Search results for: catalyst performance

Authors: Joy Marie Mora, Mark Daniel De Luna, Tsair-Wang Chung

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Transesterification reaction of soybean oil with methanol was carried out to produce fatty acid methyl esters (FAME) using calcined alkali metal (Na and Li) supported by pumice silica as the solid base catalyst. Pumice silica catalyst was activated by loading alkali metal ions to its surface via an ion-exchange method. Response surface methodology (RSM) in combination with Box-Behnken design (BBD) was used to optimize the operating parameters in biodiesel production, namely: reaction temperature, methanol to oil molar ratio, reaction time, and catalyst concentration. Using the optimized sets of parameters, FAME yields using sodium and lithium silicate catalysts were 98.80% and 98.77%, respectively. A pseudo-first order kinetic equation was applied to evaluate the kinetic parameters of the reaction. The prepared catalysts were characterized by several techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) sorptometer, and scanning electron microscopy (SEM). In addition, the reusability of the catalysts was successfully tested in two subsequent cycles.

Keywords: alkali metal, biodiesel, Box-Behnken design, heterogeneous catalyst, kinetics, optimization, pumice, transesterification

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Authors: Nadeem Bashir, Ghulam Mustafa Peerzada

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The present study pertains to the nonlinear behavior of acetaminophen based uncatalyzed Belousov-Zhabotinsky (BZ) oscillator and its dynamics in the presence of Ferroin as the catalyst. The role of free metal ions as catalysts was examined and the results compared with corresponding complexed catalysts. Free metal ions were found to be sluggish with respect to the evolution of the oscillatory regime as compared to complexed ones. Effect of change of the ligand moiety of the catalyst complex on the oscillatory parameters was monitored. Since ethanol potentiates the hepatotoxicity caused by acetaminophen in-vivo, it is thought to understand this interaction by virtue of causing perturbation of the acetaminophen based oscillator with different concentrations of the ethanol with and without ferroin as the catalyst. Another dimension to the ethanol effect was added by perturbation of the system with ethanol at different stages of the reaction so as to get an idea whether it is acetaminophen or some reactive intermediate generated in the reaction system which reacts with ethanol. Further, the ferroin-catalyzed oscillator is taken as a prototype inorganic model of the acetaminophen-ethanol syndrome, as ferroin and HOBr were inorganic replacements to Cyt P450 and NADPH in the alcohol metabolism.

Keywords: Belousov-Zhabotinsky reaction, ferroin, Paracetamol-Ethanol syndrome, kinetics

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Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh

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Metalloporphyrins are well known to mimic the activity of monooxygenase enzymes. In this regard, metalloporphyrin complexes have been largely employed as valuable biomimetic catalysts, owing to the critical roles they play in oxygen transfer processes in catalytic oxidation reactions. Investigating in this area is based on different strategies to design selective, stable and high turnover catalytic systems. Immobilization of expensive metalloporphyrin catalysts onto supports appears to be a good way to improve their stability, selectivity and the catalytic performance because of the support environment and other advantages with respect to recovery, reuse. In other words, supporting metalloporphyrins provides a physical separation of active sites, thus minimizing catalyst self-destruction and dimerization of unhindered metalloporphyrins. Furthermore, heterogeneous catalytic oxidations have become an important target since their process are used in industry, helping to minimize the problems of industrial waste treatment. Hence, the immobilization of these biomimetic catalysts is much desired. An attractive approach is the preparation of the heterogeneous catalyst involves immobilization of complexes on silica coated magnetic nano-particles. Fe3O4@SiO2 magnetic nanoparticles have been studied extensively due to their superparamagnetism property, large surface area to volume ratio and easy functionalization. Using heterogenized homogeneous catalysts is an attractive option to facile separation of catalyst, simplified product work-up and continuity of catalytic system. Homogeneous catalysts immobilized on magnetic nanoparticles (MNPs) surface occupy a unique position due to combining the advantages of both homogeneous and heterogeneous catalysts. In addition, superparamagnetic nature of MNPs enable very simple separation of the immobilized catalysts from the reaction mixture using an external magnet. In the present work, an efficient heterogeneous catalyst was prepared by immobilizing manganese porphyrin on functionalized magnetic nanoparticles through the amino propyl linkage. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, atomic absorption spectroscopy, UV-Vis spectroscopy, and scanning electron microscopy. Application of immobilized metalloporphyrin in the oxidation of various organic substrates was explored using Gas chromatographic (GC) analyses. The results showed that the supported Mn-porphyrin catalyst (Fe3O4@SiO2-NH2@MnPor) is an efficient and reusable catalyst in oxidation reactions. Our catalytic system exhibits high catalytic activity in terms of turnover number (TON) and reaction conditions. Leaching and recycling experiments revealed that nanocatalyst can be recovered several times without loss of activity and magnetic properties. The most important advantage of this heterogenized catalytic system is the simplicity of the catalyst separation in which the catalyst can be separated from the reaction mixture by applying a magnet. Furthermore, the separation and reuse of the magnetic Fe3O4 nanoparticles were very effective and economical.

Keywords: Fe3O4 nanoparticle, immobilized metalloporphyrin, magnetically separable nanocatalyst, oxidation reactions

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Authors: Maryam Kiani

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In order to enhance the efficiency and stability of an electrocatalyst for formic acid electro-oxidation reaction (FAOR), we developed a method to create Pt/Ni nanoparticles with carbon black. These nanoparticles were prepared using a simple impregnation reduction technique. During the observation, it was found that the nanoparticles had a spherical shape. Additionally, the average particle size remained consistent, falling within the range of about 4 nm. This approach aimed to obtain a loaded Pt-based electrocatalyst that would exhibit improved performance and stability when used in FAOR applications. By utilizing the impregnation reduction method and incorporating Ni nanoparticles along with Pt, we sought to enhance the catalytic properties of the material. By incorporating Ni atoms into the Pt structure, the electronic properties of Pt are modified, resulting in a delay in the chemisorption of harmful CO intermediate species. This modification also promotes the dehydrogenation pathway of the formic acid oxidation reaction (FAOR). Through electrochemical analysis, it has been observed that the Pt3Ni-C catalyst exhibits enhanced performance in FAOR compared to traditional Pt catalysts. This means that the addition of Ni atoms improves the efficiency and effectiveness of the Pt3Ni-C catalyst in facilitating the FAOR process. Overall, the utilization of these alloy nanoparticles as electrocatalysts represents a significant advancement in fuel cell technology.

Keywords: electrocatalyst, impregnation reduction method, formic acid electro-oxidation reaction, fuel cells

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Authors: A. Alkattib, M. Boumaza

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Steam reforming is industrially important as it is incorporated in several major chemical processes including the production of ammonia, methanol, hydrogen and ox alcohols. Due to the strongly endothermic nature of the process, a large amount of heat is supplied by fuel burning (commonly natural gas) in the furnace chamber. Reaction conversions, tube catalyst life, energy consumption and CO2 emission represent the principal factors affecting the performance of this unit and are directly influenced by the high operating temperatures and pressures. This study presents a simulation of the performance of the reforming of methane in a primary reformer, through a developed empirical relation which enables to investigate the effects of operating parameters such as the pressure, temperature, steam to carbon ratio on the production of hydrogen, as well as the fraction of non-converted methane. It appears from this analysis that the exit temperature Te, the operating pressure as well the steam to carbon ratio has an important effect on the reforming of methane.

Keywords: reforming, methane, performance, hydrogen, parameters

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Authors: Allah Bakhsh Javid, Ali Mashayekh-Salehi, Fatemeh Davardoost

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This study presents the preparation, characterization and catalytic activity of a novel natural mineral-based catalyst for destructive adsorption of tetracycline (TTC) as water emerging compounds. Degradation potential of raw and calcined magnetite catalyst was evaluated at different experiments situations such as pH, catalyst dose, reaction time and pollutant concentration. Calcined magnetite attained greater catalytic potential than the raw ore in the degradation of tetracycline, around 69% versus 3% at reaction time of 30 min and TTC aqueous solution of 50 mg/L, respectively. Complete removal of TTC could be obtained using 2 g/L calcined nanoparticles at reaction time of 60 min. The removal of TTC increased with the increase in solution temperature. Accordingly, considering its abundance in nature together with its very high catalytic potential, calcined pyrite is a promising and reliable catalytic material for destructive decomposition for catalytic decomposition and mineralization of such pharmaceutical compounds as TTC in water and wastewater.

Keywords: catalytic degradation, tetracycline, pyrite, emerging pollutants

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Authors: Zohreh Derikvand

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Nanoreactors Zr-MCM-41were prepared via the reaction of ZrOCl2, Fumed silica, sodium hydroxide and cethyltrimethyl ammonium bromide under hydrothermal condition. The prepared nanoreactors were characterized by FT-IR spectroscopy, X-ray diffraction (XRD), Scanning electron micrographs (SEM) and nitrogen adsorption-desorption. The XRD pattern of Zr-MCM-41 exhibits a high-intensity (100) and two low-intensity reflections (110 and 200) which are characteristic of hexagonal structure, exhibiting the long-range order and good textural uniformity of mesoporous structure. Based on the green chemistry approach, we report an efficient and environmentally benign protocol to study the catalytic activity of Zr-MCM-41 in the Biginelli type reactions initially. Nanoreactors Zr-MCM-41 were used as highly recoverable and reusable catalyst for synthesis of 3,4-dihydropyrimidin-2(1H)-one, octahydroquinazolinone, benzimidazolo-quinazolineone and 4,6-diarylpyrimidin-2(1H)-one. The methodology offers several advantages such as short reaction time, high yields and simple operation. The catalyst was active up to three cycles.

Keywords: Zr-MCM-41 nanoreactors, Biginelli like reactions, 3, 4-dihydropyrimidin-2(1H)-ones, ctahydroquinazolinones

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Authors: Alexsandro Bayestorff da Cunha, Dpebora Caline de Mello, Camila Alves Corrêa

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In the production of fiberboards, an adhesive based on urea-formaldehyde resin is used, which has the advantages of low cost, homogeneity of distribution, solubility in water, high reactivity in an acid medium, and high adhesion to wood. On the other hand, as a disadvantage, there is low resistance to humidity and the release of formaldehyde. The objective of the study was to determine the viability of adding industrial boiler ash to the urea formaldehyde-based adhesive for the production of medium-density fiberboard. The raw material used was composed of Pinus spp fibers, urea-formaldehyde resin, paraffin emulsion, ammonium sulfate, and boiler ash. The experimental plan, consisting of 8 treatments, was completely randomized with a factorial arrangement, with 0%, 1%, 3%, and 5% ash added to the adhesive, with and without the application of a catalyst. In each treatment, 4 panels were produced with density of 750 kg.m⁻³, dimensions of 40 x 40 x 1,5 cm, 12% urea formaldehyde resin, 1% paraffin emulsion and hot pressing at a temperature of 180ºC, the pressure of 40 kgf/cm⁻² for a time of 10 minutes. The different compositions of the adhesive were characterized in terms of viscosity, pH, gel time and solids, and the panels by physical and mechanical properties, in addition to evaluation using the IMAL DPX300 X-ray densitometer and formaldehyde emission by the perforator method. The results showed a significant reduction of all adhesive properties with the use of the catalyst, regardless of the treatment; while the percentage increase of ashes provided an increase in the average values of viscosity, gel time, and solids and a reduction in pH for the panels with a catalyst; for panels without catalyst, the behavior was the opposite, with the exception of solids. For the physical properties, the results of the variables of density, compaction ratio, and thickness were equivalent and in accordance with the standard, while the moisture content was significantly reduced with the use of the catalyst but without the influence of the percentage of ash. The density profile for all treatments was characteristic of medium-density fiberboard, with more compacted and dense surfaces when compared to the central layer. For thickness, the swelling was not influenced by the catalyst and the use of ash, presenting average values within the normalized parameters. For mechanical properties, the influence of ashes on the adhesive was negatively observed in the modulus of rupture from 1% and in the traction test from 3%; however, only this last property, in the percentages of 3% and 5%, were below the minimum limit of the norm. The use of catalyst and ashes with percentages of 3% and 5% reduced the formaldehyde emission of the panels; however, only the panels that used adhesive with catalyst presented emissions below 8mg of formaldehyde / 100g of the panel. In this way, it can be said that boiler ash can be added to the adhesive with a catalyst without impairing the technological properties by up to 1%.

Keywords: reconstituted wood panels, formaldehyde emission, technological properties of panels, perforator

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Authors: Bita Bayatsarmadi, Shi-Zhang Qiao

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Oxygen reduction reaction (ORR) performance of iron and nitrogen co-doped porous carbon nanoparticles (Fe-NPC) with various physical and (electro) chemical properties have been investigated. Fe-NPC nanoparticles are synthesized via a facile soft-templating procedure by using Iron (III) chloride hexa-hydrate as iron precursor and aminophenol-formaldehyde resin as both carbon and nitrogen precursor. Fe-NPC nanoparticles shows high surface area (443.83 m2g-1), high pore volume (0.52 m3g-1), narrow mesopore size distribution (ca. 3.8 nm), high conductivity (IG/ID=1.04), high kinetic limiting current (11.71 mAcm-2) and more positive onset potential (-0.106 V) compared to metal-free NPC nanoparticles (-0.295V) which make it high efficient ORR metal-free catalysts in alkaline solution. This study may pave the way of feasibly designing iron and nitrogen containing carbon materials (Fe-N-C) for highly efficient oxygen reduction electro-catalysis.

Keywords: electro-catalyst, mesopore structure, oxygen reduction reaction, soft-template

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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: Corazon Virtudazo-Ligaray, Mark Daniel G. de Luna, Meng-Wei Wan, Ming-Chun Lu

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A series of ternary compound catalyst with nanocomposites of ceria, tungsten trioxide and titania (CeO2-WOx-TiO2) with different WOx mole fraction (10, 20, 30, 40) have been synthesized by sol-gel method. These nanocomposite catalysts were used for oxidative extractive desulfurization of model fuel oil, which were composed of dibenzothiophene (DBT) dissolved in toluene. The 30% hydrogen peroxide, H2O2 was used as oxidant and acetonitrile as extractant. These catalysts were characterized by SEM-EDS to determine the morphology. Catalytic oxidation results show that the catalysts have high selectivity in refractory fuel oil with organo sulfur contents. The oxidative removal of DBT increases as the HPW content increases. The nanocomposites CeO2-WOx-TiO2 also shows high selectivity for DBT oxidation in the DBT–toluene acetonitrile system. The catalytic oxidative desulfurization ratio of model fuel reached to 100% with nanocomposites CeO2-WOx-TiO2 (35-30-35) mol percent catalyst nanocomposition under 333 K in 30 minutes.

Keywords: ceria, oxidative desulfurization, titania, phosphotungstic acid

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Authors: Y. J. Lin, Y. F. Lin

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CO2 is the primary greenhouse gas which causes global warming in recent years. As the carbon capture and storage (CCS) getting maturing, the reuse of carbon dioxide which made from CCS is the important issue. In this way, the most common method is the synthesis of cyclic carbonate chemicals from the cycloaddition reaction of carbon dioxide and epoxide. The catalyst plays an important role in the CO2/epoxide cycloaddition reactions. The Lewis acid and base sites are both needed on the catalyst surface for the help of epoxide ring opening, leading to the synthesis of cyclic carbonate. Furthermore, the larger specific surface area and more active site of the catalyst are also needed to enhance the efficiency of the CO2/epoxide cycloaddition reactions. Aerogel is a mesoporous nanomaterial (pore size between 2~50 nm) with high specific surface area and porosity (at least 90%) and low density. In this study, the ternary metal oxide aerogels, Mg-doped Al2O3 aerogels, with higher specific surface area and Lewis acid and base sites on the aerogel surface are successfully prepared by using a facile sol-gel reaction. The as-prepared Mg-doped Al2O3 aerogels are also served as heterogenous catalyst for the CO2/propylene- oxide cycloaddition reaction. Compared to the pristine Al2O3 aerogels, the Mg-doped Al2O3 aerogels possessed both Lewis acid and base sites on the surface are able to enhance the efficiency of the CO2/propylene oxide cycloaddition reactions. As a result, the as-prepared Mg-doped Al2O3 aerogels are a promising and novel catalyst for the CO2/epoxide cycloaddition reactions.

Keywords: ternary, metal oxide aerogel, CO2 reuse, cycloaddition, propylene oxide

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Authors: Nabi Ullah

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The energy crisis of the current society has attracted research attention for alternative energy sources. Methanol oxidation is the source of energy but needs efficient electrocatalysts like Pt. However, their practical ability is hindered due to cost and poisoning effects. In this regard, an efficient catalyst is required for methanol oxidation. Herein, high temperature, pressure, and diethylenetryamine (DETA) as reaction medium/structure directing agent during the solvothermal method are used for nanobelt Cu₃Se₂/Cu₁.₈Se (mostly hexagonal appearance) formation. The electrocatalyst shows optimized methanol electrooxidation reaction (MOR) response in 1 M KOH and 0.5 M methanol at a scan rate of 50 mV/s and delivers a current density of 7.12 mA/mg at a potential of 0.65 V (vs Ag/AgCl). The catalyst exhibits high electrochemical active surface area (ECSA) (0.088 mF/cm²) and low Rct with good stability for 3600 s, which favors its high MOR performance. This high response is due to its 2D hexagonal nanobelt morphology, which provides a large surface area for reaction. The space among nanobelts reduces diffusion kinetics, and the rough/irregular edge increases the reaction site to improve the methanol oxidation reaction overall.

Keywords: energy application, electrocatalysis, MOR, nanobelt

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Authors: Victor R. Thulari, John Akach, Haleden Chiririwa, Aoyi Ochieng

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Solar-light activated titanium dioxide photocatalysts were prepared by hydrolysis of titanium (IV) isopropoxide with thiourea, followed by calcinations at 450 °C. The experiments demonstrated that methyl orange in aqueous solutions were successfully degraded under solar light using doped TiO₂. The photocatalytic oxidation of a mono azo methyl-orange dye has been investigated in multi ion doped TiO₂ and solar light. Solutions were irradiated by solar-light until high removal was achieved. It was found that there was no degradation of methyl orange in the dark and in the absence of TiO₂. Varieties of laboratory prepared TiO₂ catalysts both un-doped and doped using titanium (IV) isopropoxide and thiourea as a dopant were tested in order to compare their photoreactivity. As a result, it was found that the efficiency of the process strongly depends on the working conditions. The highest degradation rate of methyl orange was obtained at optimum dosage using commercially produced TiO₂. Our work focused on laboratory synthesized catalyst and the maximum methyl orange removal was achieved at 81% with catalyst loading of 0.04 g/L, initial pH of 3 and methyl orange concentration of 0.005 g/L using multi-ion doped catalyst. The kinetics of photocatalytic methyl orange dye stuff degradation was found to follow a pseudo-first-order rate law. The presence of the multi-ion dopant (thiourea) enhanced the photoefficiency of the titanium dioxide catalyst.

Keywords: degradation, kinetics, methyl orange, photocatalysis

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Authors: Medhanie Gebremedhin Gebru, Alex Schechter

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Dimethyl ether (DME) possesses several advantages over other small organic molecules such as methanol, ethanol, and ammonia in terms of providing higher energy density, being less toxic, and having lower Nafion membrane crossover. However, the absence of an active and stable catalyst has been the bottleneck that hindered the commercialization of direct DME fuel cells. A Vulcan XC72 carbon-supported ternary metal catalyst, Pt₃Pd₃Sn₂/C is reported to have yielded the highest specific power density (90 mW mg-¹PGM) as compared to other catalysts tested fordirect DME fuel cell (DDMEFC). However, the micropores and sulfur groups present in Vulcan XC72 hinder the fuel utilization by causing Pt agglomeration and sulfur poisoning. Vulcan XC72 having a high carbon sp³ hybridization content, is also prone to corrosion. Therefore, carbon supports such as multi-walled carbon nanotube (MWCNT), black pearl 2000 (BP2000), and their cold N2 plasma-treated counterpartswere tested to further enhance the activity of the catalyst, and the outputs with these carbons were compared with the originally used support. Detailed characterization of the pristine and carbon supports was conducted. Electrochemical measurements in three-electrode cells and laboratory prototype fuel cells were conducted.Pt₃Pd₃Sn₂/BP2000 exhibited excellent performance in terms of electrochemical active surface area (ECSA), peak current density (jp), and DME oxidation charge (Qoxi). The effect of the plasma activation on the activity improvement was observed only in the case of MWCNT while having little or no effect on the other carbons. A Pt₃Pd₃Sn₂ supported on the optimized mixture of carbons containing 75% plasma-activated MWCNT and 25% BP2000 (Pt₃Pd₃Sn₂/75M25B) provided the highest reported power density of 117 mW mg-1PGM using an anode loading of1.55 mgPGMcm⁻².

Keywords: DME, DDMEFC, ternary metal catalyst, carbon support, plasma activation

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Authors: H. Boucheloukh, N. Aoun, M. Denni, A. Mahrouk, T. Sehili

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Perovskite materials with strontium alkaline earth metal have attracted researchers in photocatalysis. Thus, nanocomposite-based strontium has been synthesized by the sol-gel method, calciened at 700 °C, and characterized by different methods such as X-ray difraction (DRX), Fourier transformed infrared (FTIR), and diffuse relectance spectroscopy (DRS). After that, the photocatlytic performance of SrNO3/SnO2 has been tested under sunlight in an aqueous solution for two dyes methylene blue and congo-red. The results reveal that 70% of methylene blue has already been degraded after 45 minutes of exposure to sun light, while 80% of Congo red has been eliminated by adsorption on SrSnO₃/SnO₂ in 120 minutes of contact.

Keywords: congo-red, methylene blue, photocatalysis, perovskite

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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: Farrukh Jamil, Ala'a H. Al-Muhtaseb, Lamya Al-Haj, Mohab A. Al-Hinai

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Date pits are major agricultural waste produced in Oman. Current work was conducted to produce jet fuel and green diesel from hydrodeoxygenation of Date pits oil in the presence of Pd/C catalyst. The hydrodeoxygenation of Date pits oil occurred to be highly efficient at following mild operating conditions such as conditions temperature 300°C pressure 10bar with continuous stirring at 500rpm. Detailed product characterization revealed that large fraction of paraffinic hydrocarbons was found which accounts up to 91.1 % which attributed due to efficient hydrodeoxygenation. Based on the type of components in product oil, it was calculated that the maximum fraction of hydrocarbons formed lies within the range of green diesel 72.0 % then jet fuel 30.4% by using Pd/C catalysts. The densities of product oil were 0.88 kg/m³, the viscosity of products calculated was 3.49 mm²/s. Calorific values for products obtained were 44.11 MJ/kg when Pd/C catalyst was used for hydrodeoxygenation. Based on products analysis it can conclude that Date pits oil could successfully utilize for synthesizing green diesel and jet fuel fraction.

Keywords: biomass, jet fuel, green diesel, catalyst

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Authors: Xin Zhao. Xuerong Zheng. Andrey L. Rogach

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Using single metal atoms has been considered an efficient way to develop new HER and OER catalysts. MXenes, a class of two-dimensional materials, have attracted tremendous interest as promising substrates for single-atom metal catalysts. However, there is still a lack of systematic investigations on the interaction mechanisms between various MXenes substrates and single atoms. Besides, due to the poor interaction between metal atoms and substrates resulting in low loading and stability, dual-atom MXenes-based catalysts have not been successfully synthesized. We summarized the electrocatalytic enhancement mechanism of three MXenes-based single-atom catalysts through experimental and theoretical results demonstrating the stronger hybridization between Co 3d and surface-terminated O 2p orbitals, optimizing the electronic structure of Co single atoms in the composite. This, in turn, lowers the OER and HER energy barriers and accelerates the catalytic kinetics in the case of the Co@V2CTx composite. The poor interaction between single atoms and substrates can be improved by a surface modification to synthesize dual-atom catalysts. The synergistic electronic structure enhances the stability and electrocatalytic activity of the catalyst. Our study provides guidelines for designing single-atom and dual-atom MXene-based electrocatalysts and sheds light on the origins of the catalytic activity of single-atoms on MXene substrates.

Keywords: dual-atom catalyst, single-atom catalyst, MXene substrates, water splitting

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Authors: Yeidy Sorani Montenegro Camacho, Samir Bensaid, Nunzio Russo, Debora Fino

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LiFeO2 nano-powders were prepared via solution combustion synthesis (SCS) method and were used as carbon gasification catalyst in a reduced atmosphere. The gasification of soot with CO2 and H2O in the presence of CO and H2 (syngas atmosphere) were also investigated under atmospheric conditions using a fixed-bed micro-reactor placed in an electric, PID-regulated oven. The catalytic bed was composed of 150 mg of inert silica, 45 mg of carbon (Printex-U) and 5 mg of catalyst. The bed was prepared by ball milling the mixture at 240 rpm for 15 min to get an intimate contact between the catalyst and soot. A Gas Hourly Space Velocity (GHSV) of 38.000 h-1 was used for the tests campaign. The furnace was heated up to the desired temperature, a flow of 120 mL/min was sent into the system and at the same time the concentrations of CO, CO2 and H2 were recorded at the reactor outlet using an EMERSON X-STREAM XEGP analyzer. Catalytic and non-catalytic soot gasification reactions were studied in a temperature range of 120°C – 850°C with a heating rate of 5 °C/min (non-isothermal case) and at 650°C for 40 minutes (isothermal case). Experimental results show that the gasification of soot with H2O and CO2 are inhibited by the H2 and CO, respectively. The soot conversion at 650°C decreases from 70.2% to 31.6% when the CO is present in the feed. Besides, the soot conversion was 73.1% and 48.6% for H2O-soot and H2O-H2-soot gasification reactions, respectively. Also, it was observed that the carbon gasification in mixed atmosphere, i.e., when simultaneous carbon gasification with CO2 and steam take place, with H2 and CO as co-reagents; the gasification reaction is strongly inhibited by CO and H2, as well has been observed in single atmospheres for the isothermal and non-isothermal reactions. Further, it has been observed that when CO2 and H2O react with carbon at the same time, there is a passive cooperation of steam and carbon dioxide in the gasification reaction, this means that the two gases operate on separate active sites without influencing each other. Finally, despite the extreme reduced operating conditions, it has been demonstrated that the 32.9% of the initial carbon was gasified using LiFeO2-catalyst, while in the non-catalytic case only 8% of the soot was gasified at 650°C.

Keywords: soot gasification, nanostructured catalyst, reducing environment, syngas

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Authors: Shashank Bahri, Divyanshu Arya, Rajni Jain, Sreedevi Upadhyayula

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Petroleum products can be obtained from syngas catalytic conversion using Fischer Tropsch Reaction. The liquid fuels obtained from FTS are sulphur and nitrogen free and thus may easily meet the increasing stringent environment regulations. In the present work we have synthesized Meso porous ZSM-5 supported catalyst. Meso structure were created in H-ZSM-5 crystallites by demetalation via subsequent base and acid treatment. Desilication through base treatment provides H-ZSM-5 with pore size and volumes similar to amorphous SiO2 (Conventional Carrier). Modifying the zeolite texture and surface chemistry by Desilication and acid washing alters its accessibility and interactions with metal phase and consequently the CO adsorption behavior and hydrocarbon product distribution. Increasing the mesoporosity via desilication provides the micro porous zeolite with essential surface area to support optimally sized metal crystallites. This improves the metal dispersion and hence improve the activity of the catalyst. Transition metal (Co) was loaded using wet impregnation method. Synthesized catalysts were characterized by Infrared Spectroscopy, Powdered X-Ray Diffraction, Scanning Electron Microscopy (SEM), BET Method analytical techniques. Acidity of the catalyst which plays an important role in FTS reaction was measured by DRIFT setup pyridine adsorption instead of NH3 Temperature Programmed Desorption. The major difference is that, Pyridine Adsorption can distinguish between Lewis acidity and Bronsted Acidity, thus giving their relative strengths in the catalyst sample, whereas TPD gives total acidity including Lewis and Bronsted ones.

Keywords: mesopourus, fischer tropsch reaction, pyridine adsorrption, drift study

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Authors: Xiao-Dong Wang, Wei-Mon Yan

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The flow field design in the bipolar plates affects the performance of the proton exchange membrane (PEM) fuel cell. This work adopted a combined optimization procedure, including a simplified conjugate-gradient method and a completely three-dimensional, two-phase, non-isothermal fuel cell model, to look for optimal flow field design for a single serpentine fuel cell of size 9×9 mm with five channels. For the direct solution, the two-fluid method was adopted to incorporate the heat effects using energy equations for entire cells. The model assumes that the system is steady; the inlet reactants are ideal gases; the flow is laminar; and the porous layers such as the diffusion layer, catalyst layer and PEM are isotropic. The model includes continuity, momentum and species equations for gaseous species, liquid water transport equations in the channels, gas diffusion layers, and catalyst layers, water transport equation in the membrane, electron and proton transport equations. The Bulter-Volumer equation was used to describe electrochemical reactions in the catalyst layers. The cell output power density Pcell is maximized subjected to an optimal set of channel heights, H1-H5, and channel widths, W2-W5. The basic case with all channel heights and widths set at 1 mm yields a Pcell=7260 Wm-2. The optimal design displays a tapered characteristic for channels 1, 3 and 4, and a diverging characteristic in height for channels 2 and 5, producing a Pcell=8894 Wm-2, about 22.5% increment. The reduced channel heights of channels 2-4 significantly increase the sub-rib convection and widths for effectively removing liquid water and oxygen transport in gas diffusion layer. The final diverging channel minimizes the leakage of fuel to outlet via sub-rib convection from channel 4 to channel 5. Near-optimal design without huge loss in cell performance but is easily manufactured is tested. The use of a straight, final channel of 0.1 mm height has led to 7.37% power loss, while the design with all channel widths to be 1 mm with optimal channel heights obtained above yields only 1.68% loss of current density. The presence of a final, diverging channel has greater impact on cell performance than the fine adjustment of channel width at the simulation conditions set herein studied.

Keywords: optimization, flow field design, simplified conjugate-gradient method, serpentine flow field, sub-rib convection

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Authors: Olga A. Krysiak, Grzegorz Cichowicz, Wojciech Hyk, Michal Cyranski, Jan Augustynski

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Metal oxides are known electrocatalyst in water oxidation reaction. Due to the fact that it is desirable for efficient oxygen evolution catalyst to contain numerous redox-active metal ions to guard four electron water oxidation reaction, mixed metal oxides exhibit enhanced catalytic activity towards oxygen evolution reaction compared to single metal oxide systems. On the surface of fluorine doped tin oxide coated glass slide (FTO) deposited (doctor blade technique) mixed metal oxide layer composed of nickel, iron, and chromium. Oxide coating was acquired by heat treatment of the aqueous precursors' solutions of the corresponding salts. As-prepared electrodes were photosensitive and acted as an efficient oxygen evolution catalyst. Our results showed that obtained by this method electrodes can be activated which leads to achieving of higher current densities. The recorded current and photocurrent associated with oxygen evolution process were at least two orders of magnitude higher in the presence of oxide layer compared to bare FTO electrode. The overpotential of the process is low (ca. 0,2 V). We have also checked the activity of the catalyst at different known photoanodes used in sun-driven water splitting. Herein, we demonstrate that we were able to achieve efficient oxygen evolution catalysts using relatively cheap precursor consisting of earth abundant metals and simple method of preparation.

Keywords: chromium, electrocatalysis, iron, metal oxides, nickel, oxygen evolution

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Authors: E. Kolvari, N. Koukabi, A. Sabet, A. Fakhraee, M. Ramezanpour

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A green and efficient method for oxidation of thiols to the corresponding disulfides is reported using free nano-iron oxide in the H2O2 and methanol as solvent at room tempereture. H2O2 is anoxidant for S-S coupling variety aromatic of thiols to corresponding disulfide in the presence of supported iron oxide as recoverable catalyst. This reaction is clean, fast, mild and easy work-up with no side reaction.

Keywords: thiol, disulfide, free nano-iron oxide, H2O2, oxidation, coupling

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Authors: Nagwa Mourad Abdelazeem, Marwa El-hussieny

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Multicomponent reactions (MCRs), one-pot reactions form products from more than two different starting compounds. (MCRs) are ideal reaction systems leading to high structural diversity and molecular complexity through a single transformation. (MCRs) have a lot of advantage such as higher yield, less waste generation, use of readily available starting materials and high atom. (MCRs) provide a rapid process for efficient synthesis of key structures in discovery of drug on the other hand silica sulfuric acid (SSA) has been used as an efficient heterogeneous catalyst for many organic transformations. (SSA) is low cost, ease of preparation, catalyst recycling, and ease of handling, so in this article we used 2-(thiophen-2-yl)-1H-indole, N-substituted anilines and aldehyde in the presence of silica sulfuric acid (SSA) as a catalyst in water as solvent at room temperature to prepare 3,3'-(phenylmethylene)bis(2-(thiophen-2-yl)-1H-indole) and N-methyl-4-(phenyl(2-(thiophen-2-yl)-1H-indol-3-yl)methyl)aniline derivatives Via one-pot reaction. Compound 2-(thiophen-2-yl)-1H-indole belongs to the ubiquitous class of indoles which enjoy broad synthetic, biological and industrial applications ]. Cancer is considered the first or second most common reason of death all through the world. So the synthesized compounds will be tested as anticancer. We expected the synthesized compounds will give good results comparison to the reference drug.

Keywords: aldehydes, aza-friedel-crafts reaction, indole, multicomponent reaction

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Authors: Ouahiba Bechiri, Mostefa Abbessi

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The color removal from industrial effluents is a major concern in wastewater treatment. The main objective of this work was to study the decolorization of a mixture of Orange G acid (OG) and naphthol blue black dye (NBB) in aqueous solution by hydrogen peroxide using [H1,5Fe1,5P2W12Mo6O61,23H2O] as catalyst. [H1,5Fe1,5P2 W12Mo6O61,23H2O] is a recyclable DAWSON type heteropolyanion. Effects of various experimental parameters of the oxidation reaction of the dye were investigated. The studied parameters were: the initial pH, H2O2 concentration, the catalyst mass and the temperature. The optimum conditions had been determined, and it was found that efficiency of degradation obtained after 15 minutes of reaction was about 100%. The optimal parameters were: initial pH = 3; [H2O2]0 = 0.08 mM; catalyst mass = 0.05g; for a concentration of dyes = 30mg/L.

Keywords: Dawson type heteropolyanion, naphthol blue-black, dye degradation, orange G acid, oxidation, hydrogen peroxide

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Vasko Idakiev, Tatyana Tabakova, Krasimir Ivanov

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Formaldehyde production by selective oxidation of methanol is an important industrial process. The main by-products in the waste gas are CO and dimethyl ether (DME). The idea of this study is to combine the advantages of both Cu-Mn and Cu-Co catalytic systems by obtaining a new mixed Cu-Mn-Co catalyst with high activity and selectivity at the simultaneous oxidation of CO, methanol, and DME. Two basic Cu-Mn samples with high activity were selected for further investigation: (i) manganese-rich Cu-Mn/γ–Al2O3 catalyst with Cu/Mn molar ratio 1:5 and (ii) copper-rich Cu-Mn/γ-Al2O3 catalyst with Cu/Mn molar ratio 2:1. Manganese in these samples was replaced by cobalt in the whole concentration region, and catalytic properties were determined. The results show a general trend of decreasing the activity toward DME oxidation and increasing the activity toward CO and methanol oxidation with the increase of cobalt up to 60% for both groups of catalyst. This general trend, however, contains specific features, depending on the composition of the catalyst and the nature of the oxidized gas. The catalytic activity of the sample with Cu/(Mn+Co) molar ratio of 2:1 is gradually changed with increasing the cobalt content. The activity of the sample with Cu/(Mn+Co) molar ratio of 1: 5 passes through a maximum at 60% manganese replacement by cobalt, probably due to the formation of highly dispersed Co-based spinel structures (Co3O4 and/or MnCo2O4). In conclusion, the present study demonstrates that the Cu-Mn-Co/γ–alumina supported catalysts have enhanced activity toward CO, methanol and DME oxidation. Cu/(Mn+Co) molar ratio 1:5 and Co/Mn molar ratio 1.5 in the active component can ensure successful oxidation of CO, CH3OH and DME. The active component of the mixed Cu-Mn-Co/γ–alumina catalysts consists of at least six compounds - CuO, Co3O4, MnO2, Cu1.5Mn1.5O4, MnCo2O4 and CuCo2O4, depending on the Cu/Mn/Co molar ratio. Chemical composition strongly influences catalytic properties, this effect being quite variable with regards to the different processes.

Keywords: Cu-Mn-Co catalysts, oxidation, carbon oxide, VOCs

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Authors: Kumaresh Selvakumar, Man Young Kim

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Catalytic combustor substantially reduces emission entailing fuel-air premixing at very low equivalence ratios. The catalytic combustion of natural gas has the potential to become sufficiently active at light off temperature by the convection of heat from the catalyst surface. Only one channel is selected to investigate both the gas and surface reactions in the catalyst bed because of the honeycomb structure of the catalytic combustor. The objective of the present study is to find the methane catalytic combustion behavior inside the catalytic combustor, where the gas phase kinetics is employed by homogeneous methane combustion and surface chemistry is described with the heterogeneous catalysis of the oxidation of methane on a platinum catalyst. The reaction of the premixed mixture in the catalytic regime improves flame stability with complete combustion for lower operating flame temperature. An overview of the flow behavior is presented inside the single channel catalytic combustor including the operation of catalytic combustion with various F/A ratios and premixed inlet temperature.

Keywords: catalytic combustor, equivalence ratios, flame temperature, heterogeneous catalysis, homogeneous combustion

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Authors: Ajith J. Kings, L. R. Monisha Miriam, R. Edwin Raj, S. Julyes Jaisingh, S. Gavaskar

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Microalgae are a potential bio-source for rejuvenated solutions in various disciplines of science and technology, especially in medicine and energy. Biodiesel is being replaced for conventional fuels in automobile industries with reduced pollution and equivalent performance. Since it is a carbon neutral fuel by recycling CO2 in photosynthesis, global warming potential can be held in control using this fuel source. One of the ways to meet the rising demand of automotive fuel is to adopt with eco-friendly, green alternative fuels called sustainable microalgal biodiesel. In this work, a microalga Chlamydomonas reinhardtii was cultivated and optimized in different media compositions developed from under-utilized waste materials in lab scale. Using the optimized process conditions, they are then mass propagated in out-door ponds, harvested, dried and oils extracted for optimization in ambient conditions. The microalgal oil was subjected to two step esterification processes using acid catalyst to reduce the acid value (0.52 mg kOH/g) in the initial stage, followed by transesterification to maximize the biodiesel yield. The optimized esterification process parameters are methanol/oil ratio 0.32 (v/v), sulphuric acid 10 vol.%, duration 45 min at 65 ºC. In the transesterification process, commercially available alkali catalyst (KOH) is used and optimized to obtain a maximum biodiesel yield of 95.4%. The optimized parameters are methanol/oil ratio 0.33(v/v), alkali catalyst 0.1 wt.%, duration 90 min at 65 ºC 90 with smooth stirring. Response Surface Methodology (RSM) is employed as a tool for optimizing the process parameters. The biodiesel was then characterized with standard procedures and especially by GC-MS to confirm its compatibility for usage in internal combustion engine.

Keywords: microalgae, organic media, optimization, transesterification, characterization

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Authors: Carlos Alfredo Camargo Vila, Fredy Augusto Avellaneda Vargas, Debora Alcida Nabarlatz

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Due to the current need to implement environmentally friendly technologies, the possibility of using renewable raw materials to produce bioproducts such as biofuels, or in this case, to produce biolubricant bases, from residual oils (tallow), originating has been studied of the bovine industry. Therefore, it is hypothesized that through the study and control of the operating variables involved in the reverse transesterification method, a biolubricant base with high performance is obtained on a laboratory scale using animal fats from the bovine industry as raw materials, as an alternative for material recovery and environmental benefit. To implement this process, esterification of the crude tallow oil must be carried out in the first instance, which allows the acidity index to be decreased ( > 1 mg KOH/g oil), this by means of an acid catalysis with sulfuric acid and methanol, molar ratio 7.5:1 methanol: tallow, 1.75% w/w catalyst at 60°C for 150 minutes. Once the conditioning has been completed, the biodiesel is continued to be obtained from the improved sebum, for which an experimental design for the transesterification method is implemented, thus evaluating the effects of the variables involved in the process such as the methanol molar ratio: improved sebum and catalyst percentage (KOH) over methyl ester content (% FAME). Finding that the highest percentage of FAME (92.5%) is given with a 7.5:1 methanol: improved tallow ratio and 0.75% catalyst at 60°C for 120 minutes. And although the% FAME of the biodiesel produced does not make it suitable for commercialization, it does ( > 90%) for its use as a raw material in obtaining biolubricant bases. Finally, once the biodiesel is obtained, an experimental design is carried out to obtain biolubricant bases using the reverse transesterification method, which allows the study of the effects of the biodiesel: TMP (Trimethylolpropane) molar ratio and the percentage of catalyst on viscosity and yield as response variables. As a result, a biolubricant base is obtained that meets the requirements of ISO VG (Classification for industrial lubricants according to ASTM D 2422) 32 (viscosity and viscosity index) for commercial lubricant bases, using a 4:1 biodiesel molar ratio: TMP and 0.51% catalyst at 120°C, at a pressure of 50 mbar for 180 minutes. It is necessary to highlight that the product obtained consists of two phases, a liquid and a solid one, being the first object of study, and leaving the classification and possible application of the second one incognito. Therefore, it is recommended to carry out studies of the greater depth that allows characterizing both phases, as well as improving the method of obtaining by optimizing the variables involved in the process and thus achieving superior results.

Keywords: biolubricant base, bovine tallow, renewable resources, reverse transesterification

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