Search results for: cobalt catalyst

Authors: Tie-Qing Zhang, Seunghun Jung, Young-Bae Kim

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This research is devoted to developing a membrane reactor to flexibly meet the hydrogen demand of onboard fuel cells, which is an important part of green energy development. Among many renewable chemical products, dimethyl ether (DME) has the advantages of low reaction temperature (400 °C in this study), high hydrogen atom content, low toxicity, and easy preparation. Autothermal reforming, on the other hand, has a high hydrogen recovery rate and exhibits thermal neutrality during the reaction process, so the additional heat source in the hydrogen production process can be omitted. Therefore, the DME auto thermal reforming process was adopted in this study. To control the temperature of the reaction catalyst bed and hydrogen production rate, a Model Predictive Control (MPC) scheme was designed. Taking the above two variables as the control objectives, stable operation of the reformer can be achieved by controlling the flow rates of DME, steam, and high-purity air in real-time. To prevent catalyst poisoning in the fuel cell, the hydrogen needs to be purified to reduce the carbon monoxide content to below 50 ppm. Therefore, a Pd-Ag hydrogen semi-permeable membrane with a thickness of 3-5 μm was inserted into the auto thermal reactor, and the permeation efficiency of hydrogen was improved by steam purging on the permeation side. Finally, hydrogen with a purity of 99.99 was obtained.

Keywords: hydrogen production, auto thermal reforming, membrane, fuel cell

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Authors: S. V. Akulinichev, S. A. Chaushansky, V. I. Derzhiev

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High dose rate (HDR) brachytherapy is a method of contact radiotherapy, when a single sealed source with an activity of about 10 Ci is temporarily inserted in the tumor area. The isotopes Ir-192 and (much less) Co-60 are used as active material for such sources. The other type of brachytherapy, the low dose rate (LDR) brachytherapy, implies the insertion of many permanent sources (up to 200) of lower activity. The pulse dose rate (PDR) brachytherapy can be considered as a modification of HDR brachytherapy, when the single source is repeatedly introduced in the tumor region in a pulse regime during several hours. The PDR source activity is of the order of one Ci and the isotope Ir-192 is currently used for these sources. The PDR brachytherapy is well recommended for the treatment of several tumors since, according to oncologists, it combines the medical benefits of both HDR and LDR types of brachytherapy. One of the main problems for the PDR brachytherapy progress is the shielding of the treatment area since the longer stay of patients in a shielded canyon is not enough comfortable for them. The use of Yb-169 as an active source material is the way to resolve the shielding problem for PDR, as well as for HRD brachytherapy. The isotope Yb-169 has the average photon emission energy of 93 KeV and the half-life of 32 days. Compared to iridium and cobalt, this isotope has a significantly lower emission energy and therefore requires a much lighter shielding. Moreover, the absorption cross section of different materials has a strong Z-dependence in that photon energy range. For example, the dose distributions of iridium and ytterbium have a quite similar behavior in the water or in the body. But the heavier material as lead absorbs the ytterbium radiation much stronger than the iridium or cobalt radiation. For example, only 2 mm of lead layer is enough to reduce the ytterbium radiation by a couple of orders of magnitude but is not enough to protect from iridium radiation. We have created an original facility to produce the start stable isotope Yb-168 using the laser technology AVLIS. This facility allows to raise the Yb-168 concentration up to 50 % and consumes much less of electrical power than the alternative electromagnetic enrichment facilities. We also developed, in cooperation with the Institute of high pressure physics of RAS, a new technology for manufacturing high-density ceramic cores of ytterbium oxide. Ceramics density reaches the limit of the theoretical values: 9.1 g/cm3 for the cubic phase of ytterbium oxide and 10 g/cm3 for the monoclinic phase. Source cores from this ceramics have high mechanical characteristics and a glassy surface. The use of ceramics allows to increase the source activity with fixed external dimensions of sources.

Keywords: brachytherapy, high, pulse dose rates, radionuclides for therapy, ytterbium sources

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Authors: Sonali Panigrahy, Manjunatha K., Sudip Barman

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Electrocatalytic reduction methods hold significant promise in addressing the urgent need to mitigate excessive greenhouse gas emissions, particularly carbon dioxide (CO₂). A highly effective catalyst is essential for achieving the conversion of CO₂ into valuable products due to the complex, multi-electron, and multi-product nature of the CO₂ reduction process. The electrochemical reduction of CO₂, driven by renewable energy sources, presents a valuable opportunity for simultaneously reducing CO₂ emissions while generating valuable chemicals and fuels, with syngas being a noteworthy product. Silver-based electrodes have been the focus of extensive research due to their low overpotential and remarkable selectivity in promoting the generation of carbon monoxide (CO) in the electrocatalytic carbon dioxide reduction reaction (CO₂RR). In this study, we delve into the synthesis of carbon-supported silver nanoparticles (Ag/C), which serve as efficient electrocatalysts for the reduction of CO₂. The as-prepared catalyst, Ag/C, is not only cost-effective but also highly proficient in facilitating the conversion of CO₂ and H₂O into syngas, which is a customizable mixture of hydrogen (H₂) and carbon monoxide (CO). The highest faradic efficiency for the production of CO on Ag/C was calculated to be 56.4% at -1.4 V vs Ag/AgCl. The maximum partial current density for the generation of CO was determined to be -9.4 mA cm-2 at a potential of -1.6 V vs Ag/AgCl. This research demonstrates the potential of Ag/C as an electrocatalyst to enable the sustainable production of syngas, contributing to the reduction of CO₂ emissions and the synthesis of valuable chemical precursors and fuels.

Keywords: CO₂, carbon monooxide, electrochemical, silver

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Authors: Mannar R. Maurya, Bithika Sarkar, Fernando Avecilla

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Peroxidase activity is possibly successfully used for different industrial processes in medicine, chemical industry, food processing and agriculture. However, they bear some intrinsic drawback associated with denaturation by proteases, their special storage requisite and cost factor also. Now a day’s artificial enzyme mimics are becoming a research interest because of their significant applications over conventional organic enzymes for ease of their preparation, low price and good stability in activity and overcome the drawbacks of natural enzymes e.g serine proteases. At present, a large number of artificial enzymes have been synthesized by assimilating a catalytic center into a variety of schiff base complexes, ligand-anchoring, supramolecular complexes, hematin, porphyrin, nanoparticles to mimic natural enzymes. Although in recent years a several number of vanadium complexes have been reported by a continuing increase in interest in bioinorganic chemistry. To our best of knowledge, the investigation of artificial enzyme mimics of vanadium complexes is very less explored. Recently, our group has reported synthetic vanadium schiff base complexes capable of mimicking peroxidases. Herein, we have synthesized monoidovanadium(IV) and dioxidovanadium(V) complexes of pyrazoleone derivateis ( extensively studied on account of their broad range of pharmacological appication). All these complexes are characterized by various spectroscopic techniques like FT-IR, UV-Visible, NMR (1H, 13C and 51V), Elemental analysis, thermal studies and single crystal analysis. The peroxidase mimic activity has been studied towards oxidation of pyrogallol to purpurogallin with hydrogen peroxide at pH 7 followed by measuring kinetic parameters. The Michaelis-Menten behavior shows an excellent catalytic activity over its natural counterparts, e.g. V-HPO and HRP. The obtained kinetic parameters (Vmax, Kcat) were also compared with peroxidase and haloperoxidase enzymes making it a promising mimic of peroxidase catalyst. Also, the catalytic activity has been studied towards the oxidation of 1-phenylethanol in presence of H2O2 as an oxidant. Various parameters such as amount of catalyst and oxidant, reaction time, reaction temperature and solvent have been taken into consideration to get maximum oxidative products of 1-phenylethanol.

Keywords: oxovanadium(IV)/dioxidovanadium(V) complexes, NMR spectroscopy, Crystal structure, peroxidase mimic activity towards oxidation of pyrogallol, Oxidation of 1-phenylethanol

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Authors: I. Yunusa, M. A. Ibrahim, A. H. Yakasai, L. U. S. Ezeanyika

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This study was conducted to examine the level of heavy metals among 192 apparently healthy female adolescents randomly selected from three different boarding secondary schools in the urban area of the most populated city in north-western part of Nigeria. Atomic absorption spectrometry (AAS) was used to determine the plasma levels of the heavy metals which include cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), lead (Pb) and zinc (Zn). Our findings revealed the following mean±SD values for each of the heavy metal; 0.11±0.01µg Cd/L, 0.09 ± 0.02µg Co/L, 0.19 ± 0.02 µg Cr/L, 0.91 ± 0.02 µg Cu/L, 1.53 ± 0.31 µg Fe/L, 0.01 ± 0.04 µg Mn/L, 0.3.8 ± 0.04µg Mo/L, 0.04±0.01µg Ni/L, 0.04 ± 0.01µg Pb/L and 2.80 ± 0.24µg Zn/L respectively. It was concluded that toxicity from heavy metals did not exist among female adolescents.

Keywords: heavy metals, female, adolescents, Nigeria

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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: 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: Hongyan Chen, Megan Jobson, Andrew J. Masters, Maria Gonzalez-Miquel, Simon Halstead, Mayri Diaz de Rienzo

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Ionic liquids offer excellent advantages over conventional solvents for industrial extraction of metals from aqueous solutions, where such extraction processes bring opportunities for recovery, reuse, and recycling of valuable resources and more sustainable production pathways. Recent research on the use of ionic liquids for extraction confirms their high selectivity and low volatility, but there is relatively little focus on how their properties can be best exploited in practice. This work addresses gaps in research on process modelling and simulation, to support development, design, and optimisation of these processes, focusing on the separation of the highly similar transition metals, cobalt, and nickel. The study exploits published experimental results, as well as new experimental results, relating to the separation of Co and Ni using trihexyl (tetradecyl) phosphonium chloride. This extraction agent is attractive because it is cheaper, more stable and less toxic than fluorinated hydrophobic ionic liquids. This process modelling work concerns selection and/or development of suitable models for the physical properties, distribution coefficients, for mass transfer phenomena, of the extractor unit and of the multi-stage extraction flowsheet. The distribution coefficient model for cobalt and HCl represents an anion exchange mechanism, supported by the literature and COSMO-RS calculations. Parameters of the distribution coefficient models are estimated by fitting the model to published experimental extraction equilibrium results. The mass transfer model applies Newman’s hard sphere model. Diffusion coefficients in the aqueous phase are obtained from the literature, while diffusion coefficients in the ionic liquid phase are fitted to dynamic experimental results. The mass transfer area is calculated from the surface to mean diameter of liquid droplets of the dispersed phase, estimated from the Weber number inside the extractor. New experiments measure the interfacial tension between the aqueous and ionic phases. The empirical models for predicting the density and viscosity of solutions under different metal loadings are also fitted to new experimental data. The extractor is modelled as a continuous stirred tank reactor with mass transfer between the two phases and perfect phase separation of the outlet flows. A multistage separation flowsheet simulation is set up to replicate a published experiment and compare model predictions with the experimental results. This simulation model is implemented in gPROMS software for dynamic process simulation. The results of single stage and multi-stage flowsheet simulations are shown to be in good agreement with the published experimental results. The estimated diffusion coefficient of cobalt in the ionic liquid phase is in reasonable agreement with published data for the diffusion coefficients of various metals in this ionic liquid. A sensitivity study with this simulation model demonstrates the usefulness of the models for process design. The simulation approach has potential to be extended to account for other metals, acids, and solvents for process development, design, and optimisation of extraction processes applying ionic liquids for metals separations, although a lack of experimental data is currently limiting the accuracy of models within the whole framework. Future work will focus on process development more generally and on extractive separation of rare earths using ionic liquids.

Keywords: distribution coefficient, mass transfer, COSMO-RS, flowsheet simulation, phosphonium

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Authors: Zahid Shafiq, Li Liu, Dong Wang, Yong-Jun Chen

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As synthetic organic methods are increasingly concerned with the growing importance of sustainable chemistry, iodine recently has emerged as an inexpensive, non-toxic, readily available and environmentally benign catalyst for various organic transformations to afford the corresponding products in high yields with high regio- and chemoselectivity. Iodine has found widespread applications in various organic synthesis such as Michael addition, coupling reaction and also in the multicomponent synthesis where it can efficiently activate C=C, C=O, C=N, and so forth. Iodine not only has been shown to be an efficient mild Lewis acid in various processes, but also due to its moderate nature, and water tolerance, reactions catalyzed by iodine can be effectively carried out in neutral media under very mild conditions. We have successfully described an efficient procedure for the nucleophilic substitution of the Baylis-Hillman (BH) adducts and their corresponding acetates with indoles to get α-substitution product using catalytic Silver Triflate (AgOTf) as Lewis acid. At this point, we were interested to develop an environmentally benign catalytic system to effect this substitution reaction and to avoid the use of metal Lewis acid as a catalyst. Since, we observed the formation of -product during the course of the reaction, we also became interested to explore the reaction conditions in order to control regioselectivity and to obtain both regioisomers. The developed methodology resulted in regioselective substitution products with controlled selectivity. Further, the substitution products were used to synthesize various Tri- and Tetracyclo Azepino indole derivatives via reductive amination.

Keywords: indole, regioselective, Baylis-Hillman, substitution

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Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

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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: Hafiz Muhammad Adeel Sharif, Tian Li, Changping Li

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Recently, the emission of nitrogen-sulphur oxides (NOₓ, SO₂) has become a global issue and causing serious threats to health and the environment. Catalytic reduction of NOx and SOₓ gases into friendly gases is considered one of the best approaches. However, regeneration of the catalyst, higher bond-dissociation energy for NOx, i.e., 150.7 kcal/mol, escape of intermediate gas (N₂O, a greenhouse gas) with treated flue-gas, and limited activity of catalyst remains a great challenge. Here, a cheap, binderless naturally-extracted bass-wood thin carbon electrode (TCE) is presented, which shows excellent catalytic activity towards NOx reduction. The bass-wood carbonization at 900 ℃ followed by thermal activation in the presence of CO2 gas at 750 ℃. The thermal activation resulted in an increase in epoxy groups on the surface of the TCE and enhancement in the surface area as well as the degree of graphitization. The TCE unique 3D strongly inter-connected network through hierarchical micro/meso/macro pores that allow large electrode/electrolyte interface. Owing to these characteristics, the TCE exhibited excellent catalytic efficiency towards NOx (~83.3%) under ambient conditions and enhanced catalytic response under pH and sulphite exposure as well as excellent stability up to 168 hours. Moreover, a temperature-dependent activity trend was found where the highest catalytic activity was achieved at 80 ℃, beyond which the electrolyte became evaporative and resulted in a performance decrease. The designed electrocatalyst showed great potential for effective NOx-reduction, which is highly cost-effective, green, and sustainable.

Keywords: electrocatalyst, NOx-reduction, bass-wood electrode, integrated wet-scrubbing, sustainable

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Authors: Jessica Carolina Hernandez Galeano, Juan Carlos Moreno Pirajan, Liliana Giraldo

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Carbon gels are materials whose structure and porous texture can be designed and controlled on a nanoscale. Among their characteristics it is found their low density, large surface area and high degree of porosity. These materials are produced by a sol-gel polymerization of organic monomers using basic or acid catalysts, followed by drying and controlled carbonization. In this work, the synthesis and characterization of carbon aerogels from resorcinol, phenol and formaldehyde in ethanol is described. The aim of this study is obtaining different carbonaceous materials in the form of spheres using the Stöber method to perform a further evaluation of CO₂ adsorption of each material. In general, the synthesis consisted of a sol-gel polymerization process that generates a cluster (cross-linked organic monomers) from the precursors in the presence of NH₃ as a catalyst. This cluster was subjected to specific conditions of gelling and curing (30°C for 24 hours and 100°C for 24 hours, respectively) and CO₂ supercritical drying. Finally, the dry material was subjected to a process of carbonization or pyrolysis, in N₂ atmosphere at 350°C (1° C / min) for 2 h and 600°C (1°C / min) for 4 hours, to obtain porous solids that retain the structure initially desired. For this work, both the concentrations of the precursors and the proportion of ammonia in the medium where modify to describe the effect of the use of phenol and the amount of catalyst in the resulting material. Carbon aerogels were characterized by Scanning Electron Microscope (SEM), N₂ isotherms, infrared spectroscopy (IR) and X-ray Powder Diffraction (XRD) showing the obtention of carbon spheres in the nanometric scale with BET areas around 500 m2g-1.

Keywords: carbon aerogels, carbon spheres, CO₂ adsorption, Stöber method

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Authors: Shinta Ardiana Sari, Dini Puti Angelia

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A high number of urban population in Jakarta has been a substantial issue for mobility strategy. Transit Oriented Development (TOD) becomes one of the strategies to improve community livability based on the design of transit place and the system of its context. TOD principle is trying to win over pedestrian motorization habit, makes people would rather transit and travel more than using private vehicle. Train station takes the main role as the catalyst to emerge TOD, in Jakarta this role will be taken by Commuter line and the future MRT. For advancing its development, architectural design perspective is needed to perform evaluation while seeking for the strategies between accessibility transportation modes with convenience and safety for increasing human behavioral intention. This paper discovers design strategy for transit place that appropriates with Jakarta condition use the basic theories of liminal space and transit-oriented development goal. This paper use evidence-based approach with typology method to analyze the present condition of Commuter Line station in Jakarta and precedent of Asian Cities, Tokyo and Seoul, as the secondary sources, and also with numbers of valid questionnaires. Furthermore, the result of this paper aims to the emerging of a transit-oriented community by giving design requirements and suggestion transportation policies preparing for the operational of MRT in the future Jakarta and other similar cities.

Keywords: station design, transit place, transit-oriented development, urban

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Authors: Paola Leon, Hugo Garcia, Adan Leon, Samuel Munoz

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The enhanced oil recovery by steam injection was considered a process that only generated physical recovery mechanisms. However, there is evidence of the occurrence of a series of chemical reactions, which are called aquathermolysis, which generates hydrogen sulfide, carbon dioxide, methane, and lower molecular weight hydrocarbons. These reactions can be favored by the addition of a catalyst during steam injection; in this way, it is possible to generate the original oil in situ upgrading through the production increase of molecules of lower molecular weight. This additional effect could increase the oil recovery factor and reduce costs in transport and refining stages. Therefore, this research has focused on the experimental evaluation of the catalytic aquathermolysis on a Colombian heavy oil with 12,8°API. The effects of three different catalysts, reaction time, and temperature were evaluated in a batch microreactor. The changes in the Colombian heavy oil were quantified through nuclear magnetic resonance 1H-NMR. The relaxation times interpretation and the absorption intensity allowed to identify the distribution of the functional groups in the base oil and upgraded oils. Additionally, the average number of aliphatic carbons in alkyl chains, the number of substituted rings, and the aromaticity factor were established as average structural parameters in order to simplify the samples' compositional analysis. The first experimental stage proved that each catalyst develops a different reaction mechanism. The aromaticity factor has an increasing order of the salts used: Mo > Fe > Ni. However, the upgraded oil obtained with iron naphthenate tends to form a higher content of mono-aromatic and lower content of poly-aromatic compounds. On the other hand, the results obtained from the second phase of experiments suggest that the upgraded oils have a smaller difference in the length of alkyl chains in the range of 240º to 270°C. This parameter has lower values at 300°C, which indicates that the alkylation or cleavage reactions of alkyl chains govern at higher reaction temperatures. The presence of condensation reactions is supported by the behavior of the aromaticity factor and the bridge carbons production between aromatic rings (RCH₂). Finally, it is observed that there is a greater dispersion in the aliphatic hydrogens, which indicates that the alkyl chains have a greater reactivity compared to the aromatic structures.

Keywords: catalyst, upgrading, aquathermolysis, steam

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Authors: Anıl Dinçer, Dilek Duranoğlu

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Ketones, which are widely used as solvent and chemical intermediates in chemical process industry, are commercially produced by using catalytic dehydrogenation of secondary alcohols at higher temperature (300-500ºC), and pressure (1-5 bar). Although it is possible to obtain high conversion values (60-87%) via gas phase catalytic dehydrogenation, working high temperature and pressure can result in side reactions and shorten the catalyst life. In order to overcome these challenges, catalytic dehydrogenation in the presence of an appropriate liquid solvent has been started to use. Hence, secondary alcohols can be converted to respective ketones at relatively low temperature (150-200ºC) under atmospheric pressure. In this study, methyl ethyl ketone and acetone was produced via catalytic dehydrogenation of appropriate secondary alcohols (isopropyl alcohol and sec-butyl alcohol) in the presence of liquid solvent at 160-190ºC. Obtained methyl ethyl ketone and acetone were analyzed by using FTIR and GC spectrometer. Effects of temperature, amount of catalyst and solvent on conversion and reaction rate were investigated. Optimum process conditions, which gave high conversion and reaction rate, were determined. According to GC results, 70% of secondary butyl alcohol and 42% of isopropyl alcohol was converted to related ketone (methyl ethyl ketone and acetone, respectively) at optimum process conditions. After distillation, 99.13% methyl ethyl ketone and 99.20% acetone was obtained. Consequently, liquid phase dehydrogenation process, which can compete with commercial gas phase process, was developed.

Keywords: dehydrogenation, liquid phase, methyl ethyl ketone, secondary alcohol

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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: Ashish Bohre, Blaž Likozar, Saikat Dutta, Dionisios G. Vlachos, Basudeb Saha

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Graphene oxide, decorated with surface oxygen functionalities, has emerged as a sustainable alternative to precious metal catalysts for many reactions. Herein, we report for the first time that graphene oxide becomes super active for C-C coupling upon incorporation of multilayer crystalline features, highly oxidized surface, Brønsted acidic functionalities and defect sites on the surface and edges via modified oxidation. The resulting improved graphene oxide (IGO) demonstrates superior activity to commonly used framework zeolites for upgrading of low carbon biomass furanics to long carbon chain aviation fuel precursors. A maximum 95% yield of C15 fuel precursor with high selectivity is obtained at low temperature (60 C) and neat conditions via hydroxyalkylation/alkylation (HAA) of 2-methylfuran (2-MF) and furfural. The coupling of 2-MF with carbonyl molecules ranging from C3 to C6 produced the precursors of carbon numbers 12 to 21. The catalyst becomes inactive in the 4th cycle due to the loss of oxygen functionalities, defect sites and multilayer features; however, regains comparable activity upon regeneration. Extensive microscopic and spectroscopic characterization of the fresh and reused IGO is presented to elucidate high activity of IGO and to establish a correlation between activity and surface and structural properties. Kinetic Monte Carlo (KMC) and density functional theory (DFT) calculations are presented to further illustrate the surface features and the reaction mechanism.

Keywords: methacrylic acid, itaconic acid, biomass, monomer, solid base catalyst

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Authors: Kuan Lun Pan, Moo Been Chang

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Volatile organic compounds (VOCs) are one of major air contaminants, and they can react with nitrogen oxides (NOx) in atmosphere to form ozone (O3) and peroxyacetyl nitrate (PAN) with solar irradiation, leading to environmental hazards. In addition, some VOCs are toxic at low concentration levels and cause adverse effects on human health. How to effectively reduce VOCs emission has become an important issue. Thermal catalysis is regarded as an effective way for VOCs removal because it provides oxidation route to successfully convert VOCs into carbon dioxide (CO2) and water (H2O(g)). Single perovskite-type catalysts are promising for VOC removal, and they are of good potential to replace noble metals due to good activity and high thermal stability. Single perovskites can be generally described as ABO3 or A2BO4, where A-site is often a rare earth element or an alkaline. Typically, the B-site is transition metal cation (Fe, Cu, Ni, Co, or Mn). Catalytic properties of perovskites mainly rely on nature, oxidation states and arrangement of B-site cation. Interestingly, single perovskites could be further synthesized to form double perovskite-type catalysts which can simply be represented by A2B’B”O6. Likewise, A-site stands for an alkaline metal or rare earth element, and the B′ and B′′ are transition metals. Double perovskites possess unique surface properties. In structure, three-dimensional of B-site with ordered arrangement of B’O6 and B”O6 is presented alternately, and they corner-share octahedral along three directions of the crystal lattice, while cations of A-site position between the void of octahedral. It has attracted considerable attention due to specific arrangement of alternating B-site structure. Therefore, double perovskites may have more variations than single perovskites, and this greater variation may promote catalytic performance. It is expected that activity of double perovskites is higher than that of single perovskites toward VOC removal. In this study, double perovskite-type catalyst (La2CoMnO6) is prepared and evaluated for VOC removal. Also, single perovskites including LaCoO3 and LaMnO3 are tested for the comparison purpose. Toluene (C7H8) is one of the important VOCs which are commonly applied in chemical processes. In addition to its wide application, C7H8 has high toxicity at a low concentration. Therefore, C7H8 is selected as the target compound in this study. Experimental results indicate that double perovskite (La2CoMnO6) has better activity if compared with single perovskites. Especially, C7H8 can be completely oxidized to CO2 at 300oC as La2CoMnO6 is applied. Characterization of catalysts indicates that double perovskite has unique surface properties and is of higher amounts of lattice oxygen, leading to higher activity. For durability test, La2CoMnO6 maintains high C7H8 removal efficiency of 100% at 300oC and 30,000 h-1, and it also shows good resistance to CO2 (5%) and H2O(g) (5%) of gas streams tested. For various VOCs including isopropyl alcohol (C3H8O), ethanal (C2H4O), and ethylene (C2H4) tested, as high as 100% efficiency could be achieved with double perovskite-type catalyst operated at 300℃, indicating that double perovskites are promising catalysts for VOCs removal, and possible mechanisms will be elucidated in this paper.

Keywords: volatile organic compounds, Toluene (C7H8), double perovskite-type catalyst, catalysis

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Authors: Hyeonseok Yoo, Kiseok Oh, Jinsub Choi

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Titanium oxide nanotubes have attracted great attention because of its photocatalytic activity and large surface area. For enhancing electrochemical properties, catalysts should be doped into the structure because titanium oxide nanotubes themselves have low electroconductivity and catalytic activity. It has been reported that Ru and Ir doped titanium oxide electrodes exhibit high efficiency and low overpotential in the oxygen evolution reaction (OER) for water splitting. In general, titanium oxide nanotubes with high aspect ratio cannot be easily doped by conventional complex methods. Herein, two types of facile routes, namely single step anodization and potential shock, for Ru doping into high aspect ratio titanium oxide nanotubes are introduced in detail. When single step anodization was carried out, stability of electrodes were increased. However, onset potential was shifted to anodic direction. On the other hand, when high potential shock voltage was applied, a large amount of ruthenium/ruthenium oxides were doped into titanium oxide nanotubes and thick barrier oxide layers were formed simultaneously. Regardless of doping routes, ruthenium/ ruthenium oxides were homogeneously doped into titanium oxide nanotubes. In spite of doping routes, doping in aqueous solution generally led to incorporate high amount of Ru in titanium oxide nanotubes, compared to that in non-aqueous solution. The amounts of doped catalyst were analyzed by X-ray photoelectron spectroscopy (XPS). The optimum condition for water splitting was investigated in terms of the amount of doped Ru and thickness of barrier oxide layer.

Keywords: doping, potential shock, single step anodization, titanium oxide nanotubes

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Authors: Adilson C. Barros, Kayo Okazaki, Valter Arthur

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The radio-protective substances protect the organism from ionizing radiation when previously ingested. Synthetic radio-protectives produce unpleasant side effects and are expensive. This article reports the search for natural radio-protective agents in foods, whose occurrence is widespread, costs are lower and the side effects are non-existent. In this work, we studied the eggplant, a food widely used in Brazil, comparing the radiosensitivity of insects reared on diet eggplant and outside this diet. The eggplant causes change in LD50 parameter of insects population but the response curve needs to be better shaped to conclude something about radioprotection. What we can see is that it seems to contain some radiomodifier substance.

Keywords: radioprotector, radiobiology, Solanun melongena L., Lasioderma serricorne

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Authors: Anna Wolowicz, Katarzyna Staszak, Zbigniew Hubicki

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Nowadays heavy metal ions as well as surfactants are widely used throughout the world due to their useful properties. The consequence of such widespread use is their significant production. On the other hand, the increasing demand for surfactants and heavy metal ions results in production of large amounts of wastewaters which are discharged to the environment from mining, metal plating, pharmaceutical, cosmetic, fertilizer, paper, pesticide and electronic industries, pigments producing, petroleum refining and from autocatalyst, fibers, food, polymer industries etc. Heavy metal ions are non-biodegradable in the environment, cable of accumulation in living organisms and organs, toxic and carcinogenic. On the other hand, not only heavy metal ions but also surfactants affect the purity of water and soils. Some of surfactants are also toxic, harmful and dangerous because they are able to penetrate into surface waters causing foaming, blocked diffusion of oxygen from the atmosphere and act as emulsifiers of hydrophobic substances and increase solubility of many the dangerous pollutants. Among surfactants the anionic ones dominate and their share in the global production of surfactants is around 50 ÷ 60%. Due to the negative impact of heavy metals and surfactants on aquatic ecosystems and living organisms, removal and monitoring of their concentration in the environment is extremely important. Surfactants and heavy metal ions removal can be achieved by different biological and physicochemical methods. The adsorption as well as the ion-exchange methods play here a significant role. The aim of this study was heavy metal ions removal from aqueous solutions using different types of ion exchangers in the presence of anionic surfactants. Preliminary studies of copper(II), nickel(II), zinc(II) and cobalt(II) removal from acidic solutions using ion exchangers (Lewatit MonoPlus TP 220, Lewatit MonoPlus SR 7, Purolite A 400 TL, Purolite A 830, Purolite S 984, Dowex PSR 2, Dowex PSR3, Lewatit AF-5) allowed to select the most effective ones for the above mentioned sorbates and then to checking their removal efficiency in the presence of anionic surfactants. As it was found out Lewatit MonoPlus TP 220 of the chelating type, show the highest sorption capacities for copper(II) ions in comparison with the other ion exchangers under discussion, e.g. 9.98 mg/g (0.1 M HCl); 9.12 mg/g (6 M HCl). Moreover, cobalt(II) removal efficiency was the highest in 0.1 M HCl using also Lewatit MonoPlus TP 220 (6.9 mg/g) similar to zinc(II) (9.1 mg/g) and nickiel(II) (6.2 mg/g). As the anionic surfactant sodium dodecyl sulphate (SDS) was used and surfactant parameters such as viscosity (η), density (ρ) and critical micelle concentration (CMC) were obtained: η = 1.13 ± 0,01 mPa·s; ρ = 999.76 mg/cm3; CMC = 2.26 g/cm3. The studies of copper(II) removal from acidic solutions in the presence of SDS of different concentration show negligible effects on copper(II) removal efficiency. The sorption capacity of Cu(II) from 0.1 M acidic solution of 500 mg/L initial concentration was equal to 46.8 mg/g whereas in the presence of SDS 45.3 mg/g (0.1 mg SDS/L), 47.1 mg/g (0.5 mg SDS/L), 46.6 mg/g (1 mg SDS/L).

Keywords: anionic surfactant, heavy metal ions, ion exchanger, removal

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Authors: Ravinder Kataria, Jatinder Kumar, B. S. Pabla

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Ultrasonic machining is one of the most widely used non-traditional machining processes for machining of materials that are relatively brittle, hard, and fragile such as advanced ceramics, refractories, crystals, quartz etc. Present article has been targeted at investigating the impact of different experimental conditions (power rating, cobalt content, tool material, thickness of work piece, tool geometry, and abrasive grit size) on over cut in ultrasonic drilling of WC-Co composite material. Taguchi’s L-36 orthogonal array has been employed for conducting the experiments. Significant factors have been identified using analysis of variance (ANOVA) test. The experimental results revealed that abrasive grit size and tool material are most significant factors for over cut.

Keywords: ANOVA, abrasive grit size, Taguchi, WC-Co, ultrasonic machining

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Authors: Kefale W. Yizengaw, Delele Worku Ayele, Jyh-Chiang Jiang

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The catalytic co-conversion of CO₂ and CH₄ to value-added compounds has become one of the promising approaches to addressing global climate change by having valuable fossil fuels. Thedirect co-conversion of CO₂ and CH₄ to value-added compounds is attractive but tremendously challenging because of both molecules' thermodynamic stability and kinetic inertness. In the present study, a single iridium atom doped and a single oxygen atom defect hematite (110)surface model catalyst, which can comprehend direct C–O coupling based on simultaneous activation of CO2 and CH4 was studied using density functional theory plus U (DFT + U)calculations. The presence of dual active sites on the Ir/Fe₂O₃(110)-OV surface catalyst enablesCO₂ activation on the Ir site and CH₄ activation at the defect site. The electron analysis for the theco-adsorption of CO₂ and CH₄ deals with the electron redistribution on the surface and clearly shows the synergistic effect for simultaneous CO₂ and CH₄ activation on Ir/α- Fe₂O₃(110)-OVsurface. The microkinetic analysis shows that the dissociation of CH4 to CH3 * and H* plays an excellent role in the C–O coupling. The coverage analysis for the intermediate products of the microkinetic simulation results indicates that C–O coupling is the reaction limiting step. Finally, after the CH₃O* intermediate product species is produced, the radical hydrogen species spontaneously diffuse to the CH3O* intermediate product to form methanol at around 490 [K]. The present work provides mechanistic and kinetic insights into the direct C–O coupling of CO₂and CH₄, which could help design more-efficient catalysts.

Keywords: co-conversion, C–O coupling, doping, oxygen vacancy, microkinetic

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Authors: Ipek Gunay, Efe B. Orman, Metin Ozer, Bekir Salih, Ali R. Ozkaya

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Phthalocyanines with macrocyclic ring containing at least three heteroatoms have nine or more membered structures. Metal-free phthalocyanines react with metal salts to obtain chelate complexes. This is one of the most important features of metal-free phthalocyanine as ligand structure. Although phthalocyanines have very similar properties with porphyrins, they have some advantages such as lower cost, easy to prepare, and chemical and thermal stability. It’s known that Pc compounds have shown one-electron metal-and/or ligand-based reversible or quasi-reversible reduction and oxidation processes. The redox properties of phthalocyanines are critically related to the desirable properties of these compounds in their technological applications. Thus, Pc complexes have also been receiving increasing interest in the area of fuel cells due to their high electrocatalytic activity in dioxygen reduction and fuel cell applications. In this study, novel phthalocyanine complexes coordinated with Fe(II) and Co (II) to be used as catalyst were synthesized. Aiming this goal, a new nitrile ligand was synthesized starting from 4-hydroxy-3,5-dimethoxy benzyl alcohol and 4-nitrophthalonitrile in the presence of K2CO3 as catalyst. After the isolation of the new type of nitrile and metal complexes, the characterization of mentioned compounds was achieved by IR, H-NMR and UV-vis methods. In addition, the electrochemical behaviour of Pc complexes was identified by cyclic voltammetry, square wave voltammetry and in situ spectroelectrochemical measurements. Furthermore, the catalytic performances of Pc complexes for oxygen reduction were tested by dynamic voltammetry measurements, carried out by the combined system of rotating ring-disk electrode and potentiostat, in a medium similar to fuel-cell working conditions.

Keywords: phthalocyanine, electrocatalysis, electrochemistry, in-situ spectroelectrochemistry

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Authors: Riad Benelmir, Muhammad Shoaib Ahmed Khan

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The socio-economic importance of the olive oil production is significant in the Mediterranean region, both in terms of wealth and tradition. However, the extraction of olive oil generates huge quantities of wastes that may have a great impact on land and water environment because of their high phytotoxicity. Especially olive mill wastewater (OMWW) is one of the major environmental pollutants in olive oil industry. This work projects to design a smart and sustainable integrated thermochemical catalytic processes of residues from olive mills by hydrothermal carbonization (HTC) of olive mill wastewater (OMWW) and fast pyrolysis of olive mill wastewater sludge (OMWS). The byproducts resulting from OMWW-HTC treatment are a solid phase enriched in carbon, called biochar and a liquid phase (residual water with less dissolved organic and phenolic compounds). HTC biochar can be tested as a fuel in combustion systems and will also be utilized in high-value applications, such as soil bio-fertilizer and as catalyst or/and catalyst support. The HTC residual water is characterized, treated and used in soil irrigation since the organic and the toxic compounds will be reduced under the permitted limits. This project’s concept includes also the conversion of OMWS to a green diesel through a catalytic pyrolysis process. The green diesel is then used as biofuel in an internal combustion engine (IC-Engine) for automotive application to be used for clean transportation. In this work, a theoretical study is considered for the use of heat from the pyrolysis non-condensable gases in a sorption-refrigeration machine for pyrolysis gases cooling and condensation of bio-oil vapors.

Keywords: biomass, olive oil extraction, adsorption cooling, pyrolisis

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Authors: Michael Huber, Maximilian J. Poller, Jens Tochtermann, Wolfgang Korth, Andreas Jess, Jakob Albert

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Aside from the desulfurisation, the denitrogenation of fuels is of great importance to minimize the environmental impact of transport emissions. The oxidative reaction pathway of organic nitrogen in the catalytic oxidative denitrogenation could be successfully elucidated. This is the first time such a pathway could be traced in detail in non-microbial systems. It was found that the organic nitrogen is first oxidized to nitrate, which is subsequently reduced to molecular nitrogen via nitrous oxide. Hereby, the organic substrate serves as a reducing agent. The discovery of this pathway is an important milestone for the further development of fuel denitrogenation technologies. The United Nations aims to counteract global warming with Net Zero Emissions (NZE) commitments; however, it is not yet foreseeable when crude oil-based fuels will become obsolete. In 2021, more than 50 million barrels per day (mb/d) were consumed for the transport sector alone. Above all, heteroatoms such as sulfur or nitrogen produce SO₂ and NOx during combustion in the engines, which is not only harmful to the climate but also to health. Therefore, in refineries, these heteroatoms are removed by hy-drotreating to produce clean fuels. However, this catalytic reaction is inhibited by the basic, nitrogenous reactants (e.g., quinoline) as well as by NH3. The ion pair of the nitrogen atom forms strong pi-bonds to the active sites of the hydrotreating catalyst, which dimin-ishes its activity. To maximize the desulfurization and denitrogenation effectiveness in comparison to just extraction and adsorption, selective oxidation is typically combined with either extraction or selective adsorption. The selective oxidation produces more polar compounds that can be removed from the non-polar oil in a separate step. The extraction step can also be carried out in parallel to the oxidation reaction, as a result of in situ separation of the oxidation products (ECODS; extractive catalytic oxidative desulfurization). In this process, H8PV5Mo7O40 (HPA-5) is employed as a homogeneous polyoxometalate (POM) catalyst in an aqueous phase, whereas the sulfur containing fuel components are oxidized after diffusion from the organic fuel phase into the aqueous catalyst phase, to form highly polar products such as H₂SO₄ and carboxylic acids, which are thereby extracted from the organic fuel phase and accumulate in the aqueous phase. In contrast to the inhibiting properties of the basic nitrogen compounds in hydrotreating, the oxidative desulfurization improves with simultaneous denitrification in this system (ECODN; extractive catalytic oxidative denitrogenation). The reaction pathway of ECODS has already been well studied. In contrast, the oxidation of nitrogen compounds in ECODN is not yet well understood and requires more detailed investigations.

Keywords: oxidative reaction pathway, denitrogenation of fuels, molecular catalysis, polyoxometalate

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Authors: Chinwendu R. Nnabalu, Gioia Falcone, Imma Bortone

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Petroleum refining is a chemical process in which the raw material (crude oil) is converted to finished commercial products for end users. The fluid catalytic cracking (FCC) unit is a key asset in refineries, requiring optimised processes in the context of engineering design. Following the first stage of separation of crude oil in a distillation tower, an additional 40 per cent quantity is attainable in the gasoline pool with further conversion of the downgraded product of crude oil (residue from the distillation tower) using a catalyst in the FCC process. Effective removal of sulphur oxides, nitrogen oxides, carbon and heavy metals from FCC gasoline requires greater separation efficiency and involves an enormous environmental significance. The FCC unit is primarily a reactor and regeneration system which employs cyclone systems for separation.  Catalyst losses in FCC cyclones lead to high particulate matter emission on the regenerator side and fines carryover into the product on the reactor side. This paper aims at demonstrating the importance of FCC unit design criteria in terms of technical performance and compliance with environmental legislation. A systematic review of state-of-the-art FCC technology was carried out, identifying its key technical challenges and sources of emissions.  Case studies of petroleum refineries in Nigeria were assessed against selected global case studies. The review highlights the need for further modelling investigations to help improve FCC design to more effectively meet product specification requirements while complying with stricter environmental legislation.

Keywords: design, emission, fluid catalytic cracking, petroleum refineries

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Authors: Bhairi Lakshminarayana, Surajit Sarker, Ch. Subrahmanyam

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The present study reports the development of noble metal free nano catalysts for low-temperature CO oxidation and water gas shift reaction. Mn-substituted CeO2 solid solution catalysts were synthesized by co-precipitation, combustion and hydrothermal methods. The formation of solid solution was confirmed by XRD with Rietveld refinement and the percentage of carbon and nitrogen doping was ensured by CHNS analyzer. Raman spectroscopic confirmed the oxygen vacancies. The surface area, pore volume and pore size distribution confirmed by N2 physisorption analysis, whereas, UV-visible diffuse reflectance spectroscopy and XPS data confirmed the oxidation state of the Mn ion. The particle size and morphology (spherical shape) of the material was confirmed using FESEM and HRTEM analysis. Ce0.8Mn0.2O2-δ was calcined at 400 °C, 600 °C and 800 °C. Raman spectroscopy confirmed that the catalyst calcined at 400 °C has the best redox properties. The activity of the designed catalysts for CO oxidation (0.2 vol%), carried out with GHSV of 21,000 h-1 and it has been observed that co-precipitation favored the best active catalyst towards CO oxidation and water gas shift reaction, due to the high surface area, improved reducibility, oxygen mobility and highest quantity of surface oxygen species. The activation energy of low temperature CO oxidation on Ce0.8Mn0.2O2- δ (combustion) was 5.5 kcal.K-1.mole-1. The designed catalysts were tested for water gas shift reaction. The present study demonstrates that Mn ion substituted ceria at 400 °C calcination temperature prepared by co-precipitation method promise to revive a green sustainable energy production approach.

Keywords: Ce0.8Mn0.2O2-ð, CO oxidation, physicochemical characterization, water gas shift reaction (WGS)

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Authors: C. Rajalakshmi, Vibin Ipe Thomas

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Sonogashira coupling reactions are widely employed in the synthesis of molecules of biological and pharmaceutical importance. Copper catalyzed Sonogashira coupling reactions are gaining importance owing to the low cost and less toxicity of copper as compared to the palladium catalyst. In the present work, a detailed computational study has been carried out on the Sonogashira coupling reaction between aryl halides and terminal alkynes catalyzed by Copper (I) species with trans-1, 2 Diaminocyclohexane as ligand. All calculations are performed at Density Functional Theory (DFT) level, using the hybrid Becke3LYP functional. Cu and I atoms are described using an effective core potential (LANL2DZ) for the inner electrons and its associated double-ζ basis set for the outer electrons. For all other atoms, 6-311G+* basis set is used. We have identified that the active catalyst species is a neutral 3-coordinate trans-1,2 diaminocyclohexane ligated Cu (I) alkyne complex and found that the oxidative addition and reductive elimination occurs in a single step proceeding through one transition state. This is owing to the ease of reductive elimination involving coupling of Csp2-Csp carbon atoms and the less stable Cu (III) intermediate. This shows the mechanism of copper catalyzed Sonogashira coupling reactions are quite different from those catalyzed by palladium. To gain further insights into the mechanism, substrates containing various functional groups are considered in our study to traverse their effect on the feasibility of the reaction. We have also explored the effect of ligand on the catalytic cycle of the coupling reaction. The theoretical results obtained are in good agreement with the experimental observation. This shows the relevance of a combined theoretical and experimental approach for rationally improving the cross-coupling reaction mechanisms.

Keywords: copper catalysed, density functional theory, reaction mechanism, Sonogashira coupling

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