Search results for: catalytic cracking

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: Anton G. Kalmykov, Andrew Yu. Bychkov, Georgy A. Kalmykov

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Nowadays, most oil reserves in Russia and all over the world are hard to recover. That is the reason oil companies are searching for new sources for hydrocarbon production. One of the sources might be high-carbon formations with unconventional reservoirs. Bazhenov formation is a huge source rock formation located in West Siberia, which contains unconventional reservoirs on some of the areas. These reservoirs are formed by secondary processes with low predicting ratio. Only one of five wells is drilled through unconventional reservoirs, in others kerogen has low thermal maturity, and they are of low petroliferous. Therefore, there was a request for tertiary methods for in-situ cracking of kerogen and production of oil. Laboratory experiments of Bazhenov formation rock hydrous pyrolysis were used to investigate features of the oil generation process. Experiments on Bazhenov rocks with a different mineral composition (silica concentration from 15 to 90 wt.%, clays – 5-50 wt.%, carbonates – 0-30 wt.%, kerogen – 1-25 wt.%) and thermal maturity (from immature to late oil window kerogen) were performed in a retort under reservoir conditions. Rock samples of 50 g weight were placed in retort, covered with water and heated to the different temperature varied from 250 to 400°C with the durability of the experiments from several hours to one week. After the experiments, the retort was cooled to room temperature; generated hydrocarbons were extracted with hexane, then separated from the solvent and weighted. The molecular composition of this synthesized oil was then investigated via GC-MS chromatography Characteristics of rock samples after the heating was measured via the Rock-Eval method. It was found, that the amount of synthesized oil and its composition depending on the experimental conditions and composition of rocks. The highest amount of oil was produced at a temperature of 350°C after 12 hours of heating and was up to 12 wt.% of initial organic matter content in the rocks. At the higher temperatures and within longer heating time secondary cracking of generated hydrocarbons occurs, the mass of produced oil is lowering, and the composition contains more hydrocarbons that need to be recovered by catalytical processes. If the temperature is lower than 300°C, the amount of produced oil is too low for the process to be economically effective. It was also found that silica and clay minerals work as catalysts. Selection of heating conditions allows producing synthesized oil with specified composition. Kerogen investigations after heating have shown that thermal maturity increases, but the yield is only up to 35% of the maximum amount of synthetic oil. This yield is the result of gaseous hydrocarbons formation due to secondary cracking and aromatization and coaling of kerogen. Future investigations will allow the increase in the yield of synthetic oil. The results are in a good agreement with theoretical data on kerogen maturation during oil production. Evaluated trends could be tooled up for in-situ oil generation by shale rocks thermal action.

Keywords: Bazhenov formation, fossil fuels, hydropyrolysis, synthetic oil

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Authors: Auezhan Amanov, Inho Cho, Young-Sik Pyun

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Control element drive mechanism (CEDM) nozzle is manufactured as welded on the reactor vessel and currently uses Alloy 690 material. The top of the reactor is equipped with about 100 CEDM nozzles with an internal diameter of about 70 mm. Relatively large Inlet/Outlet nozzles are equipped with two outlet nozzles and four inlet nozzles on the reactor wall. The inner diameter of the nozzle is vulnerable to stress corrosion cracking (SCC), and in order to solve this problem, an ultrasonic nanocrystal surface modification (UNSM) treatment is performed on the inner diameter of the nozzle and the weld surface. The ultimate goal is to improve the service life of parts by applying compressive residual stress and suppressing primary water stress corrosion cracking (PWSCC). The main purpose is to design and fabricate a UNSM treatment device for the internal diameter processing of CEDM nozzles and inlet/outlet nozzles. In order to develop the system, the basic technology such as the development of UNSM tooling is developed and the mechanical properties and fatigue performance of before and after UNSM treatment of reactor nozzle material made of Ni-based alloys using the specimen are compared and evaluated. The inner diameter of the nozzle was treated by a newly developed UNSM treatment under the optimized treatment parameters. It was found that the mechanical properties and fatigue performance of nozzle were improved in comparison with the untreated nozzle, which may be attributed to the increase in hardness, induced compressive residual stress.

Keywords: control element drive mechanism nozzle, fatigue, Ni-based alloy, ultrasonic nanocrystal surface modification, UNSM

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Authors: Ali Ashtiani, Hamid Shirazi

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This paper reviews the status of existing practice and research related to measuring pavement cracking and using crack density as a pavement surface evaluation protocol. Crack density for pavement evaluation is currently not widely used within the airport community and its use by the highway community is limited. However, surface cracking is a distress that is closely monitored by airport staff and significantly influences the development of maintenance, rehabilitation and reconstruction plans for airport pavements. Therefore crack density has the potential to become an important indicator of pavement condition if the type, severity and extent of surface cracking can be accurately measured. A pavement distress survey is an essential component of any pavement assessment. Manual crack surveying has been widely used for decades to measure pavement performance. However, the accuracy and precision of manual surveys can vary depending upon the surveyor and performing surveys may disrupt normal operations. Given the variability of manual surveys, this method has shown inconsistencies in distress classification and measurement. This can potentially impact the planning for pavement maintenance, rehabilitation and reconstruction and the associated funding strategies. A substantial effort has been devoted for the past 20 years to reduce the human intervention and the error associated with it by moving toward automated distress collection methods. The automated methods refer to the systems that identify, classify and quantify pavement distresses through processes that require no or very minimal human intervention. This principally involves the use of a digital recognition software to analyze and characterize pavement distresses. The lack of established protocols for measurement and classification of pavement cracks captured using digital images is a challenge to developing a reliable automated system for distress assessment. Variations in types and severity of distresses, different pavement surface textures and colors and presence of pavement joints and edges all complicate automated image processing and crack measurement and classification. This paper summarizes the commercially available systems and technologies for automated pavement distress evaluation. A comprehensive automated pavement distress survey involves collection, interpretation, and processing of the surface images to identify the type, quantity and severity of the surface distresses. The outputs can be used to quantitatively calculate the crack density. The systems for automated distress survey using digital images reviewed in this paper can assist the airport industry in the development of a pavement evaluation protocol based on crack density. Analysis of automated distress survey data can lead to a crack density index. This index can be used as a means of assessing pavement condition and to predict pavement performance. This can be used by airport owners to determine the type of pavement maintenance and rehabilitation in a more consistent way.

Keywords: airport pavement management, crack density, pavement evaluation, pavement management

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Authors: Rajashekar Badam, Vedarajan Raman, Noriyoshi Matsumi

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Efficiency of energy converting and storage systems like fuel cells and Li-Air battery principally depended on oxygen reduction reaction (ORR) which occurs at cathode. As the kinetics of the ORR is very slow, it becomes the rate determining step. Exploring carbon substrates for enhancing the dispersion and activity of the metal catalyst and commercially viable simple preparation method is a very crucial area of research in the field of energy materials. Hence, many researchers made large number of carbon-based ORR materials today. But, there are hardly few studies on the effect of interaction between Pt-carbon and carbon-electrolyte on activity. In this work, we have prepared functionalized carbon-based Pt catalyst (Pt-FAB) with enhanced interfacial properties that lead to efficient ORR catalysis. The present work deals with a single-pot method to exfoliate and functionalized acetylene black with enhanced interaction with Pt as well as electrolyte. Acetylene black was functionalized and exfoliated using a facile single pot acid treatment method. The resulted FAB was further decorated with Pt-nano particles (Pt-np). The TEM images of Pt-FAB with uniformly decorated Pt-np of ~3 nm. Further, XPS studies of Pt 4f peak revealed that Pt0 peak was shifted by 0.4 eV in Pt-FAB compared to binding energy of typical Pt⁰ found in Pt/C. The shift can be ascribed to the modulation of electronic state and strong electronic interaction of Pt with carbon. Modulated electronic structure of Pt and strong electronic interaction of Pt with FAB enhances the catalytic activity and durability respectively. To understand the electrode electrolyte interface, electrochemical impedance spectroscopy was carried out. These measurements revealed that the charge transfer resistance of electrode to electrolyte for Pt-FAB is 10 times smaller than that of conventional Pt/C. The interaction with electrolyte helps reduce the interface boundaries, which in turn affects the overall catalytic performance of the electrode. Cyclic voltammetric measurements in 0.1M HClO₄ aq. at a potential scan rate of 50 mVs-1 was employed to evaluate electrochemical surface area (ECSA) of Pt. ECSA of Pt-FAB was found to be as high as 67.2 m²g⁻¹. The three-electrode system showed very high ORR catalytic activity. Mass activity at 0.9 V vs. RHE showed 460 A/g which is much higher than the DOE target values for the year 2020. Further, it showed enhanced performance by showing 723 mW/cm² of highest power density and 1006 mA/cm² of current density at 0.6 V in fuel cell single cell type configuration and 1030 mAhg⁻¹ of rechargeable capacity in Li air battery application. The higher catalytic activity can be ascribed to the improved interaction of FAB with Pt and electrolyte. The aforementioned results evince that Pt-FAB will be a promising cathode material for efficient ORR with significant cyclability for its application in fuel cells and Li-Air batteries. In conclusion, a disordered material was prepared from AB and was systematically characterized. The extremely high ORR activity and ease of preparation make it competent for replacing commercially available ORR materials.

Keywords: functionalized acetylene black, oxygen reduction reaction, fuel cells, Functionalized battery

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Authors: Berkas Khaoula

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Based on selection characteristics, high-density polyethylene (HDPE) extruded pipes are among the most economical and durable materials as well-designed solutions for water and gas transmission systems. The main reasons for such a choice are the high quality-performance ratio and the long-term service durability under aggressive conditions. Due to inevitable interactions with soils of different chemical compositions and transported fluids, aggressiveness becomes a key factor in studying resilient strength and life prediction limits. This phenomenon is known as environmental stress cracking resistance (ESCR). In this work, the effect of 3 acidic environments (5% acetic, 20% hydrochloric and 20% sulfuric) on HDPE-100 samples (~10x11x24 mm3). The results presented in the form (Δm/m0, %) as a function of √t indicate that the absorption, in the case of strong acids (HCl and H2SO4), evolves towards negative values involving material losses such as antioxidants and some additives. On the other hand, acetic acid and deionized water (DW) give a form of linear Fickean (LF) and B types, respectively. In general, the acids cause a slow but irreversible alteration of the chemical structure, composition and physical integrity of the polymer. The DW absorption is not significant (~0.02%) for an immersion duration of 69 days. Such results are well accepted in actual applications, while changes caused by acidic environments are serious and must be subjected to particular monitoring of the OIT factor (Oxidation Induction Time). After 55 days of aging, the H2SO4 and HCl media showed particular values with a loss of % mass in the interval [0.025-0.038] associated with irreversible chemical reactions as well as physical degradations. This state is usually explained by hydrolysis of the polymer, causing the loss of functions and causing chain scissions. These results are useful for designing and estimating the lifetime of the tube in service and in contact with adverse environments.

Keywords: HDPE, environmental stress cracking, absorption, acid media, chemical aging

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Authors: Mohit Chauhan, Atul Narayan

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Moisture damage is the continuous deterioration of asphalt concrete mixtures by the loss of adhesive bond between the asphalt binder and aggregates, or loss of cohesive bonds within the asphalt binder in the presence of moisture. Moisture has been known to either cause or exacerbates distresses in asphalt concrete pavements. Since moisture would often retain for a relatively long duration at the bottom of asphalt concrete layer, the movement of traffic loading in this saturated condition would cause excess stresses or strains within the mixture. This would accelerate the degradation of the adhesion and cohesion within the mixture and likely to contribute the development of fatigue cracking in asphalt concrete pavements. In view of this, it is important to investigate the effect of moisture on the fatigue behavior of asphalt concrete mixtures. In this study, changes in fatigue characteristics after moisture conditioning were evaluated by conducting four-point beam fatigue tests on dry and moisture conditioned specimens. For this purpose, mixtures with two different types of binders were prepared and saturated with moisture using 700 mm Hg vacuum. Beam specimens, in this way, were taken to a saturation level of 65-75 percent. After preconditioning specimens in this degree of saturation and 60°C for a period of 24 hours, they were subjected to four point beam fatigue tests in strain-controlled mode with a strain amplitude of 400 microstrain. The results were then compared with the fatigue test results obtained with beam specimens that were not subjected to moisture conditioning. Test results show that the conditioning reduces both fatigue life and initial flexural stiffness of specimen significantly. The moisture conditioning was also found to increase the rate of reduction of flexural stiffness. Moreover, it was observed that the fatigue life ratio (FLR), the ratio of the fatigue life of the moisture conditioned sample to that of the dry sample, is significantly lower than the flexural stiffness ratio (FSR). The study indicates that four-point bending test is an appropriate tool with FLR and FSR as the potential parameters for moisture-sensitivity evaluation.

Keywords: asphalt concrete, fatigue cracking, moisture damage, preconditioning

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Authors: H. A. Jawan

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This review describes the models of environmental-related crack propagation of aluminum alloys (7xxx) during the last few decades. Acknowledge on effects of different factors on the susceptibility to SCC permits to propose valuable mechanisms on crack advancement. The reliable mechanism of cracking give a possibility to propose the optimum chemical composition and thermal treatment conditions resulting in microstructure the most suitable for real environmental condition and stress state.

Keywords: microstructure, environmental, propagation, mechanism

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Authors: Masood Otarod, Ronald M. Supkowski

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This abstract discusses a method that reduces the general dispersion model in cylindrical coordinates to a second order linear ordinary differential equation with constant coefficients so that it can be utilized to conduct kinetic studies in packed bed tubular catalytic reactors at a broad range of Reynolds numbers. The model was tested by 13CO isotope transient tracing of the CO adsorption of Boudouard reaction in a differential reactor at an average Reynolds number of 0.2 over Pd-Al2O3 catalyst. Detailed experimental results have provided evidence for the validity of the theoretical framing of the model and the estimated parameters are consistent with the literature. The solution of the general dispersion model requires the knowledge of the radial distribution of axial velocity. This is not always known. Hence, up until now, the implementation of the dispersion model has been largely restricted to the plug-flow regime. But, ideal plug-flow is impossible to achieve and flow regimes approximating plug-flow leave much room for debate as to the validity of the results. The reduction of the general dispersion model transpires as a result of the application of a factorization theorem. Factorization theorem is derived from the observation that a cross section of a catalytic bed consists of a solid phase across which the reaction takes place and a void or porous phase across which no significant measure of reaction occurs. The disparity in flow and the heterogeneity of the catalytic bed cause the concentration of reacting compounds to fluctuate radially. These variabilities signify the existence of radial positions at which the radial gradient of concentration is zero. Succinctly, factorization theorem states that a concentration function of axial and radial coordinates in a catalytic bed is factorable as the product of the mean radial cup-mixing function and a contingent dimensionless function. The concentration of adsorbed compounds are also factorable since they are piecewise continuous functions and suffer the same variability but in the reverse order of the concentration of mobile phase compounds. Factorability is a property of packed beds which transforms the general dispersion model to an equation in terms of the measurable mean radial cup-mixing concentration of the mobile phase compounds and mean cross-sectional concentration of adsorbed species. The reduced model does not require the knowledge of the radial distribution of the axial velocity. Instead, it is characterized by new transport parameters so denoted by Ωc, Ωa, Ωc, and which are respectively denominated convection coefficient cofactor, axial dispersion coefficient cofactor, and radial dispersion coefficient cofactor. These cofactors adjust the dispersion equation as compensation for the unavailability of the radial distribution of the axial velocity. Together with the rest of the kinetic parameters they can be determined from experimental data via an optimization procedure. Our data showed that the estimated parameters Ωc, Ωa Ωr, are monotonically correlated with the Reynolds number. This is expected to be the case based on the theoretical construct of the model. Computer generated simulations of methanation reaction on nickel provide additional support for the utility of the newly conceptualized dispersion model.

Keywords: factorization, general dispersion model, isotope transient kinetic, partial differential equations

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Authors: Neslihan Beyazit, Sahin Bayraktar, Cahit Demetgul

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Transition metal ions have an important role in biochemistry and biomimetic systems and may provide the basis of models for active sites of biological targets. The presence of copper(II), iron(II) and zinc(II) is crucial in many biological processes. Tetradentate N2O2 donor Schiff base ligands are well known to form stable transition metal complexes and these complexes have also applications in clinical and analytical fields. In this study, we present salient structural features and the details of cathecholase activity of Fe(II) complex of a new Schiff Base ligand. A new asymmetrical N2O2 donor Schiff base ligand and its Fe(II) complex were synthesized by condensation of 4-nitro-1,2 phenylenediamine with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one and by using an appropriate Fe(II) salt, respectively. Schiff base ligand and its metal complex were characterized by using FT-IR, 1H NMR, 13C NMR, UV-Vis, elemental analysis and magnetic susceptibility. In order to determine the kinetics parameters of catechol oxidase-like activity of Schiff base Fe(II) complex, the oxidation of the 3,5-di-tert-butylcatechol (3,5-DTBC) was measured at 25°C by monitoring the increase of the absorption band at 390-400 nm of the product 3,5-di-tert-butylcatequinone (3,5-DTBQ). The compatibility of catalytic reaction with Michaelis-Menten kinetics also investigated by the method of initial rates by monitoring the growth of the 390–400 nm band of 3,5-DTBQ as a function of time. Kinetic studies showed that Fe(II) complex of the new N2O2 donor Schiff base ligand was capable of acting as a model compound for simulating the catecholase properties of type-3 copper proteins.

Keywords: catecholase activity, Michaelis-Menten kinetics, Schiff base, transition metals

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Authors: H. Jawan

Abstract:

This review describes the models of environmental-related crack propagation of aluminum alloys (7xxx) during the last few decades. Acknowledge on effects of different factors on the susceptibility to SCC permits to propose valuable mechanisms on crack advancement. The reliable mechanism of cracking give a possibility to propose the optimum chemical composition and thermal treatment conditions resulting in microstructure the most suitable for real environmental condition and stress state.

Keywords: microstructure, environmental, propagation, mechanism

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Authors: Karima Benfadel, Lamia Talbi, Sabiha Anas Boussaa, Afaf Brik, Assia Boukezzata, Yahia Ouadah, Samira Kaci

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In order to prevent global warming, which is mainly caused by the increase in carbon dioxide levels in the atmosphere, it is interesting to produce renewable energy in the form of chemical energy by converting carbon dioxide into alternative fuels and other energy-dense products. Photoelectrochemical reduction of carbon dioxide to value-added products and fuels is a promising and current method. The objective of our study is to develop Cu₂S-based photoélectrodes, in which Cu₂S is used as a CO₂ photoelectrocatalyst deposited on nanostructured silicon substrates. Cu₂S thin layers were deposited using the chemical bath deposition (CBD) technique. Silicon nanowires and nanopyramids were obtained by alkaline etching. SEM and UV-visible spectroscopy was used to analyse the morphology and optical characteristics. By using a potentiostat station, we characterized the photoelectrochemical properties. We performed cyclic voltammetry in the presence and without CO₂ purging as well as linear voltammetry (LSV) in the dark and under white light irradiation. We perform chronoamperometry to study the stability of our photocathodes. The quality of the nanowires and nanopyramids was visible in the SEM images, and after Cu₂S deposition, we could see how the deposition was distributed over the textured surfaces. The inclusion of the Cu₂S layer applied on textured substrates significantly reduces the reflectance (R%). The catalytic performance towards CO₂ conversion of Cu₂S/Si-based photocathodes revealed that the texturing of the silicon surface with nanowires and pyramids has a better photoelectrochemical behavior than those without surface modifications.

Keywords: CO₂ conversion, Cu₂S photocathode, silicone nanostructured, electrochemistry

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Authors: Matthew E. Potter, Daniel J. Stewart, Lindsay M. Armstrong, Pier J. A. Sazio, Robert R. Raja

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Rising CO₂ levels in the atmosphere means that CO₂ is a highly desirable feedstock. This requires specific catalysts to be designed to activate this inert molecule, combining a catalytic site tailored for CO₂ transformations with a support that can readily adsorb CO₂. Metal organic frameworks (MOFs) are regularly used as CO₂ sorbents. The organic nature of the linker molecules, connecting the metal nodes, offers many post-synthesis modifications to introduce catalytic active sites into the frameworks. However, the metal nodes may be coordinatively unsaturated, allowing them to bind to organic moieties. Imidazoles have shown promise catalyzing the formation of cyclic carbonates from epoxides with CO₂. Typically, this synthesis route employs toxic reagents such as phosgene, liberating HCl. Therefore an alternative route with CO₂ is highly appealing. In this work we design active sites for CO₂ activation, by tethering substituted-imidazole organocatalytic species to the available Cr3+ metal nodes of a Cr-MIL-101 MOF, for the first time, to create a tailored species for carbon capture utilization applications. Our tailored design strategy combining a CO₂ sorbent, Cr-MIL-101, with an anchored imidazole results in a highly active and selective multifunctional catalyst, achieving turnover frequencies of over 750 hr-1. These findings demonstrate the synergy between the MOF framework and imidazoles for CO₂ utilization applications. Further, the effect of substrate variation has been explored yielding mechanistic insights into this process. Through characterization, we show that the structural and compositional integrity of the Cr-MIL-101 has been preserved on functionalizing the imidazoles. Further, we show the binding of the imidazoles to the Cr3+ metal nodes. This can be seen through our EPR study, where the distortion of the Cr3+ on binding to the imidazole shows the CO₂ binding site is close to the active imidazole. This has a synergistic effect, improving catalytic performance. We believe the combination of MOF support and organocatalyst allows many possibilities to generate new multifunctional catalysts for CO₂ utilisation. In conclusion, we have validated our design procedure, combining a known CO₂ sorbent, with an active imidazole species to create a unique tailored multifunctional catalyst for CO₂ utilization. This species achieves high activity and selectivity for the formation of cyclic carbonates and offers a sustainable alternative to traditional synthesis methods. This work represents a unique design strategy for CO₂ utilization while offering exciting possibilities for further work in characterization, computational modelling, and post-synthesis modification.

Keywords: carbonate, catalysis, MOF, utilisation

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Authors: Hellal Abdelkader, Chafaa Salah, Touafri Lasnouni

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A simple, efficient and general method has been developed for the high diastereoselective synthesis of diethyl α-aminophosphonates in water through “one-pot” three-component reaction of aromatic aldehydes, aminophenols and dialkyl phosphites in the presence of a low catalytic amount (10mol%) of phosphorous acid as highly stable catalyst is described.

Keywords: DFT, HOMO-LUMO, phosphonic acid, aminophenols

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Authors: Chaouki Ghenai

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Computational fluid dynamics analysis of the burning of syngas fuels derived from biomass and plastic solid waste mixture through gasification process is presented in this paper. The syngas fuel is burned in gas turbine can combustor. Gas turbine can combustor with swirl is designed to burn the fuel efficiently and reduce the emissions. The main objective is to test the impact of the alternative syngas fuel compositions and lower heating value on the combustion performance and emissions. The syngas fuel is produced by blending Palm Kernel Shell (PKS) with Polyethylene (PE) waste via catalytic steam gasification (fluidized bed reactor). High hydrogen content syngas fuel was obtained by mixing 30% PE waste with PKS. The syngas composition obtained through the gasification process is 76.2% H2, 8.53% CO, 4.39% CO2 and 10.90% CH4. The lower heating value of the syngas fuel is LHV = 15.98 MJ/m3. Three fuels were tested in this study natural gas (100%CH4), syngas fuel and pure hydrogen (100% H2). The power from the combustor was kept constant for all the fuels tested in this study. The effect of syngas fuel composition and lower heating value on the flame shape, gas temperature, mass of carbon dioxide (CO2) and nitrogen oxides (NOX) per unit of energy generation is presented in this paper. The results show an increase of the peak flame temperature and NO mass fractions for the syngas and hydrogen fuels compared to natural gas fuel combustion. Lower average CO2 emissions at the exit of the combustor are obtained for the syngas compared to the natural gas fuel.

Keywords: CFD, combustion, emissions, gas turbine combustor, gasification, solid waste, syngas, waste to energy

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Authors: Catherine Joke Adeseko

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Enzymatic browning is an economically important disorder that degrades organoleptic properties and prevent the consumer from purchasing fresh fruit and vegetables. Prevention and control of enzymatic browning in fruit and its product is imperative. Therefore, this study sought to investigate the catalytic effect of polyphenol oxidase (PPO) in the adverse browning of African bush mango (Irvingia gabonensis) fruit peel and pulp. PPO was isolated and purified, and its physicochemical properties, such as the effect of pH with SDS, temperature, and thermodynamic studies, which invariably led to thermal inactivation of purified PPO at 80 °C, were evaluated. The pH and temperature optima of PPO were found at 7.0 and 50, respectively. There was a gradual increase in the activity of PPO as the pH increases. However, the enzyme exhibited a higher activity at neutral pH 7.0, while enzymatic inhibition was observed at acidic region, pH 2.0. The presence of SDS at pH 5.0 downward was found to inhibit the activity of PPO from the peel and pulp of I. gabonensis. The average value of enthalpy (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) obtained at 20 min of incubation and temperature 30 – 80 °C were respectively 39.93 kJ.mol-1, 431.57 J.mol-1 .K-1 and -107.99 kJ.mol-1 for peel PPO, and 37.92 kJ.mol-1, -442.51J.mol-1.K-1, and -107.22 kJ.mol-1 for pulp PPO. Thermal inactivation of PPO from I. gabonensis exhibited a reduction in catalytic activity as the temperature and duration of heat inactivation increases using catechol, reflected by an increment in k value. The half-life of PPO (t1/2) decreases as the incubation temperature increases due to the instability of the enzyme at high temperatures and was higher in pulp than peel. Both D and Z values decrease with increase in temperature. The information from this study suggests processing parameters for controlling PPO in the potential industrial application of I. gabonensis fruit in order to prolong the shelf-life of this fruit for maximum utilization.

Keywords: enzymatic, browning, characterization, activity

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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: A. Hamza, H. Kathyayini, N. Nagaraju

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Aluminophosphates, both amorphous and crystalline materials find applications as adsorbents, ceramics, and pigments and as catalysts/catalyst supports in organic fine chemical synthesis. Most of the applications are varied depending on the type of metal incorporated, particle size, surface area, porosity and morphology of aluminophosphate. The porous and surface properties of these materials are normally fine-tuned by adopting various preparation methodologies. Numerous crystalline microporous and mesoporous aluminophosphates and metal-aluminophosphates have been reported in literature, in which the synthesis has been carried out by using structure directing organic molecules/surfactants. In present work, amorphous aluminophosphate (AlP) and metal-aluminophosphates MAlP (M = Cu, Zn, Cr, Fe, Ce and Zr) and their mixed forms M-1M2AlP are prepared under a typical precipitation condition, i.e. at low temperature in order to keep the Von-Weirmann relative super saturation of the precipitating medium and obtain small size precipitate particles. These materials are prepared without using any surfactants. All materials are thoroughly characterised for surface and bulk properties by N2 adsorption-desorption technique, XRD, FT-IR, TG and SEM. The materials are also analysed for the amount and the strength of their surface acid sites, by NH3-TPD and CO2-TPD techniques respectively. All the materials prepared in the work are investigated for their catalytic activity in following applications in the synthesis of industrially important Jasminaldehyde via, aldol condensation of n-heptanal and benzaldehyde, in the synthesis of biologically important chalcones by Claisen-shmidth condensation of benzaldehyde and substituted chalcones. The effect of the amount of the catalysts, duration of the reaction, temperature of the reaction, molar ratio of the reactants has been studied. The porosity of pure aluminophosphate is found to be changed significantly by the incorporation of transition metals during preparation of aluminophosphate. The pore size increased from microporous to mesoporous and finally to macroporous by following order of metals Cu = Zn < Cr < Ce < Fe = Zr. The change in surface area and porosity of double metal-aluminophosphates depended on the concentration of both the metals. The acidity of aluminophosphate is either increased or decreased which depended on the type and valence of metals loaded. A good number of basic sites are created in metal-aluminophosphates irrespective of the metals used. A maximum catalytic activity for synthesis of both jasminaldehyde and chalcone is obtained by FeAlP as catalysts; these materials are characterized by decreased strength and concentration of acidic sites with optimum level basic sites.

Keywords: amorphous metal-aluminophosphates, surface properties, acidic-basic properties, Aldol, Claisen-Shmidth condensation, jasminaldehyde, chalcone

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Authors: Koilpitchai Sivamuthuraman, Venkitasamy Kesavan

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3-substituted 3-amino-2-oxindole skeleton bearing adjacent tetrasubstituted stereogenic centers is of great importance because of these heterocyclic motifs possess a wide range of pharmacological activity. The catalytic asymmetric construction of multi functionalised heterocyclic compound with adjacent tetrasubstituted stereocenters is one of the most difficult tasks in organic synthesis. To date, the most straightforward methodologies have been developed for synthesis of chiral 3-substituted 3-amino-2-oxindoles through the addition of carbon nucleophiles to isatin-derived ketimines. However, only a few successful examples have been described for the assembly of vicinal tetrasubstituted stereocenters using isatin derived ketimines as electrophiles. On the other hand, 2,2-Disubstituted benzofuran-3(2H)-ones and related frameworks are characteristic of a quaternary stereogenic center at C2 position present in quite a number of natural products and bioactive Molecules.Despite the intensive efforts devoted for the construction of 2,2-Disubstituted Benzofuran-3[2H]-one, there are only a few asymmetric methods such as organocatalytic Michael addition and enantioselective halogenations were reported till now. Due to the biological importance of oxindole and benzofuran-3-one, it is proposed here with the synthesis of hybrid molecule containing tetrasubstituted stereo centers through asymmetric organocatalysis. The addition of 2-substituted Benzofuran-3-one(1a) to isatin-derived ketimines(2a) using a bifunctional organocatalyst(catalyst IV or V), leading to chiral heterocyclic compounds containing both 3-amino 2-oxindole and benzofurn-3-one bearing vicinal quaternary stereocenters with good yields and excellent enantioselectivity. The present study extends the scope of the catalytic asymmetric Mannich reaction with isatin-derived ketimines, providing a new class of amino oxindole derivatives having benzofuran-3-one.

Keywords: asymmetric synthesis, benzofuran-3-one, isatin-derived ketimines, quaternary stereocenters

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Authors: Bhavana Gulaty, Arshia Chaudhri

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Great civic projects contribute integrally to a city, and every city undergoes a recurring cycle of urban transformations and regeneration by their insertion. The M.I.C.E. (Meetings, Incentives, Convention and Exhibitions) industry is the forbearer of one category of such catalytic civic projects. Through a specific focus on M.I.C.E. destinations, this paper illustrates the multifarious dimensions that urban catalysts impact the city on S.P.U.R. (Seed. Profile. Urbane. Reflections), the theoretical framework of this paper aims to unearth these dimensions in the realm of the COEX (Convention & Exhibition) biosphere. The ‘COEX Biosphere’ is the filter of such catalysts being ecosystems unto themselves. Like a ripple in water, the impact of these strategic interventions focusing on art, culture, trade, and promotion expands right from the trigger; the immediate context to the region and subsequently impacts the global scale. These ripples are known to bring about significant economic, social, and political and network changes. The COEX inventory in the Asian context has one such prominent addition; the proposed India International Convention and Exhibition Centre (IICC) at New Delhi. It is envisioned to be the largest facility in Asia currently and would position India on the global M.I.C.E map. With the first phase of the project scheduled to open for use in the end of 2019, this flagship project of the Government of India is projected to cater to a peak daily footfall of 3,20,000 visitors and estimated to generate 5,00,000 jobs. While the economic benefits are yet to manifest in real time and ‘Good design is good business’ holds true, for the urban transformation to be meaningful, the benefits have to go beyond just a balance sheet for the city’s exchequer. This aspect has been found relatively unexplored in research on these developments. The methodology for investigation will comprise of two steps. The first will be establishing an inventory of the global success stories and associated benefits of COEX projects over the past decade. The rationale for capping the timeframe is the significant paradigm shift that has been observed in their recent conceptualization; for instance ‘Innovation Districts’ conceptualised in the city of Albuquerque that converges into the global economy. The second step would entail a comparative benchmarking of the projected transformations by IICC through a toolkit of parameters. This is posited to yield a matrix that can form the test bed for mapping the catalytic trajectory for projects in the pipeline globally. As a ready reckoner, it purports to be a catalyst to substantiate decision making in the planning stage itself for future projects in similar contexts.

Keywords: catalysts, COEX, M.I.C.E., urban transformations

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Authors: Berkas Khaoula, Chaoui Kamel

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Polyethylene (PE) pipes are one of the best options for water and gas transmission networks. The main reason for such a choice is its high-quality performance in service conditions over long periods of time. PE pipes are installed in contact with different soils having various chemical compositions with confirmed aggressiveness. As a result, PE pipe surfaces undergo unwanted oxidation reactions. Usually, the polymer mixture is designed to include some additives, such as anti-oxidants, to inhibit or reduce the degradation effects. Some other additives are intended to increase resistance to the ESC phenomenon associated with polymers (ESC: Environmental Stress Cracking). This situation occurs in contact with aggressive external environments following different contaminations of soil, groundwater and transported fluids. In addition, bacterial activity and other physical or chemical media, such as temperature and humidity, can play an enhancing role. These conditions contribute to modifying the PE pipe structure and degrade its properties during exposure. In this work, the effect of distilled water, sodium hypochlorite (bleach), diluted sulfuric acid (H2SO4) and toluene-methanol (TM) mixture are studied when extruded PE samples are exposed to those environments for given periods. The chosen exposure periods are 7, 14 and 28 days at room temperature and in sealed glass containers. Post-exposure observations and ISO impact tests are presented as a function of time and chemical medium. Water effects are observed to be limited in explaining such use in real applications, whereas the changes in TM and acidic media are very significant. For the TM medium, the polymer toughness increased drastically (from 15.95 kJ/m² up to 32.01 kJ/m²), while sulfuric acid showed a steady augmentation over time. This situation may correspond to a hardening phenomenon of PE increasing its brittleness and its ability for structural degradation because of localized oxidation reactions and changes in crystallinity.

Keywords: polyethylene, toluene-methanol mixture, environmental stress cracking, degradation, impact resistance

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Authors: Jasneet Kaur, Swapandeep Singh Chimni

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The unfavorable use of metal-based catalysts that are often extortionate and toxic can be overcome by using small organic molecules known as organocatalysts. A variety of small organic molecules, including Brønsted/Lewis bases and acids, based on sulfonic acids, phosphoric acids, amines, phosphines or carbenes, Cinchona alkaloids, have been used as organocatalysts. One of the key reasons for using organocatalysis is their ability to be effectively removed from the final product in comparison to the metallic counterparts, which are exceedingly difficult to remove. The present investigation seeks to explore the catalytic nature of Cinchona alkaloids as an organocatalyst for enantioselective synthesis of 3-substituted-3-aminooxindole, which is known to exhibit a variety of biological activities and pharmacological activities. In this context, an organocatalytic asymmetric route for the synthesis of 3-aminooxindoles via reaction of isatin imine with α-acetoxy-β-ketoesters has been developed. The bifunctional Cinchona derived thiourea catalyzed the reaction of α-acetoxy-β-ketoesters derivatives with isatin imine to afford 3-substituted-aminooxindole derivatives in up to 93% yield, 95% enantiomeric excess and >20:1 diastereomeric ratio. The reaction was performed at room temperature for two hours using 10 mol% of catalyst, in the presence of 4Å molecular sieves in tetrahydrofuran as a solvent at ambient temperature. After the completion of the reaction, the pure product could be easily separated by using column chromatography using hexane and ethyl acetate as solvents. In conclusion, the catalytic potential of Cinchona derived chiral thiourea-tertiary amine catalyst was explored for an organocatalytic enantioselective Mannich reaction of β-ketoester derivatives with various isatin imine derivatives under mild conditions.

Keywords: asymmetric synthesis, aminooxindoles, enantioselective, isatin imine

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Authors: Renu Gautam, S. M. S. Chauhan

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The magnetic Fe3O4 nanoparticles has been used as an efficient and facile acid catalyst for the synthesis of calix[4]pyrrole in moderate to excellent yields by the one pot condensation of different ketones and pyrrole. The catalyst was easily recovered using external magnet and reused over several cycles without losing its catalytic activity.

Keywords: calix[4]pyrrole, magnetic, Fe3O4 nanoparticles, catalysis

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Authors: Kyung Suk Cho, Heung Youl Kim

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The analysis of the petrologic characteristics and thermal properties of crushed aggregates for concrete such as granite, gneiss, dolomite, shale and andesite found that rock-forming minerals decided the thermal properties of the aggregates. The thermal expansion coefficients of aggregates containing lots of quartz increased rapidly at 573 degrees due to quartz transition. The mass of aggregate containing carbonate minerals decreased rapidly at 750 degrees due to decarboxylation, while its specific heat capacity increased relatively. The mass of aggregates containing hydrated silicate minerals decreased more significantly, and their specific heat capacities were greater when compared with aggregates containing feldspar or quartz. It is deduced that the hydroxyl group (OH) in hydrated silicate dissolved as its bond became loose at high temperatures. Aggregates containing mafic minerals turned red at high temperatures due to oxidation response. Moreover, the comparison of cooling methods showed that rapid cooling using water resulted in more reduction in aggregate mass than slow cooling at room temperatures. In order to observe the fire resistance performance of concrete composed of the identical but coarse aggregate, mass loss and compressive strength reduction factor at 200, 400, 600 and 800 degrees were measured. It was found from the analysis of granite and gneiss that the difference in thermal expansion coefficients between cement paste and aggregates caused by quartz transit at 573 degrees resulted in thermal stress inside the concrete and thus triggered concrete cracking. The ferromagnesian hydrated silicate in andesite and shale caused greater reduction in both initial stiffness and mass compared with other aggregates. However, the thermal expansion coefficient of andesite and shale was similar to that of cement paste. Since they were low in thermal conductivity and high in specific heat capacity, concrete cracking was relatively less severe. Being slow in heat transfer, they were judged to be materials of high heat capacity.

Keywords: crush-aggregates, fire resistance, thermal expansion, heat transfer

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Authors: Basanti Ekka, Talis Juhna

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Dairy industrial effluents originated by the typical processing activities are composed of various organic and inorganic constituents, and these include proteins, fats, inorganic salts, antibiotics, detergents, sanitizers, pathogenic viruses, bacteria, etc. These contaminants are harmful to not only human beings but also aquatic flora and fauna. Because consisting of large classes of contaminants, the specific targeted removal methods available in the literature are not viable solutions on the industrial scale. Therefore, in this on-going research, a series of coagulation, electrochemical, and catalytic methods will be employed. The bulk coagulation and electrochemical methods can wash off most of the contaminants, but some of the harmful chemicals may slip in; therefore, specific catalysts designed and synthesized will be employed for the removal of targeted chemicals. In the context of Latvian dairy industries, presently, work is under progress on the characterization of dairy effluents by total organic carbon (TOC), Inductively Coupled Plasma Mass Spectrometry (ICP-MS)/ Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), High-Performance Liquid Chromatography (HPLC), Gas Chromatography-Mass Spectrometry (GC-MS), and Mass Spectrometry. After careful evaluation of the dairy effluents, a cost-effective natural coagulant will be employed prior to advanced electrochemical technology such as electrocoagulation and electro-oxidation as a secondary treatment process. Finally, graphene oxide (GO) based hybrid materials will be used for post-treatment of dairy wastewater as graphene oxide has been widely applied in various fields such as environmental remediation and energy production due to the presence of various oxygen-containing groups. Modified GO will be used as a catalyst for the removal of remaining contaminants after the electrochemical process.

Keywords: catalysis, dairy wastewater, electrochemical method, graphene oxide

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Authors: Vidula Shevade, B. J. Nagare, Sajeev Chacko

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First principles simulation, meaning density functional theory (DFT) calculations with plane waves and pseudopotential, has become a prized technique in condensed matter theory. Nanoparticles (NP) have been known to possess good catalytic activities, especially for molecules such as CO, O₂, etc. Among the metal NPs, Aluminium based NPs are also widely known for their catalytic properties. Aluminium metal is a lightweight, excellent electrical, and thermal abundant chemical element in the earth’s crust. Aluminium NPs, when added to solid rocket fuel, help improve the combustion speed and considerably increase combustion heat and combustion stability. Adding aluminium NPs into normal Al/Al₂O₃ powder improves the sintering processes of the ceramics, with high heat transfer performance, increased density, and enhanced thermal conductivity of the sinter. We used VASP and Gaussian 0₃ package to compute the geometries, electronic structure, and bonding properties of Al₁₂Ni as well as its interaction with O₂ and CO molecules. Several MD simulations were carried out using VASP at various temperatures from which hundreds of structures were optimized, leading to 24 unique structures. These structures were then further optimized through a Gaussian package. The lowest energy structure of Al₁₂Ni has been reported to be a singlet. However, through our extensive search, we found a triplet state to be lower in energy. In our structure, the Ni atom is found to be on the surface, which gives the non-zero magnetic moment. Incidentally, O2 and CO molecules are also triplet in nature, due to which the Al₁₂-Ni cluster is likely to facilitate the oxidation process of the CO molecule. Our results show that the most favourable site for the CO molecule is the Ni atom and that for the O₂ molecule is the Al atom that is nearest to the Ni atom. Al₁₂Ni-O₂ and Al₁₂-Ni-CO structures we extracted using VMD. Al₁₂Ni nanocluster, due to in triplet electronic structure configuration, indicates it to be a potential candidate as a catalyst for oxidation of CO molecules.

Keywords: catalyst, gaussian, nanoparticles, oxidation

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Authors: Hossein Anaraki-Ardakani, Tayebe Heidari-Rakati

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An environmentally benign protocol for the one-pot, three-component synthesis of Triazolo[1,2-a]indazole-1,3,8-trione derivatives by condensation of dimedone, urazole and aromatic aldehydes catalyzed by HClO4/SiO2 NPS as an ecofriendly catalyst with high catalytic activity and reusability at 100 ºC under solvent-free conditions is reported. The reaction proceeds to completion within 20-30 min in 77-86 % yield.

Keywords: one-pot reaction, dimedone, triazoloindazole, urazole

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Authors: S. Srinivas, N. Ramesh Babu

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This paper presents a model to predict the depth of penetration in polycrystalline ceramic material cut by abrasive waterjet. The proposed model considered the interaction of cylindrical jet with target material in upper region and neglected the role of threshold velocity in lower region. The results predicted with the proposed model are validated with the experimental results obtained with Silicon Carbide (SiC) blocks.

Keywords: abrasive waterjet cutting, analytical modeling, ceramics, micro-cutting and inter-grannular cracking

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Authors: Sadok Aboubakr

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The mechanical behavior of cracks from several manufacturing defect in an oil pipeline, is characterized by the fact that defects'm taking several forms: circumferential, longitudinal and inclined crack that evolve over time. Increased lifetime of the constructions and in particular cylindrical tubes under internal pressure requires knowledge improving these defects during loading. From this study we simulated various forms of cracking and also their pipeline repair patch.

Keywords: stress intensity factor, pressure, Young's modulus, Poisson's ratio, Shear modulus, Longueur du pipeline, the angle of crack, crack length

Procedia PDF Downloads 345