Search results for: supported catalysts

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

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In the recent 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: Jingyu Zhou, Hongfang Ma, Haitao Zhang, Weiyong Ying

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High surface area MgAl2O4 supported Nickel catalysts with PVA loadings varying from 0% to 15% were prepared by precipitation and impregnation method. The catalysts were characterized by low temperature N2 adsorption/desorption, X-ray diffraction and H2 temperature programmed reduction. Compared with Ni/γ-Al2O3 catalyst, Ni/MgAl2O4 catalysts exhibited higher activity and selectivity in high temperature. Among the catalysts, Ni/MgAl2O4-5P with 5 wt% PVA showed the best performance, and achieved 95% CO conversion and 96% CH4 selectivity at 600°C, 2.0 MPa, and a WHSV of 12,000 mL·g⁻¹.h⁻¹. It also maintained good stability in 50h life test.

Keywords: methanation, MgAl2O4 support, PVA, high surface area

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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 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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Authors: Liang-Yi Lin, Hsunling Bai

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In this work, transition metal (metal= Co, Fe, Ni, Cu, and Mn) modified cerium oxide catalysts supported on mesoporous aluminosilicate particles (Ce/Al-MSPs) were prepared using waste silicate as the precursors through aerosol-assisted flow process, and their catalytic performances were investigated for acetone incineration. Tests on the bimetallic Ce/Al-MSPs and Mn/Al-MSPs and trimetallic Mn-Ce, Fe-Ce, Co-Ce, Ni-Ce, and Cu-Ce/Al-MSPs in the temperature range of 100-300 oC demonstrated that Ce was the main active metal while Mn acted as a suitable promoter in acetone incineration reactions. Among tested catalysts, Mn-Ce/Al-MSPs with a Mn/Ce molar ratio of 2/1 exhibited the highest acetone catalytic activity. Moreover, the synergetic effect was observed for trimetallic Mn-Ce/Al-MSPs on the acetone removal as compared to the bimetallic Ce/Al-MSPs or Mn/Al-MSPs catalysts.

Keywords: acetone, catalytic oxidation, cerium oxide, mesoporous silica

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Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov

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

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

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Authors: Hilal Kivrak, Aykut ÇağLar, Nahit Aktaş, Ali Osman Solak

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At present, Cd/TiO₂ and CdTe/TiO₂ catalysts are prepared via sodium borohydride (NaBH4) reduction method. These catalysts are characterized by fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). These Cd/TiO₂ and CdTe/TiO₂ are employed as catalysts for the photocatalytic oxidation of glucose. Cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) measurements are used to investigate their glucose electrooxidation activities of catalysts at long and under UV illumination (ʎ=354 nm). CdTe/TiO₂ catalyst is showed the best photocatalytic glucose electrooxidation activity compared to Cd/TiO₂ catalyst.

Keywords: cadmium, NaBH4 reduction method, photocatalytic glucose electrooxidation, Tellerium, TiO2

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Authors: Jian Huang, Weixin Qian, Hongfang Ma, Haitao Zhang, Weiyong Ying

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Cobalt catalysts were supported on extruded silica carrier and different-type (SiO₂, γ-Al₂O₃) commercial supports with different shapes and sizes to produce heavy hydrocarbons for Fischer-Tropsch synthesis. The catalysts were characterized by N₂ physisorption and H₂-TPR. The catalytic performance of the catalysts was tested in a fixed bed reactor. The results of Fischer-Tropsch synthesis performance showed that the cobalt catalyst supported on spherical silica supports displayed a higher activity and a higher selectivity to C₅⁺ products, due to the fact that the active components were only distributed in the surface layer of spherical carrier, and the influence of gas diffusion restriction on catalytic performance was weakened. Therefore, it can be concluded that the eggshell cobalt catalyst was superior to precious metals modified catalysts in the synthesis of heavy hydrocarbons.

Keywords: fischer-tropsch synthesis, cobalt catalyst, support shape, heavy hydrocarbons

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Authors: Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Petya Cv. Petrova, Georgi V. Avdeev, Diana D. Nihtianova, Krasimir I. Ivanov, Tatyana T. Tabakova

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Recently, copper and manganese-containing systems are recognized as active and selective catalysts in many oxidation reactions. The main idea of this study is to obtain more information about γ-Al₂O₃ supported Cu-La catalysts and to evaluate their activity to simultaneous oxidation of CO, CH₃OH and dimethyl ether (DME). The catalysts were synthesized by impregnation of support with a mixed aqueous solution of nitrates of copper, manganese and lanthanum under different conditions. XRD, HRTEM/EDS, TPR and thermal analysis were performed to investigate catalysts’ bulk and surface properties. The texture characteristics were determined by Quantachrome Instruments NOVA 1200e specific surface area and pore analyzer. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor in a wide temperature range. On the basis of XRD analysis and HRTEM/EDS, it was concluded that the active component of the mixed Cu-Mn-La/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio and consisted of at least four compounds – CuO, La₂O₃, MnO₂ and Cu_1.5Mn_1.5O₄. A homogeneous distribution of the active component on the carrier surface was found. The chemical composition strongly influenced catalytic properties. This influence was quite variable with regards to the different processes.

Keywords: Cu-Mn-La oxide catalysts, carbon oxide, VOCs, deep oxidation

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Authors: Neha Thakur, Pravin S. More

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The interaction of CO, H2 and LPG with Cu-dosed SnO2 catalysts was studied by means of Fourier transform infrared spectroscopy (FTIR). With increasing Cu loading, pronounced and progressive red shifts of the C–O stretching frequency associated with molecular CO adsorbed on the Cu/SnO2 component were observed. This decrease in n(CO) correlates with enhancement of CO dissociation at higher temperatures on Cu promoted SnO2 catalysts under conditions, where clean Cu is almost ineffective. In the conclusion, the capability of our technique is discussed, and a technique for enhancing the sensitivity in our technique is proposed.

Keywords: FTIR, spectroscopic, dissociation, n(CO)

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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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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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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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Authors: Nathalie Elia, Samer Aouad, Jane Estephane, Christophe Poupin, Bilal Nsouli, Edmond Abi Aad

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Carbon dioxide is one of the main contributors to greenhouse effect and hence to climate change. As a result, the methanation reaction CO2(g) + 4H2(g) →CH4(g) + 2H2O (ΔH°298 = -165 kJ/mol), also known as Sabatier reaction, has received great interest as a process for the valorization of the greenhouse gas CO2 into methane which is a hydrogen-carrier gas. The methanation of CO2 is an exothermic reaction favored at low temperature and high pressure. However, this reaction requires a high energy input to activate the very stable CO2 molecule, and exhibits serious kinetic limitations. Consequently, the development of active and stable catalysts is essential to overcome these difficulties. Catalytic methanation of CO2 has been studied using catalysts containing Rh, Pd, Ru, Co and Ni on various supports. Among them, the Ni-based catalysts have been extensively investigated under various conditions for their comparable methanation activity with highly improved cost-efficiency. The addition of promoters are common strategies to increase the performance and stability of Ni catalysts. In this work, a small amount of Ru was used as a promoter for Ni catalysts supported on ceria and tested in the CO2 methanation reaction. The nickel loading was 5 wt. % and ruthenium loading is 0.5wt. %. The catalysts were prepared by successive impregnation method using Ni(NO3)2.6H2O and Ru(NO)(NO3)3 as precursors. The calcined support was impregnated with Ni(NO3)2.6H2O, dried, calcined at 600°C for 4h, and afterward, was impregnated with Ru(NO)(NO3)3. The resulting solid was dried and calcined at 600°C for 4 h. Supported monometallic catalysts were prepared likewise. The prepared solids Ru(0.5%)/CeO2, Ni(5%)/CeO2 and Ru(0.5%)-Ni(5%)/CeO2 were then reduced prior to the catalytic test under a flow of 50% H2/Ar (50 ml/min) for 4h at 500°C. Finally, their catalytic performances were evaluated in the CO2 methanation reaction, in the temperature range of 100–350°C by using a gaseous mixture of CO2 (10%) and H2 (40%) in Ar balanced at a total flow rate of 100 mL/min. The effect of pressure on the CO2 methanation was studied by varying the pressure between 1 and 10 bar. The various catalysts showed negligible CO2 conversion at temperatures lower than 250°C. The conversion of CO2 increases with increasing reaction temperature. The addition of Ru as promoter to Ni/CeO2 improved the CO2 methanation. It was shown that the CO2 conversion increases from 15 to 70% at 350°C and 1 bar. The effect of pressure on CO2 conversion was also studied. Increasing the pressure from 1 to 5 bar increases the CO2 conversion from 70% to 87%, while increasing the pressure from 5 to 10 bar increases the CO2 conversion from 87% to 91%. Ru–Ni catalysts showed excellent catalytic performance in the methanation of carbon dioxide with respect to Ni catalysts. Therefore the addition of Ru onto Ni catalysts improved remarkably the catalytic activity of Ni catalysts. It was also found that the pressure plays an important role in improving the CO2 methanation.

Keywords: CO2, methanation, nickel, ruthenium

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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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Authors: Ali Zazi, Ouiza Cherifi

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The Catalysts materials Ni-SiO₂, Ni-Co-SiO₂ and Ni-Ce-SiO₂ were synthetized by classical method impregnation and supported by silica. This involves combing the silica with an adequate rate of the solution of nickel nitrates, or nickel nitrate and cobalt nitrate, or nickel nitrate and cerium nitrate, mixed, dried and calcined at 700 ° c. These catalysts have been characterized by different physicochemical analysis techniques. The atomic absorption spectrometry indicates that the real contents of nickel, cerium and cobalt are close to the theoretical contents previously assumed, which let's say that the nitrate solutions have impregnated well the silica support. The BET results show that the surface area of the specific surfaces decreases slightly after impregnation with nickel nitrates or Co and Ce metals and a further slight decrease after the reaction. This is likely due to coke deposition. X-ray diffraction shows the presence of the different SiO₂ and NiO phases for all catalysts—theCoO phase for that promoted by Co and the Ce₂O₂ phase for that promoted by Ce. The methane steam reforming reaction was carried out on a quartz reactor in a fixed bed. Reactants and products of the reaction were analyzed by a gas chromatograph. This study shows that the metal addition of Cerium or Cobalt improves the majority of the catalytic performance of Ni for the steam reforming reaction of methane. And we conclude the classification of our Catalysts in order of decreasing activity and catalytic performances as follows: Ni-Ce / SiO₂ >Ni-Co / SiO₂> Ni / SiO₂ .

Keywords: cerium, cobalt, heterogeneous catalysis, hydrogen, methane, steam reforming, synthesis gas

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Authors: Talat Baran

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The Suzuki C(sp2)-C(sp2) coupling reaction is considered to be one of the best ways for the synthesis of biaryl compounds. There are many studies reporting the catalytic performance of palladium catalyst in Suzuki coupling reactions. Natural biopolymer (such as zeolite, carbon, silica, and chitosan) supporting catalysts have been lately attracted interest because of their low-cost, nontoxicity, and eco-friendliness. One of the most important natural biopolymer is cellulose, which is widely considered as an eco-friendly biopolymer due to its biodegradable, non-toxic and renewable nature. In this study, (1) cellulose supported Pd(II) catalyst was synthesized (2) its chemical structure was characterized by FT-IR, SEM/EDAX, XRD, TG-DTG, ICP-OES techniques (3) to investigate the performance of the catalyst in Suzuki coupling reactions by using microwave irradiation technique (4) reusability of the catalyst was done under optimum conditions. This cellulose supported Pd(II) catalyst exhibited high selectivity and efficiency in Suzuki coupling reactions under mild conditions (50°C). High TON and TOF values were recorded for the catalyst. Also, the reusability tests showed the catalysts could be used for several times in consequence of reusability tests.

Keywords: palladium, cellulose, Schiff base, reusability

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Authors: Panumard Kaewmora, Thirasak Rirksomboon, Vissanu Meeyoo

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Due to the globally growing demands of petroleum fuel and fossil fuels, the scarcity or even depletion of fossil fuel sources could be inevitable. Alternatively, the utilization of renewable sources, such as biomass, has become attractive to the community. Biomass can be converted into bio-oil by fast pyrolysis. In water phase of bio-oil, acetic acid which is one of its main components can be converted to hydrogen with high selectivity over effective catalysts in steam reforming process. Steam reforming of acetic acid as model compound has been intensively investigated for hydrogen production using various metal oxide supported nickel catalysts and yet they seem to be rapidly deactivated depending on the support utilized. A catalyst support such as Ce1-xZrxO2 mixed oxide was proposed for alleviating this problem with the anticipation of enhancing hydrogen yield. However, catalyst preparation methods play a significant role in catalytic activity and performance of the catalysts. In this work, Ce0.75Zr0.25O2 mixed oxide solid solution support was prepared by urea hydrolysis using microwave as heat source. After that nickel metal was incorporated at 15 wt% by incipient wetness impregnation method. The catalysts were characterized by several techniques including BET, XRD, H2-TPR, XRF, SEM, and TEM as well as tested for the steam reforming of acetic acid at various operating conditions. Preliminary results showed that a hydrogen yield of ca. 32% with a relatively high acetic conversion was attained at 650°C.

Keywords: acetic acid, steam reforming, microwave, nickel, ceria, zirconia

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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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Authors: Ali Zazi, Ouiza Cherifi

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Natural gas currently represents a raw material of choice for the manufacture of a wide range of chemical products via synthesis gas, among the routes of transformation of methane into synthesis gas The reaction of the oxidation of methane by gas vapor 'water. This work focuses on the study of the effect of cerieum on the nickel-based catalyst supported by silica for the methane vapor reforming reaction, with a variation of certain parameters of the reaction. The reaction temperature, the H₂O / CH₄ ratio and the flow rate of the reaction mixture (CH₄-H₂O). Two catalysts were prepared by impregnation of Degussa silica with a solution of nickel nitrates and a solution of cerium nitrates [Ni (NO₃) 2 6H₂O and Ce (NO₃) 3 6H₂O] so as to obtain the 1.5% nickel concentrations. For both catalysts and plus 1% cerium for the second catalyst. These Catalysts have been characterized by physical and chemical analysis techniques: BET technique, Atomic Absorption, IR Spectroscopy, X-ray diffraction. These characterizations indicated that the nitrates had impregnated the silica. And that the NiO and Ce₂O3 phases are present and Ni°(after reaction). The BET surface of the silica decreases without being affected. The catalytic tests carried out on the two catalysts for the steam reforming reactions show that the addition of cerium to the nickel improves the catalytic performances of the nickel. And that these performances also depend on the parameters of the reaction, namely the temperature, the rate of the reaction mixture, and the ratio (H₂O / CH₄).

Keywords: heterogeneous catalysis, steam reforming, Methane, Nickel, Cerium, synthesis gas, hydrogen

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Krasimir Ivanov

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

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

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Authors: N. Stoeva, I. Spassova, R. Nickolov, M. Khristova

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Exhaust gases from stationary and mobile combustion sources contain nitrogen oxides that cause a variety of environmentally harmful effects. The most common approach of their elimination is the catalytic reaction in the exhaust using various reduction agents such as NH3, CO and hydrocarbons. Transition metals (Co, Ni, Cu, etc.) are the most widely used as active components for deposition on various supports. However, since the interaction between different catalyst components have been extensively studied in different types of reaction systems, the possible cooperation between active components and the support material and the underlying mechanisms have not been thoroughly investigated. The support structure may affect how these materials maintain an active phase. The objective is to investigate the addition of carbonaceous materials with different nature and texture characteristics on the properties of the resulting silica-carbon support and how it influences of the catalytic properties of the supported copper and cobalt catalysts for reduction of NO with CO. The versatility of the physico-chemical properties of the composites and the supported copper and cobalt catalysts are discussed with an emphasis on the relationship of the properties with the catalytic performance. The catalysts were prepared by sol-gel process and were characterized by XRD, XPS, AAS and BET analysis. The catalytic experiments were carried out in catalytic flow apparatus with isothermal flow reactor in the temperature range 20–300оС. After the catalytic test temperature-programmed desorption (TPD) was carried out. The transient response method was used to study the interaction of the gas phase with the catalyst surface. The role of the interaction between the support and the active phase on the catalyst’s activity in the studied reaction was discussed. We suppose the carbon particles with small sizes to participate in the formation of the active sites for the reduction of NO with CO along with their effect on the kind of deposited metal oxide phase. The existence of micropore texture for some of composites also influences by mass-transfer limitations.

Keywords: catalysts, no reduction, composites, bet analysis

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Authors: Hossein Bayahia, Mohammed Saad Motlaq Al-Gahmdi

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The gas-phase deoxygenation of propionic acid was investigated in the presence of Co-Mo catalysts in N2 or H2 flow at 200-400 °C. In the presence of N2 the main product was 3-pentanone with other deoxygenates and some light gases: ethane and ethene. Using H2 flow, the catalyst was active for decarboxylation and decarbonylation of acid and the yields of ethane and ethene. The decarboxylation and decarbonylation reactions increased with increasing temperature. Cobalt-molybdenum supported on alumina showed better performance than bulk catalyst, especially at 400 °C in the presence of N2 for the ketonisation of propionic acid to form 3-pentanone as the main product. Bulk and supported catalysts were characterized by surface area porosity (BET), thermogravimetric analysis (TGA) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of pyridine adsorption.

Keywords: deoxygenation, propionic acid, gas-phase, catalyst

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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

Abstract:

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: Khaled Alshammari

Abstract:

A facile approach to synthesizing highly active and stable Au/NiO catalysts for the hydrogenation of nitro-aromatics is reported. Preformed gold nanoparticles have been immobilized onto NiO using a colloidal method. In this article, the reduction of 4-nitrophenol with NaBH4 has been used as a model reaction to investigate the catalytic activity of synthesized Au/NiO catalysts. In addition, we report a systematic study of the reduction kinetics and the influence of specific reaction parameters such as (i) temperature, (ii) stirring rate, (iii) sodium borohydride concentration and (iv) substrate/metal molar ratio. The reaction has been performed at a substrate/metal molar ratio of 7.4, a ratio significantly higher than previously reported. The reusability of the catalyst has been examined, with little to no decrease in activity observed over 5 catalytic cycles. Systematic variation of Au loading reveals the successful synthesis of low-cost and efficient Au/NiO catalysts at very low Au content and using high substrate/metal molar ratios.

Keywords: nonochemistry, catalyst, nanoparticles supported, characterization of materials, colloidal nanoparticles

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Authors: Przemyslaw J. Jodlowski, Roman J. Jedrzejczyk, Damian K. Chlebda, Anna Dziedzicka, Lukasz Kuterasinski, Anna Gancarczyk, Maciej Sitarz

Abstract:

The aim of this study was to obtain highly active catalysts based on non-noble metal oxides supported on zirconia prepared via a sonochemical method. In this study, the influence of the stabilizers addition during the preparation step was checked. The final catalysts were characterized by using such characterization methods as X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The proposed preparation method allowed to obtain uniformly dispersed metal-oxide nanoparticles at the support’s surface. The catalytic activity of prepared catalyst samples was measured in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was considerably higher than their counterparts prepared by the incipient wetness method.

Keywords: methane catalytic combustion, nanoparticles, non-noble metals, sonochemistry

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Authors: Sushil Kumar Saraswat, K. K. Pant

Abstract:

Co metal supported on SiO2 and Al2O3 catalysts with a metal loading varied from 30 of 70 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nano materials. The catalytic runs were carried out from 550-800 oC under atmospheric pressure using fixed bed vertical flow reactor. The fresh and spent catalysts were characterized by BET surface area analyzer, TPR, XRD, SEM, TEM, and TG analysis. The data showed that 50% Co/Al2O3 catalyst exhibited remarkable higher activity and stability up to 10 h time-on-stream at 750 oC with respect to H2 production compared to rest of the catalysts. However, the catalytic activity and durability was greatly declined at a higher temperature. The main reason for the catalytic inhibition of Co containing SiO2 catalysts is the higher reduction temperature of Co2SiO4. TEM images illustrate that the carbon materials with various morphologies, carbon nanofibers (CNFs), helical-shaped CNFs, and branched CNFs depending on the catalyst composition and reaction temperature, were obtained. The TG data showed that a higher yield of MWCNTs was achieved over 50% Co/Al2O3 catalyst compared to other catalysts.

Keywords: carbon nanotubes, cobalt, hydrogen production, methane decomposition

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Authors: Iwona Misztalewska-Turkowicz, Agnieszka Z. Wilczewska, Karolina H. Markiewicz

Abstract:

Carbenes - species which possess neutral carbon atom with two shared and two unshared valence electrons, are known for their high reactivity and instability. Nevertheless, it is also known, that some carbenes i.e. N-heterocyclic carbenes (NHCs), can form stable crystals. The usability of NHCs in organic synthesis was studied. Due to their exceptional properties (high nucleophilicity) NHCs are commonly used as organocatalysts and also as ligands in transition metal complexes. NHC ligands possess better electron-donating properties than phosphines. Moreover, they exhibit lower toxicity. Due to these features, phosphines are frequently replaced by NHC ligands. In this research is discussed the synthesis of five-membered NHCs which are mainly obtained by deprotonation of azolium salts, e.g., imidazolium or imidazolinium salts. Some of them are immobilized on a solid support what leads to formation of heterogeneous, recyclable catalysts. Magnetic nanoparticles (MNPs) are often used as a solid support for catalysts. MNPs can be easily separated from the reaction mixture using an external magnetic field. Due to their low size and high surface to volume ratio, they are a good choice for immobilization of catalysts. Herein is presented synthesis of N-heterocyclic carbene copper complexes directly on the surface of magnetic nanoparticles. Formation of four different catalysts is discussed. They vary in copper oxidation state (Cu(I) and Cu(II)) and structure of NHC ligand. Catalysts were tested in Huisgen reaction, a type of copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Huisgen reaction represents one of the few universal and highly efficient reactions in which 1,2,3-triazoles can be obtained. The catalytic activity of all synthesized catalysts was compared with activity of commercially available ones. Different reaction conditions (solvent, temperature, the addition of reductant) and reusability of the obtained catalysts were investigated and are discussed. The project was financially supported by National Science Centre, Poland, grant no. 2016/21/N/ST5/01316. Analyses were performed in Centre of Synthesis and Analyses BioNanoTechno of University of Bialystok. The equipment in the Centre of Synthesis and Analysis BioNanoTechno of University of Bialystok was funded by EU, as a part of the Operational Program Development of Eastern Poland 2007-2013, project: POPW.01.03.00-20-034/09-00 and POPW.01.03.00-20-004/11.

Keywords: N-heterocyclic carbenes, click reaction, magnetic nanoparticles, copper catalysts

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Authors: Huanru Wang, Jianzhun Jiang

Abstract:

At present, the preparation of the catalyst by carbon carrier is one of the improvement directions of the C₂ pre-hydrogenation catalyst. Carbon materials can be prepared from coal direct liquefaction residues, coconut shells, biomass, etc., and the pore structure of carbon carrier materials can be adjusted through the preparation process; at high temperatures, the carbon carrier itself also shows certain catalytic activity. Therefore, this paper mainly selected typical activated carbon and coconut shell carbon as carbon carrier materials, studied their microstructure and surface properties, prepared a series of carbon-based catalysts loaded with Pd, and investigated the effects of the content of promoter Ag and the concentration of reductant on the structure and performance of the catalyst and its catalytic performance for the pre hydrogenation of C₂. In this paper, the carbon supports from two sources and the catalysts prepared by them were characterized in detail. The results showed that the morphology and structure of different supports and the performance of the catalysts prepared were also obviously different. The catalyst supported on coconut shell carbon has a small specific surface area and large pore diameter. The catalyst supported on activated carbon has a large specific surface area and rich pore structure. The active carbon support is mainly a mixture of amorphous graphite and microcrystalline graphite. For the catalyst prepared with coconut shell carbon as the carrier, the sample is very uneven, and its specific surface area and pore volume are irregular. Compared with coconut shell carbon, activated carbon is more suitable as the carrier of the C₂ hydrogenation catalyst. The conversion of acetylene, methyl acetylene, and butadiene decreased, and the ethylene selectivity increased after Ag was added to the supported Pd catalyst. When the amount of promoter Ag is 0.01-0.015%, the catalyst has relatively good catalytic performance. Ag and Pd form an alloying effect, thus reducing the effective demand for Ag. The Pd Ag ratio is the key factor affecting the catalytic performance. When the addition amount of Ag is 0.01-0.015%, the dispersion of Pd on the carbon support surface can be significantly improved, and the size of active particles can be reduced. The Pd Ag ratio is the main factor in improving the selectivity of the catalyst. When the additional amount of sodium formate is 1%, the catalyst prepared has both high acetylene conversion and high ethylene selectivity.

Keywords: C₂ hydrogenation, activated carbon, Ag promoter, Pd catalysts

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Authors: Wael A. Aboutaleb, Ahmed M. A. El Naggar, Heba M. Gobara

Abstract:

This research work reports the photocatalytic production of hydrogen from water-methanol mixture using three different 15% ceria/iron oxide catalysts. The catalysts were prepared by physical mixing, precipitation, and ultrasonication methods and labeled as catalysts A-C. The structural and texture properties of the obtained catalysts were confirmed by X-ray diffraction (XRD), BET-surface area analysis and transmission electron microscopy (TEM). The photocatalytic activity of the three catalysts towards hydrogen generation was then tested. Promising hydrogen productivity was obtained by the three catalysts however different gases compositions were obtained by each type of catalyst. Specifically, catalyst A had produced hydrogen mixed with CO₂ while the composite structure (catalyst B) had generated only pure H₂. In the case of catalyst C, syngas made of H₂ and CO was revealed, as a novel product, for the first time, in such process.

Keywords: hydrogen production, water splitting, photocatalysts, clean energy

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Authors: Lin Huang, Bo Wang, Armando Borgna

Abstract:

Dehydration of glycerol to acrolein was conducted with solid acid catalysts in liquid phase in a batch reactor and in gas phase in a fix-bed reactor, respectively. In the liquid-phase reaction, ZSM-5, H3PO4-modified ZSM-5 and heteropolyacids including H3PW12O40•xH2O (HPW) and Cs2.5H0.5PW12O40 (CsPW) were studied as catalysts. High temperatures and high boiling point solvents such as sulfolane improved the selectivity to acrolein through suppressing the formation of polyglycerols and coke. Catalytic results and temperature-programmed desorption of ammonia showed that the yield of acrolein increased with increasing catalyst acidity within the range of weak acid strength. Weak acid sites favored the selectivity to acrolein whereas strong acid sites promoted the formation of coke. ZSM-5 possessing only acid sites led to a high acrolein yield, while heteropolyacid catalysts with strong acid sites produced a low acrolein yield. In the gas-phase reaction, HPW and CsPW supported on metal oxides such as SiO2, γ-Al2O3, SiO2-Al2O3, ZrO2 and silicate TUD-1 were studied as catalysts. HPW/TUD-1 was most active for the production of acrolein, followed by HPW/SiO2. An acrolein yield of 61 % was obtained over HPW/TUD-1. X-ray diffraction study suggested that HPW and CsPW were stable and more dispersed on SiO2, silicate TUD-1 and SiO2-Al2O3. It was found that the structures of HPW and CsPW were destroyed by interaction with γ-Al2O3 and ZrO2. Compared to CsPW/TUD-1, the higher acrolein yield with HPW/TUD-1 may be attributed to more Brønsted acid sites on HPW/TUD-1, based on preliminary pyridine adsorption IR study.

Keywords: dehydration, glycerol, acrolein, solid acid catalysts, gas-phase, liquid-phase

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