Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 602

Search results for: platinum on alumina catalysts

602 Microkinetic Modelling of NO Reduction on Pt Catalysts

Authors: Vishnu S. Prasad, Preeti Aghalayam

Abstract:

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, platinum on alumina catalysts, selective catalytic reduction

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601 Single-Walled Carbon Nanotube Synthesis by Chemical Vapor Deposition Using Platinum-Group Metal Catalysts

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, platinum, rhodium, palladium

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600 Volatile Organic Compounds (VOCS) Destruction by Catalytic Oxidation for Environmental Applications

Authors: Mohammed Nasir Kajama, Ngozi Claribelle Nwogu, Edward Gobina

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Pt/γ-Al2O3 membrane catalysts were prepared via an evaporative-crystallization deposition method. The obtained Pt/γ-Al2O3 catalyst activity was tested after characterization (SEM-EDAX observation, BET measurement, permeability assessment) in the catalytic oxidation of selected volatile organic compound (VOC) i.e. propane, fed in mixture of oxygen. The VOC conversion (nearly 90%) obtained by varying the operating temperature showed that flow-through membrane reactor might do better in the abatement of VOCs.

Keywords: VOC combustion, flow-through membrane reactor, platinum supported alumina catalysts

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599 Alumina Supported Copper-manganese Catalysts for Combustion of Exhaust Gases: Catalysts Characterization

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

Abstract:

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 most of the investigations are focused on the hopcalite catalyst (CuMn2O4) as the best copper-manganese 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 continuous flow equipment with a four-channel isothermal stainless steel reactor. 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 (- 196 oС) 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, VOCs oxidation, combustion of exhaust gases

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598 Propane Dehydrogenation with Better Stability by a Modified Pt-Based Catalyst

Authors: Napat Hataivichian

Abstract:

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, CO-chemisorption 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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597 Alumina Supported Cu-Mn-Cr Catalysts for CO and VOCs oxidation

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

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

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

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596 Production of Renewable and Clean Bio-Fuel (DME) from Biomethanol over Copper Modified Alumina Catalyst

Authors: Ahmed I. Osman, Jehad K. Abu-Dahrieh, David W. Rooney, Jillian Thompson

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The effect of loading of copper on the catalytic performance of different alumina support during the dehydration of methanol to dimethyl ether (DME) was performed in a fixed bed reactor. There are two levels of loading; low loading (1, 2, 4 and 6% Cu wt/wt) and high loading (10 and 15% Cu wt/wt) on both AC350 (alumina catalyst calcined at 350) and AC550 (alumina catalyst calcined at 550), to study the effect of loading and the effect of the support during methanol dehydration to DME (MTD). The catalysts were characterized by TGA, XRD, BET, TPD-NH3, TEM and DRIFT-Pyridine. Under reaction conditions where the temperature ranged from 180-300˚C with a WHSV= 12.1 h-1 it was found that all the catalysts calcined at 550˚C showed higher activity than those calcined at 350˚C. In this study, the optimum catalyst was 6% Cu/AC550. This catalyst showed a high degree of stability, had one half activity of the pure catalyst (AC550) and double the activity of the optimum catalyst calcined at 350˚C (6% Cu/AC350). So, we recommended 6% Cu/AC550 for the production of DME from methanol.

Keywords: bio-fuel, nano composite catalyst, DME, Cu-Al2O3

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595 Method Validation for Determining Platinum and Palladium in Catalysts Using Inductively Coupled Plasma Optical Emission Spectrometry

Authors: Marin Senila, Oana Cadar, Thorsten Janisch, Patrick Lacroix-Desmazes

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The study presents the analytical capability and validation of a method based on microwave-assisted acid digestion for quantitative determination of platinum and palladium in catalysts using inductively coupled plasma optical emission spectrometry (ICP-OES). In order to validate the method, the main figures of merit such as limit of detection and limit of quantification, precision and accuracy were considered and the measurement uncertainty was estimated based on the bottom-up approach according to the international guidelines of ISO/IEC 17025. Limit of detections, estimated from blank signal using 3 s criterion, were 3.0 mg/kg for Pt and respectively 3.6 mg/kg for Pd, while limits of quantification were 9.0 mg/kg for Pt and respectively 10.8 mg/kg for Pd. Precisions, evaluated as standard deviations of repeatability (n=5 parallel samples), were less than 10% for both precious metals. Accuracies of the method, verified by recovery estimation certified reference material NIST SRM 2557 - pulverized recycled monolith, were 99.4 % for Pt and 101% for Pd. The obtained limit of quantifications and accuracy were satisfactory for the intended purpose. The paper offers all the steps necessary to validate the determination method for Pt and Pd in catalysts using inductively coupled plasma optical emission spectrometry.

Keywords: catalyst analysis, ICP-OES, method validation, platinum, palladium

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594 Comparison of Catalyst Support for High Pressure Reductive Amination

Authors: Tz-Bang Du, Cheng-Han Hsieh, Li-Ping Ju, Hung-Jie Liou

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Polyether amines synthesize by secondary hydroxyl polyether diol play an important role in epoxy hardener. The low molecular weight product is used in low viscosity and high transparent polyamine product for the logo, ground cover, especially for wind turbine blade, while the high molecular weight products are used in advanced agricultures such as a high-speed railway. High-pressure reductive amination process is required for producing these amines. In the condition of higher than 150 atm pressure and 200 degrees Celsius temperature, supercritical ammonia is used as a reactant and also a solvent. It would be a great challenge to select a catalyst support for such high-temperature alkaline circumstance. In this study, we have established a six-autoclave-type (SAT) high-pressure reactor for amination catalyst screening, which six experiment conditions with different temperature and pressure could be examined at the same time. We synthesized copper-nickel catalyst on different shaped alumina catalyst support and evaluated the catalyst activity for high-pressure reductive amination of polypropylene glycol (PPG) by SAT reactor. Ball type gamma alumina, ball type activated alumina and pellet type gamma alumina catalyst supports are evaluated in this study. Gamma alumina supports have shown better activity on PPG reductive amination than activated alumina support. In addition, the catalysts are evaluated in fixed bed reactor. The diamine product was successfully synthesized via this catalyst and the strength of the catalysts is measured. The crush strength of blank supports is about 13.5 lb for both gamma alumina and activated alumina. The strength increases to 20.3 lb after synthesized to be copper-nickel catalyst. After test in the fixed bed high-pressure reductive amination process for 100 hours, the crush strength of the used catalyst is 3.7 lb for activated alumina support, 12.0 lb for gamma alumina support. The gamma alumina is better than activated alumina to use as catalyst support in high-pressure reductive amination process.

Keywords: high pressure reductive amination, copper nickel catalyst, polyether amine, alumina

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593 Mordenite as Catalyst Support for Complete Volatile Organic Compounds Oxidation

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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592 Alumina Supported Cu-Mn-La Catalysts for CO and VOCs Oxidation

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 Cu1.5Mn1.5O4. 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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591 The Study and the Use of the Bifunctional Catalyst Pt/Re for Obtaining High Octane Number of the Gasoline

Authors: Menouar Hanafi

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The original function of the process of platforming is to develop heavy naphtha (HSRN), coming from the atmospheric unit of distillation with a weak octane number (NO=44), to obtain a mixture of fuels â number octane raised by catalytically supporting specific groups of chemical reactions. The installation is divided into two sections: Section hydrobon. Section platforming. The rafinat coming from the bottom of column 12C2 to feed the section platforming, is divided into two parts whose flows are controlled and mixed with gas rich in hydrogen. Bottom of the column, we obtain stabilized reformat which is aspired by there pump to ensure the heating of the column whereas a part is sent towards storage after being cooled by the air cooler and the condenser. In catalytic catalyst of reforming, there is voluntarily associated a hydrogenating function-dehydrogenating, brought by platinum deposited, with an acid function brought by the alumina support (Al 2 0 3). The mechanism of action of this bifunctional catalyst depends on the severity of the operation, of the quality of the load and the type of catalyst. The catalyst used in the catalytic process of reforming is a very elaborate bifunctional catalyst whose performances are constantly improved thanks to the experimental research supported on an increasingly large comprehension of the phenomena. The American company Universel 0i1 petroleum (UOP) marketed several series of bimetallic catalysts such as R16, R20, R30, and R62 consisted Platinum/Rhenium on an acid support consisted the alumina added with a halogenous compound (chlorine).

Keywords: platforming, amelioration, octane number, catalyst

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590 Alumina Supported Copper-Manganese Catalysts for Combustion of Exhaust Gases: Effect of Preparation Method

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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589 One Pot Synthesis of Ultrasmall NiMo Catalysts Supported on Amorphous Alumina with Enhanced type 2 Sites for Hydrodesulfurization Reaction: A Combined Experimental and Theoretical Study

Authors: Shalini Arora, Sri Sivakumar

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The deep removal of high molecular weight sulphur compounds (e.g., 4,6, dimethyl dibenzothiophene) is challenging due to their steric hindrance. Hydrogenation desulfurization (HYD) pathway is the main pathway to remove these sulfur compounds, and it is mainly governed by the number of type 2 sites. The formation of type 2 sites can be enhanced by modulating the pore structure and the interaction between the active metal and support. To this end, we report the enhanced HDS catalytic activity of ultrasmall NiMo supported on amorphous alumina (A-Al₂O₃) catalysts by one pot colloidal synthesis method followed by calcination and sulfidation. The amorphous alumina (A-Al₂O₃) was chosen as the support due to its lower surface energy, better physicochemical properties, and enhanced acidic sites (due to the dominance of tetra and penta coordinated [Al] sites) than crystalline alumina phase. At 20% metal oxide composition, NiMo supported on A-Al₂O₃ catalyst showed 1.4 and 1.2 times more reaction rate constant and turn over frequency (TOF) respectively than the conventional catalyst (wet impregnated NiMo catalysts) for HDS reaction of dibenzothiophene reactant molecule. A-Al₂O₃ supported catalysts represented enhanced type 2 sites formation (because this catalystpossesses higher sulfidation degree (80%) and NiMoS sites (19.3 x 10¹⁷ sites/mg) with desired optimum stacking degree (2.5) than wet impregnated catalyst at same metal oxide composition 20%) along with higher active metal dispersion, Mo edge site fraction. The experimental observations were also supported by DFT simulations. Lower heat of adsorption (< 4.2 ev for MoS2 interaction and < 3.15 ev for Ni doped MoS2 interaction) values for A-Al₂O₃ confirmed the presence of weaker metal-support interaction in A-Al₂O₃ in contrast to crystalline ℽ-Al₂O3. The weak metal-support interaction for prepared catalysts clearly suggests the higher formation of type 2 sites which leads to higher catalytic activity for HDS reaction.

Keywords: amorphous alumina, colloidal, desulfurization, metal-support interaction

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588 Structure-Activity Relationship of Gold Catalysts on Alumina Supported Cu-Ce Oxides for CO and Volatile Organic Compound Oxidation

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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587 Carbon-Foam Supported Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

Authors: Albert Mufundirwa, Satoru Yoshioka, K. Ogi, Takeharu Sugiyama, George F. Harrington, Bretislav Smid, Benjamin Cunning, Kazunari Sasaki, Akari Hayashi, Stephen M. Lyth

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Polymer electrolyte membrane fuel cells (PEMFCs) are electrochemical energy conversion devices used for portable, residential and vehicular applications due to their low emissions, high efficiency, and quick start-up characteristics. However, PEMFCs generally use expensive, Pt-based electrocatalysts as electrode catalysts. Due to the high cost and limited availability of platinum, research and development to either drastically reduce platinum loading, or replace platinum with alternative catalysts is of paramount importance. A combination of high surface area supports and nano-structured active sites is essential for effective operation of catalysts. We synthesize carbon foam supports by thermal decomposition of sodium ethoxide, using a template-free, gram scale, cheap, and scalable pyrolysis method. This carbon foam has a high surface area, highly porous, three-dimensional framework which is ideal for electrochemical applications. These carbon foams can have surface area larger than 2500 m²/g, and electron microscopy reveals that they have micron-scale cells, separated by few-layer graphene-like carbon walls. We applied this carbon foam as a platinum catalyst support, resulting in the improved electrochemical surface area and mass activity for the oxygen reduction reaction (ORR), compared to carbon black. Similarly, silver-decorated carbon foams showed higher activity and efficiency for electrochemical carbon dioxide conversion than silver-decorated carbon black. A promising alternative to Pt-catalysts for the ORR is iron-impregnated nitrogen-doped carbon catalysts (Fe-N-C). Doping carbon with nitrogen alters the chemical structure and modulates the electronic properties, allowing a degree of control over the catalytic properties. We have adapted our synthesis method to produce nitrogen-doped carbon foams with large surface area, using triethanolamine as a nitrogen feedstock, in a novel bottom-up protocol. These foams are then infiltrated with iron acetate (FeAc) and pyrolysed to form Fe-N-C foams. The resulting Fe-N-C foam catalysts have high initial activity (half-wave potential of 0.68 VRHE), comparable to that of commercially available Pt-free catalysts (e.g., NPC-2000, Pajarito Powder) in acid solution. In alkaline solution, the Fe-N-C carbon foam catalysts have a half-wave potential of 0.89 VRHE, which is higher than that of NPC-2000 by almost 10 mVRHE, and far out-performing platinum. However, the durability is still a problem at present. The lessons learned from X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements will be used to carefully design Fe-N-C catalysts for higher performance PEMFCs.

Keywords: carbon-foam, polymer electrolyte membrane fuel cells, platinum, Pt-free, Fe-N-C, ORR

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586 The Catalytic Properties of PtSn/Al2O3 for Acetic Acid Hydrogenation

Authors: Mingchuan Zhou, Haitao Zhang, Hongfang Ma, Weiyong Ying

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Alumina supported platinum and tin catalysts with different loadings of Pt and Sn were prepared and characterized by low temperature N2 adsorption/desorption, H2-temperature programed reduction and CO pulse chemisorption. Pt and Sn below 1% loading were suitable for acetic acid hydrogenation. The best performance over 0.75Pt1Sn/Al2O3 can reach 87.55% conversion of acetic acid and 47.39% selectivity of ethanol. The operating conditions of acetic acid hydrogenation over 1Pt1Sn/Al2O3 were investigated. High reaction temperature can enhance the conversion of acetic acid, but it decreased total selectivity of ethanol and acetyl acetate. High pressure and low weight hourly space velocity were beneficial to both conversion of acetic acid and selectivity to ethanol.

Keywords: acetic acid, hydrogenation, operating condition, PtSn

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585 Effect of Water Addition on Catalytic Activity for CO2 Purification from Oxyfuel Combustion

Authors: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin

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Oxyfuel combustion is a promising method that enables to obtain a CO2 rich stream, with water vapor ( ̴10%), unburned components such as CO and NO, which must be cleaned before the use of CO2. Our objective is then the final treatment of CO and NO by catalysis. Three-way catalysts are well-developed material for simultaneous conversion of NO, CO and hydrocarbons. Pt and/or Rh ensure a quasi-complete removal of NOx, CO and HC and there is also a growing interest in partly replacing Pt with less-expensive Pd. The use of alumina and ceria as support ensures, respectively, the stabilization of such species in active state and discharging or storing oxygen to control the oxidation of CO and HC and the reduction of NOx. In this work, we will compare different metals (Pd, Rh and Pt) supported on Al2O3 and CeO2, for CO2 purification from oxyfuel combustion. The catalyst must reduce NO by CO in an oxidizing environment, in the presence of CO2 rich stream and resistant to water. In this study, Al2O3 and CeO2 were used as support materials of the catalysts. 1wt% M/Support where M = Pd, Rh or Pt catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2], rhodium [Rh(NO3)3] and platinum [Pt(NO2)2(NO3)2]. Materials were characterized by BET surface area, H2 chemisorption, and TEM. Catalytic activity was evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200 mL.min−1, with same GHSV (2.24x104 h-1). The catalytic performances of the samples were investigated with and without water. It shows that the total oxidation of CO occurred over the different materials. This study evidenced an important effect of the nature of the metals, supports and the presence or absence of H2O during the reduction of NO by CO in oxyfuel combustions conditions. Rh based catalysts show that the addition of water has a very positive influence especially on the Rh catalyst on CeO2. Pt based catalysts keep a good activity despite the addition of water on the both supports studied. For the NO reduction, addition of water act as a poison with Pd catalysts. The interesting results of Rh based catalysts with water can be explained by a production of hydrogen through the water gas shift reaction. The produced hydrogen acts as a more effective reductant than CO for NO removal. Furthermore, in TWCs, Rh is the main component responsible for NOx reduction due to its especially high activity for NO dissociation. Moreover, cerium oxide is a promotor for WGSR.

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis

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584 Alumina Supported Copper-Manganese-Cobalt Catalysts for CO and VOCs Oxidation

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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583 Water Gas Shift Activity of PtBi/CeO₂ Catalysts for Hydrogen Production

Authors: N. Laosiripojana, P. Tepamatr

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The influence of bismuth on the water gas shift activities of Pt on ceria was studied. The flow reactor was used to study the activity of the catalysts in temperature range 100-400°C. The feed gas composition contains 5%CO, 10% H₂O and balance N₂. The total flow rate was 100 mL/min. The outlet gas was analyzed by on-line gas chromatography with thermal conductivity detector. The catalytic activities of bimetallic 1%Pt1%Bi/CeO₂ catalyst were greatly enhanced when compared with the activities of monometallic 2%Pt/CeO₂ catalyst. The catalysts were characterized by X-ray diffraction (XRD), Temperature-Programmed Reduction (TPR) and surface area analysis. X-ray diffraction pattern of Pt/CeO₂ and PtBi/CeO₂ indicated slightly shift of diffraction angle when compared with pure ceria. This result was due to strong metal-support interaction between platinum and ceria solid solution, causing conversion of Ce⁴⁺ to larger Ce³⁺. The distortions inside ceria lattice structure generated strain into the oxide lattice and facilitated the formation of oxygen vacancies which help to increase water gas shift performance. The H₂-Temperature Programmed Reduction indicated that the reduction peak of surface oxygen of 1%Pt1%Bi/CeO₂ shifts to lower temperature than that of 2%Pt/CeO₂ causing the enhancement of the water gas shift activity of this catalyst. Pt played an important role in catalyzing the surface reduction of ceria and addition of Bi alter the reduction temperature of surface ceria resulting in the improvement of the water gas shift activity of Pt catalyst.

Keywords: bismuth, platinum, water gas shift, ceria

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582 Catalytic Combustion of Methane over Pd-Meox-CeO₂/Al₂O₃ (Me= Co or Ni) Catalysts

Authors: Silviya Todorova, Anton Naydenov, Ralitsa Velinova, Alexander Larin

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Catalytic combustion of methane has been extensively investigated for emission control and power generation during the last decades. The alumina-supported palladium catalyst is widely accepted as the most active catalysts for catalytic combustion of methane. The activity of Pd/Al₂O₃ decreases during the time on stream, especially underwater vapor. The following order of activity in the reaction of complete oxidation of methane was established: Co₃O₄> CuO>NiO> Mn₂O₃> Cr₂O₃. It may be expected that the combination between Pd and these oxides could lead to the promising catalysts in the reaction of complete methane. In the present work, we investigate the activity of Pd/Al₂O₃ catalysts promoted with other metal oxides (MOx; M= Ni, Co, Ce). The Pd-based catalysts modified by metal oxide were prepared by sequential impregnation of Al₂O₃ with aqueous solutions of Me(NO₃)₂.6H₂O and Pd(NO₃)₂H₂O. All samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). An improvement of activity was observed after modification with different oxides. The results demonstrate that the Pd/Al₂O₃ catalysts modified with Co and Ce by impregnation with a common solution of respective salts, exhibit the most promising catalytic activity for methane oxidation. Most probably, the presence of Co₃O₄ and CeO₂ on catalytic surface increases surface oxygen and therefore leads to the better reactivity in methane combustion.

Keywords: methane combustion, palladium, Co-Ce, Ni-Ce

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581 Preparation and Characterization of α–Alumina with Low Sodium Oxide

Authors: Gyung Soo Jeon, Hong Bae Kim, Chi Jung Oh

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In order to prepare the α-alumina with low content of sodium oxide from aluminum trihydroxide as a reactant, three kinds of methods were employed as follows; the mixture of Chamotte (aggregate composed of silica and alumina), ammonium chloride and aluminum fluoride with aluminum trihydroxide under 1600°C, respectively. The sodium oxide in α-alumina produced above methods was analyzed by XRF and the particle size distribution was determined by particle size analyzer, and the specific surface area of α-alumina was measured by BET method, and phase of α-alumina produced was confirmed by XRD. Acknowledgement: This research was supported by Development Program of Technical Innovation funded by Korea Technology and Information Promotion Agency for SMEs (KTIP-2016-S2401821).

Keywords: α-alumina, sodium oxide, aluminum trihydroxide, Chamotte, ammonium chloride, aluminum fluoride

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580 Use of Cobalt Graphene in Place of Platnium in Catalytic Converter

Authors: V. Srinivasan, S. M. Sriram Nandan

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Today in the modern world the most important problem faced by the mankind is increasing the pollution in a very high rate. It affects the ecosystem of the environment and also aids to increase the greenhouse effect. The exhaust gases from the automobile is the major cause of a pollution. Automobiles have increased to a large number which has increased the pollution of our world to an alarming rate. There are two methods of controlling the pollution namely, pre-pollution control method and post-pollution control method. This paper is based on controlling the emission by post-pollution control method. The ratio of surface area of nanoparticles to the volume of the nanoparticles is inversely proportional to the radius of the nanoparticles. So decreasing the radius, this ratio is leading resulting in an increased rate of reaction and thus the concentration of the pollution is decreased. To achieve this objective, use of cobalt-graphene element is proposed. The proposed method is mainly to decrease the cost of platinum as it is expensive. This has a longer life than the platinum-based catalysts.

Keywords: automobile emissions, catalytic converter, cobalt-graphene, replacement of platinum

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579 Percentages of Alumina Phase and Different Ph on The Ha- Al2o3 Nano Composite

Authors: S. Tayyebi, F. Mirjalili, H. Samadi, A. Nemati

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In this study, hydroxyapatite-Alumina nano composite powder, containing 15,20 and 25% weight percent of reinforced alumina were prepared by chemical precipitation from the reaction between calcium nitrate tetrahydrate and di-ammonium hydrogen phosphate with ratio of Ca / p = 1.67 and different percentage of aluminum nitrate nona hydrate in different pH of 9,10 and 11. The microstructure and thermal stability of samples were measured by X-ray diffraction (XRD), infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM). The results showed that the presence of reinforced alumina phase reduced the degree of crystallinity of hydroxyapatite phase and increased its decomposition to tricalcium phosphate phase. Microstructural analysis showed that the hydroxyapatite-alumina nano composite powder was obtained with spherical shape and size of less than 100 nm.

Keywords: biomaterial, hydroxyapatite, alumina, nano composite, precipitation method

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578 Adsorption: A Decision Maker in the Photocatalytic Degradation of Phenol on Co-Catalysts Doped TiO₂

Authors: Dileep Maarisetty, Janaki Komandur, Saroj S. Baral

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In the current work, photocatalytic degradation of phenol was carried both in UV and visible light to find the slowest step that is limiting the rate of photo-degradation process. Characterization such as XRD, SEM, FT-IR, TEM, XPS, UV-DRS, PL, BET, UPS, ESR and zeta potential experiments were conducted to assess the credibility of catalysts in boosting the photocatalytic activity. To explore the synergy, TiO₂ was doped with graphene and alumina. The orbital hybridization with alumina doping (mediated by graphene) resulted in higher electron transfer from the conduction band of TiO₂ to alumina surface where oxygen reduction reactions (ORR) occur. Besides, the doping of alumina and graphene introduced defects into Ti lattice and helped in improving the adsorptive properties of modified photo-catalyst. Results showed that these defects promoted the oxygen reduction reactions (ORR) on the catalyst’s surface. ORR activity aims at producing reactive oxygen species (ROS). These ROS species oxidizes the phenol molecules which is adsorbed on the surface of photo-catalysts, thereby driving the photocatalytic reactions. Since mass transfer is considered as rate limiting step, various mathematical models were applied to the experimental data to probe the best fit. By varying the parameters, it was found that intra-particle diffusion was the slowest step in the degradation process. Lagergren model gave the best R² values indicating the nature of rate kinetics. Similarly, different adsorption isotherms were employed and realized that Langmuir isotherm suits the best with tremendous increase in uptake capacity (mg/g) of TiO₂-rGO-Al₂O₃ as compared undoped TiO₂. This further assisted in higher adsorption of phenol molecules. The results obtained from experimental, kinetic modelling and adsorption isotherms; it is concluded that apart from changes in surface, optoelectronic and morphological properties that enhanced the photocatalytic activity, the intra-particle diffusion within the catalyst’s pores serve as rate-limiting step in deciding the fate of photo-catalytic degradation of phenol.

Keywords: ORR, phenol degradation, photo-catalyst, rate kinetics

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577 Effect of Catalyst Preparation Method on Dry Reforming of Methane with Supported and Promoted Catalysts

Authors: Sanjay P. Gandhi, Sanjay S. Patel

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Dry (CO2) reforming of methane (DRM) is both scientific and industrial importance. In recent decades, CO2 utilization has become increasingly important in view of the escalating global warming phenomenon. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer–Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800–1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The catalysts used are often composed of transition Methods like Nickel, supported on metallic and non-metallic oxides such as alumina and silica. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. CO2 reforming methane over promoted catalyst was studied. The influence of ZrO2, CeO2 and the behavior of Ni-Al2O3 Catalyst, prepare by wet-impregnation and Co-precipitated method was studied. XRD, BET Analysis for different promoted and unprompted Catalyst was studied.

Keywords: CO2 reforming of methane, Ni catalyst, promoted and unprompted catalyst, effect of catalyst preparation

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576 Optimization of Platinum Utilization by Using Stochastic Modeling of Carbon-Supported Platinum Catalyst Layer of Proton Exchange Membrane Fuel Cells

Authors: Ali Akbar, Seungho Shin, Sukkee Um

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The composition of catalyst layers (CLs) plays an important role in the overall performance and cost of the proton exchange membrane fuel cells (PEMFCs). Low platinum loading, high utilization, and more durable catalyst still remain as critical challenges for PEMFCs. In this study, a three-dimensional material network model is developed to visualize the nanostructure of carbon supported platinum Pt/C and Pt/VACNT catalysts in pursuance of maximizing the catalyst utilization. The quadruple-phase randomly generated CLs domain is formulated using quasi-random stochastic Monte Carlo-based method. This unique statistical approach of four-phase (i.e., pore, ionomer, carbon, and platinum) model is closely mimic of manufacturing process of CLs. Various CLs compositions are simulated to elucidate the effect of electrons, ions, and mass transport paths on the catalyst utilization factor. Based on simulation results, the effect of key factors such as porosity, ionomer contents and Pt weight percentage in Pt/C catalyst have been investigated at the represented elementary volume (REV) scale. The results show that the relationship between ionomer content and Pt utilization is in good agreement with existing experimental calculations. Furthermore, this model is implemented on the state-of-the-art Pt/VACNT CLs. The simulation results on Pt/VACNT based CLs show exceptionally high catalyst utilization as compared to Pt/C with different composition ratios. More importantly, this study reveals that the maximum catalyst utilization depends on the distance spacing between the carbon nanotubes for Pt/VACNT. The current simulation results are expected to be utilized in the optimization of nano-structural construction and composition of Pt/C and Pt/VACNT CLs.

Keywords: catalyst layer, platinum utilization, proton exchange membrane fuel cell, stochastic modeling

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575 Preparation and Characterization of Mixed Cu-Ag-Pd Oxide Supported Catalysts for Complete Catalytic Oxidation of Methane

Authors: Ts. Lazarova, V. Tumbalev, S. Atanacova-Vladimirova, G. Ivanov, A. Naydenov, D. Kovacheva

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Methane is a major Greenhouse Gas (GHG) that accounts for 14% of the world’s total amount of GHG emissions, originating mainly from agriculture, Coal mines, land fields, wastewater and oil and gas facilities. Nowadays the problem caused by the methane emissions has been a subject of an increased concern. One of the methods for neutralization of the methane emissions is it's complete catalytic oxidation. The efforts of the researchers are focused on the development of new types of catalysts and optimizing the existing catalytic systems in order to prevent the sintering of the palladium, providing at the same time a sufficient activity at temperatures below 500oC. The aim of the present work is to prepare mixed Cu-Ag-Pd oxide catalysts supported on alumina and to test them for methane complete catalytic oxidation. Cu-Ag-Pd/Al2O3 were prepared on a γ-Al2O3 (BET surface area = 220 m2/g) by the incipient wetness method using the corresponding metal nitrates (Cu:Ag = 90:10, Cu:Pd =97:3, Cu:Ag:Pd= 87:10:3) as precursors. A second set of samples were prepared with addition of urea to the metal nitrate solutions with the above mentioned ratios assuming increased dispersivity of the catalysts. The catalyst samples were dried at 100°C for 3 hours and calcined at 550°C for 30 minutes. Catalysts samples were characterized using X-ray diffraction (XRD), low temperature adsorption of nitrogen (BET) and scanning electron microscopy (SEM). The catalytic activity tests were carried out in a continuous flow type of reactor at atmospheric pressure. The effect of catalyst aging at 500 oC for 120 h on the methane combustion activity was also investigated. The results clearly indicate the synergetic effect of Ag and Pd on the catalytic activity.

Keywords: catalysts, XRD, BET, SEM, catalytic oxidation

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574 Properties of Hot-Pressed Alumina-Graphene Composites

Authors: P. Rutkowski, G. Górny, L. Stobierski, D. Zientara, W. Piekarczyk, K. Tran

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The polycrystalline dense alumina shows thermal conductivity about 30 W/mK and very high electrical resistivity. These last two properties can be modified by introducing commercial relatively cheap graphene nanoparticles which, as two-dimensional flakes show very high thermal and electrical properties. The aim of this work is to show that it is possible to manufacture the anisotropic alumina-graphene material with directed multilayer graphene particles. Such materials can show the anisotropic properties mentioned before.

Keywords: alumina, composite, hot-pressed, graphene, properties

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573 A Study of the Alumina Distribution in the Lab-Scale Cell during Aluminum Electrolysis

Authors: Olga Tkacheva, Pavel Arkhipov, Alexey Rudenko, Yurii Zaikov

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The aluminum electrolysis process in the conventional cryolite-alumina electrolyte with cryolite ratio of 2.7 was carried out at an initial temperature of 970 °C and the anode current density of 0.5 A/cm2 in a 15A lab-scale cell in order to study the formation of the side ledge during electrolysis and the alumina distribution between electrolyte and side ledge. The alumina contained 35.97% α-phase and 64.03% γ-phase with the particles size in the range of 10-120 μm. The cryolite ratio and the alumina concentration were determined in molten electrolyte during electrolysis and in frozen bath after electrolysis. The side ledge in the electrolysis cell was formed only by the 13th hour of electrolysis. With a slight temperature decrease a significant increase in the side ledge thickness was observed. The basic components of the side ledge obtained by the XRD phase analysis were Na3AlF6, Na5Al3F14, Al2O3, and NaF.5CaF2.AlF3. As in the industrial cell, the increased alumina concentration in the side ledge formed on the cell walls and at the ledge-electrolyte-aluminum three-phase boundary during aluminum electrolysis in the lab cell was found (FTP No 05.604.21.0239, IN RFMEFI60419X0239).

Keywords: alumina distribution, aluminum electrolyzer, cryolie-alumina electrolyte, side ledge

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