protective layer and the base metal alloy.  Energy Dispersive Spectroscopy (EDS) analysis of the heat-treated Fe-Cr-Al sintered-metal-fibers confirmed the high aluminum content on the surface of the protective layer, and the low aluminum content on the exposed base metal alloy surface. In conclusion, the failure of the oxide-scale protective layer exposes the base metal alloy to further oxidation, and the fragile non-uniform oxide-scale is not suitable as a support for catalysts.

Keywords: High-temperature oxidation, alumina protective layer, iron-chromium-aluminum alloy, sintered-metal-fibers.

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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: T. Maruyama, T. Saida, S. Naritsuka, S. Iijima

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Single-walled carbon nanotubes (SWCNTs) are generally synthesized by chemical vapor deposition (CVD) using Fe, Co, and Ni as catalysts. However, due to the Ostwald ripening of metal catalysts, the diameter distribution of the grown SWCNTs is considerably wide (>2 nm), which is not suitable for electronics applications. In addition, reduction in the growth temperature is desirable for fabricating SWCNT devices compatible with the LSI process. Herein, we performed SWCNT growth by alcohol catalytic CVD using platinum-group metal catalysts (Pt, Rh, and Pd) because these metals have high melting points, and the reduction in the Ostwald ripening of catalyst particles is expected. Our results revealed that web-like SWCNTs were obtained from Pt and Rh catalysts at growth temperature between 500 °C and 600 °C by optimizing the ethanol pressure. The SWCNT yield from Pd catalysts was considerably low. By decreasing the growth temperature, the diameter and chirality distribution of SWCNTs from Pt and Rh catalysts became small and narrow. In particular, the diameters of most SWCNTs grown using Pt catalysts were below 1 nm and their diameter distribution was considerably narrow. On the contrary, SWCNTs can grow from Rh catalysts even at 300 °C by optimizing the growth condition, which is the lowest temperature recorded for SWCNT growth. Our results demonstrated that platinum-group metals are useful for the growth of small-diameter SWCNTs and facilitate low-temperature growth.

Keywords: Carbon nanotube, chemical vapor deposition, catalyst, Pt, Rh, Pd.

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Authors: PoiSim Khiew, MuiYen Ho, ThianKhoonTan, WeeSiong Chiu, Roslinda Shamsudin, Muhammad Azmi Abd-Hamid, ChinHua Chia

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In the present work, we have developed a symmetric electrochemical capacitor based on the nanostructured iron oxide (Fe3O4)-activated carbon (AC) nanocomposite materials. The physical properties of the nanocomposites were characterized by Scanning Electron Microscopy (SEM) and Brunauer-Emmett-Teller (BET) analysis. The electrochemical performances of the composite electrode in 1.0 M Na2SO3 and 1.0 M Na2SO4 aqueous solutions were evaluated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The composite electrode with 4 wt% of iron oxide nanomaterials exhibits the highest capacitance of 86 F/g. The experimental results clearly indicate that the incorporation of iron oxide nanomaterials at low concentration to the composite can improve the capacitive performance, mainly attributed to the contribution of the pseudocapacitance charge storage mechanism and the enhancement on the effective surface area of the electrode. Nevertheless, there is an optimum threshold on the amount of iron oxide that needs to be incorporated into the composite system. When this optimum threshold is exceeded, the capacitive performance of the electrode starts to deteriorate, as a result of the undesired particle aggregation, which is clearly indicated in the SEM analysis. The electrochemical performance of the composite electrode is found to be superior when Na2SO3 is used as the electrolyte, if compared to the Na2SO4 solution. It is believed that Fe3O4 nanoparticles can provide favourable surface adsorption sites for sulphite (SO3 2-) anions which act as catalysts for subsequent redox and intercalation reactions.

Keywords: Metal oxide nanomaterials, Electrochemical Capacitor, Double Layer Capacitance, Pseduocapacitance

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Authors: Katya Milenova, Penko Nikolov, Irina Stambolova, Plamen Nikolov, Vladimir Blaskov

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In this article a comparison was made between Cu and TiO2 supported catalysts on activated carbon for ozone decomposition reaction. The activated carbon support in the case of TiO2/AC sample was prepared by physicochemical pyrolysis and for Cu/AC samples the supports are chemically modified carbons. The prepared catalysts were synthesized by impregnation method. The samples were annealed in two different regimes- in air and under vacuum. To examine adsorption efficiency of the samples BET method was used. All investigated catalysts supported on chemically modified carbons have higher specific surface area compared to the specific surface area of TiO2 supported catalysts, varying in the range 590÷620 m2/g. The method of synthesis of the precursors had influenced catalytic activity.

Keywords: Activated carbon, adsorption, copper, ozone decomposition, TiO2.

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Authors: K. Aranyarat, S. Maksasithorn, K. Suriye, S. Kunjara Na Ayudhya, J. Panpranot

Abstract:

The effect of N2 pretreatment on the catalytic activity of tungsten-based catalysts was investigated in the metathesis of ethylene and trans-2-butene at 450oC and atmospheric pressure. The presence of tungsten active species was confirmed by UV-Vis and Raman spectroscopy. Compared to the WO3-based catalysts treated in air, higher amount of WO4 2-tetrahedral species and lower amount of WO3 crystalline species were observed on the N2-treated ones. These contribute to the higher conversion of 2-butene and propylene selectivity during 10 h time-on-stream. Moreover, N2 treatment led to lower amount of coke formation as revealed by TPO of the spent catalysts.

Keywords: Metathesis, Pretreatment, Propylene, Tungsten.

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Authors: Jyh-Cherng Chen, Chang-Yong Liu

Abstract:

This study investigates the in-situ regeneration of deactivated Pt-Pd catalyst in a laboratory-scale catalysis reactor. Different regeneration conditions are tested and the activity and characteristics of regenerated catalysts are analyzed. Experimental results show that the conversion efficiencies of C3H6 by different regenerated Pt-Pd catalysts were significantly improved from 77%, 55% and 41% to 86%, 98% and 99%, respectively. The best regeneration conditions was 52ppm ozone, 500oC, and 10min. Regeneration temperature has more influences than ozone concentration and regeneration time. With the comparisons of characteristics of deactivated catalyst and regenerated catalyst, the major poison species (carbon, metals, chloride, and sulfate) on the spent catalysts can be effectively removed by ozone regeneration. 

Keywords: Catalyst, deactivated, ozone, regeneration.

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Authors: Pandian Elavarasan, Kishore Kondamudi, Sreedevi Upadhyayula

Abstract:

Ionic liquids are well known as green solvents, reaction media and catalysis. Here, three different sulfonic acid functional ionic liquids prepared in the laboratory are used as catalysts in alkylation of p-cresol with tert-butyl alcohol. The kinetics on each of the catalysts was compared and a kinetic model was developed based on the product distribution over these catalysts. The kinetic parameters were estimated using Marquadt's algorithm to minimize the error function. The Arrhenius plots show a curvature which is best interpreted by the extended Arrhenius equation.

Keywords: Alkylation, p-cresol, tert-butyl alcohol, kinetics, activation parameter, extended Arrhenius equation.

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Authors: Rana Th. A. Al-Rubaye, Burcin Atilgan, Richard J. Holmes, Arthur A. Garforth

Abstract:

Structured catalysts formed from the growth of zeolites on substrates is an area of increasing interest due to the increased efficiency of the catalytic process, and the ability to provide superior heat transfer and thermal conductivity for both exothermic and endothermic processes. However, the generation of structured catalysts represents a significant challenge when balancing the relationship variables between materials properties and catalytic performance, with the Na2O, H2O and Al2O3 gel composition paying a significant role in this dynamic, thereby affecting the both the type and range of application. The structured catalyst films generated as part of this investigation have been characterised using a range of techniques, including X-ray diffraction (XRD), Electron microscopy (SEM), Energy Dispersive X-ray analysis (EDX) and Thermogravimetric Analysis (TGA), with the transition from oxide-on-alloy wires to hydrothermally synthesised uniformly zeolite coated surfaces being demonstrated using both SEM and XRD. The robustness of the coatings has been ascertained by subjecting these to thermal cycling (ambient to 550oC), with the results indicating that the synthesis time and gel compositions have a crucial effect on the quality of zeolite growth on the FeCrAlloy wires. Finally, the activity of the structured catalyst was verified by a series of comparison experiments with standard zeolite Y catalysts in powdered pelleted forms.

Keywords: FeCrAlloy, Structured catalyst, and Zeolite Y.

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