Search results for: catalytic cracking

Authors: Emmanuel A. Oriaifo, Noel Perera, Alan Guy, Pak. S. Leung, Kian T. Tan

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Concerns on corrosion and effective coating protection of double hull tankers and bulk carriers in service have been raised especially in water ballast tanks (WBTs). Test protocols/methodologies specifically that which is incorporated in the International Maritime Organisation (IMO), Performance Standard for Protective Coatings for Dedicated Sea Water ballast tanks (PSPC) are being used to assess and evaluate the performance of the coatings for type approval prior to their application in WBTs. However, some of the type approved coatings may be applied as very thick films to less than ideally prepared steel substrates in the WBT. As such films experience hygrothermal cycling from operating and environmental conditions, they become embrittled which may ultimately result in cracking. This embrittlement of the coatings is identified as an undesirable feature in the PSPC but is not mentioned in the test protocols within it. There is therefore renewed industrial research aimed at understanding this issue in order to eliminate cracking and achieve the intended coating lifespan of 15 years in good condition. This paper will critically review test protocols currently used for assessing and evaluating coating performance, particularly the IMO PSPC.

Keywords: corrosion test, hygrothermal cycling, coating test protocols, water ballast tanks

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Authors: Seyed Mohammad Asgharzadeh, Moein Biglari

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Asphalt overlay is the most commonly used technique of pavement rehabilitation. However, the reflective cracks which occur on the overlay surface after a short period of time are the most important distresses threatening the durability of new overlays. Stress Absorbing Membrane Interlayers (SAMIs) are used to postpone the reflective cracking in the overlays. Sand asphalt mixtures, in unmodified or crumb rubber modified (CRM) conditions, can be used as an SAMI material. In this research, the performance properties of different SAMI applications were evaluated in the laboratory using an Indirect Tensile (IDT) fracture energy. The IDT fracture energy of sand asphalt samples was also evaluated and then compared to that of the regular dense graded asphalt used as an overlay. Texas boiling water and modified Lottman tests were also conducted to evaluate the moisture susceptibility of sand asphalt mixtures. The test results showed that sand asphalt mixtures can stand higher levels of energy before cracking, and this is even more pronounced for the CRM sand mix. Sand asphalt mixture using CRM binder was also shown to be more resistance to moisture induced distresses.

Keywords: SAMI, sand asphalt, crumb rubber, indirect tensile test

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Authors: Turin Datta, Kisor K. Sahu

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Structural materials used in today’s oil and gas exploration and drilling of both onshore and offshore oil and gas wells must possess superior tensile properties, excellent resistance to corrosive degradation that includes general, localized (pitting and crevice) and environment assisted cracking such as stress corrosion cracking and hydrogen embrittlement. The High Pressure and High Temperature (HPHT) wells are typically operated at temperature and pressure that can exceed 300-3500F and 10,000psi (69MPa) respectively which necessitates the use of exotic materials in these exotic sources of natural resources. This research investigation is focussed on the evaluation of tensile properties and corrosion behavior of AISI 4140 High-Strength Low Alloy Steel (HSLA) possessing tempered martensitic microstructure and Duplex 2205 Stainless Steel (DSS) having austenitic and ferritic phase. The selection of this two alloys are primarily based on economic considerations as 4140 HSLA is cheaper when compared to DSS 2205. Due to the harsh aggressive chemical species encountered in deep oil and gas wells like chloride ions (Cl-), carbon dioxide (CO2), hydrogen sulphide (H2S) along with other mineral organic acids, DSS 2205, having a dual-phase microstructure can mitigate the degradation resulting from the presence of both chloride ions (Cl-) and hydrogen simultaneously. Tensile properties evaluation indicates a ductile failure of DSS 2205 whereas 4140 HSLA exhibit quasi-cleavage fracture due to the phenomenon of ‘tempered martensitic embrittlement’. From the potentiodynamic polarization testing, it is observed that DSS 2205 has higher corrosion resistance than 4140 HSLA; the former exhibits passivity signifying resistance to localized corrosion while the latter exhibits active dissolution in all the environmental parameters space that was tested. From the Scanning Electron Microscopy (SEM) evaluation, it is understood that stable pits appear in DSS 2205 only when the temperature exceeds the critical pitting temperature (CPT). SEM observation of the corroded 4140 HSLA specimen tested in aqueous 3.5 wt.% NaCl solution reveals intergranular cracking which appears due to the adsorption and diffusion of hydrogen during polarization, thus, causing hydrogen-induced cracking/hydrogen embrittlement. General corrosion testing of DSS 2205 in acidic brine (pH~3.0) solution at ambient temperature using coupons indicate no weight loss even after three months whereas the corrosion rate of AISI 4140 HSLA is significantly higher after one month of testing.

Keywords: DSS 2205, polarization, pitting, SEM

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Authors: K. S. Ghosh, Sagnik Bose, Kapil Tripati

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Potentiodynamic polarization studies carried out on AA2024 and AA2014 Al-Cu-Mg alloys of various tempers in 3.5 wt. % NaCl and in 3.5 wt. % NaCl + 1.0 % H2O2 solution characteristic E-i curves. Corrosion potential (Ecorr) value has shifted towards more negative potential with the increase of artificial aging time. The Ecorr value for the alloy tempers has also shifted anodically in presence of H2O2 in 3.5 % NaCl solution. Further, passivity phenomenon has been observed in all the alloy tempers when tested in 3.5 wt. % NaCl solution at pH 12. Stress corrosion cracking (SCC) behaviour of friction stir weld (FSW) joint of AA2014 alloy has been studied bu slow strain rate test (SSRT) in 3.5 wt. % NaCl solution. Optical micrographs of the corroded surfaces of polarised samples showed general corrosion, extensive pitting and intergranular corrosion as well. Further, potentiodynamic cyclic polarization curves displayed wide hysteresis loop indicating that the alloy tempers are susceptible to pit growth damage. Attempts have been made to explain the variation of observed electrochemical and SCC behaviour of the alloy tempers and the electrolyte conditions with the help of microstructural features.

Keywords: AA 2014 and AA 2024 Al-C-Mg alloy, artificial ageing, potentiodynamic polarization, TEM micrographs, stress corrosion cracking (SCC)

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Authors: Renzhi Qi, Zhaoping Zhong

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Under the dual pressure of the global energy crisis and environmental pollution, avoiding the consumption of non-renewable fossil fuels based on carbon as the energy carrier and developing and utilizing non-carbon energy carriers are the basic requirements for the future new energy economy. Electrocatalyst for water splitting plays an important role in building sustainable and environmentally friendly energy conversion. The oxygen evolution reaction (OER) is essentially limited by the slow kinetics of multi-step proton-electron transfer, which limits the efficiency and cost of water splitting. In this work, CeO₂@NiCo-NRGO/NF hybrid materials were prepared using nickel foam (NF) and nitrogen-doped reduced graphene oxide (NRGO) as conductive substrates by multi-step hydrothermal method and were used as highly efficient catalysts for OER. The well-connected nanosheet array forms a three-dimensional (3D) network on the substrate, providing a large electrochemical surface area with abundant catalytic active sites. The doping of CeO₂ in NiCo-NRGO/NF electrocatalysts promotes the dispersion of substances and its synergistic effect in promoting the activation of reactants, which is crucial for improving its catalytic performance against OER. The results indicate that CeO₂@NiCo-NRGO/NF only requires a lower overpotential of 250 mV to drive the current density of 10 mA cm-2 for an OER reaction of 1 M KOH, and exhibits excellent stability at this current density for more than 10 hours. The double layer capacitance (Cdl) values show that CeO₂@NiCo-NRGO/NF significantly affects the interfacial conductivity and electrochemically active surface area. The hybrid structure could promote the catalytic performance of oxygen evolution reaction, such as low initial potential, high electrical activity, and excellent long-term durability. The strategy for improving the catalytic activity of NiCo-LDH can be used to develop a variety of other electrocatalysts for water splitting.

Keywords: CeO₂, reduced graphene oxide, NiCo-layered double hydroxide, oxygen evolution reaction

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Authors: Khaled Alshammari

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

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

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Authors: Seyed Javad Vaziri Kang Olyaei, Asma Sadat Dabiri, Hassan Fazaeli, Amir Ali Amini

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Cracks in concrete pavements are places for the entrance of water and corrosive substances to the pavement, which can reduce the durability of concrete in the long term as well as the serviceability of road. The use of fibers in concrete pavement is one of the effective methods to control and mitigate cracking. This study investigates the effect of the addition of micro and macro polypropylene fibers in different types and volumes and also in combination with the mechanical properties of concrete used in concrete pavements, including compressive strength, splitting tensile strength, modulus of rupture, and average residual strength. The fibers included micro-polypropylene, macro-polypropylene, and hybrid micro and micro polypropylene in different percentages. The results showed that macro polypropylene has the most significant effect on improving the mechanical properties of concrete. Also, the hybrid micro and macro polypropylene fibers increase the mechanical properties of concrete more. It was observed that according to the results of the average residual strength, macro polypropylene fibers alone and together with micro polypropylene fibers could have excellent performance in controlling the sudden formation of cracks and their growth after the formation of cracking which is an essential property in concrete pavements.

Keywords: concrete pavement, mechanical properties, macro polypropylene fibers, micro polypropylene fibers

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Authors: M. Masar, P. Janota, J. Sedlak, M. Machovsky, I. Kuritka

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Zinc oxide (ZnO) nano crystals assembled porous architecture was prepared by thermal decomposition of zinc oxalate precursor at various temperatures ranging from 400-900°C. The effect of calcining temperature on structure and morphology was examined by scanning electron microscopy (SEM), X-ray diffractometry, thermogravimetry, and BET adsorption analysis. The porous nano crystalline ZnO morphology was developed due to the release of volatile precursor products, while the overall shape of ZnO micro crystals was retained as a legacy of the precursor. The average crystallite size increased with increasing temperature of calcination from approximately 21 nm to 79 nm, while the specific surface area decreased from 30 to 1.7 m2g-1. The photo catalytic performance of prepared ZnO powders was evaluated by degradation of methyl violet 2B, a model compound. The significantly highest photo catalytic activity was achieved with powder calcined at 500°C. This may be attributed to the sufficiently well-developed crystalline arrangement, while the specific surface area is still high enough.

Keywords: ZnO, porous structure, photodegradation, methyl violet

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

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

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

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Authors: A. Brahma

Abstract:

Drying is a phenomenon that accompanies the hardening of hydraulic materials. It can, if it is not prevented, lead to significant spontaneous dimensional variations, which the cracking is one of events. In this context, cracking promotes the transport of aggressive agents in the material, which can affect the durability of concrete structures. Drying shrinkage develops over a long period almost 30 years although most occurred during the first three years. Drying shrinkage stabilizes when the material is water balance with the external environment. The drying shrinkage of cementitious materials is due to the formation of capillary tensions in the pores of the material, which has the consequences of bringing the solid walls of each other. Knowledge of the shrinkage characteristics of concrete is a necessary starting point in the design of structures for crack control. Such knowledge will enable the designer to estimate the probable shrinkage movement in reinforced or prestressed concrete and the appropriate steps can be taken in design to accommodate this movement. This study is concerned the modelling of drying shrinkage of the hydraulic materials and the prediction of the rate of spontaneous deformations of hydraulic materials during hardening. The model developed takes in consideration the main factors affecting drying shrinkage. There was agreement between drying shrinkage predicted by the developed model and experimental results. In last we show that developed model describe the evolution of the drying shrinkage of high performances concretes correctly.

Keywords: drying, hydraulic concretes, shrinkage, modeling, prediction

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Authors: D. Amaranatha Reddy

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Highly efficient and stable co-catalysts materials is of great important for boosting photo charge carrier’s separation, transportation efficiency, and accelerating the catalytic reactive sites of semiconductor photocatalysts. As a result, it is of decisive importance to fabricate low price noble metal free co-catalysts with high catalytic reactivity, but it remains very challenging. Considering this challenge here, dual metal organic frame work derived N-Doped Fe3C nanocages have been rationally designed and decorated with ultrathin ZnIn2S4 nanosheets for efficient photocatalytic hydrogen generation. The fabrication strategy precisely integrates co-catalyst nanocages with ultrathin two-dimensional (2D) semiconductor nanosheets by providing tightly interconnected nano-junctions and helps to suppress the charge carrier’s recombination rate. Furthermore, constructed highly porous hybrid structures expose ample active sites for catalytic reduction reactions and harvest visible light more effectively by light scattering. As a result, fabricated nanostructures exhibit superior solar driven hydrogen evolution rate (9600 µmol/g/h) with an apparent quantum efficiency of 3.6 %, which is relatively higher than the Pt noble metal co-catalyst systems and earlier reported ZnIn2S4 based nanohybrids. We believe that the present work promotes the application of sulfide based nanostructures in solar driven hydrogen production.

Keywords: photocatalysis, water splitting, hydrogen fuel production, solar-driven hydrogen

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Authors: Sushma Yadav, Anil K. Saroha

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Complex industrial effluent generated from chemical industry is contaminated with toxic and hazardous organic compounds and not amenable to direct biological treatment. To effectively remove many toxic organic pollutants has made it evident that new, compact and more efficient systems are needed. Catalytic Wet Air Oxidation (CWAO) is a promising treatment technology for the abatement of organic pollutants in wastewater. A lot of information is available on using CWAO for the treatment of synthetic solution containing single organic pollutant. But the real industrial effluents containing multi-component mixture of organic compounds were less studied. The main objective of this study is to use the CWAO process for converting the organics into compounds more amenable to biological treatment; complete oxidation may be too expensive. Therefore efforts were made in the present study to explore the potential of alumina based Platinum (Pt) catalyst for the treatment of industrial organic raffinate containing toxic constituents like ammoniacal nitrogen, pyridine etc. The catalysts were prepared by incipient wetness impregnation method and characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and BET (Brunauer, Emmett, and Teller) surface area. CWAO experiments were performed at atmospheric pressure and (30 °C - 70 °C) temperature conditions and the results were evaluated in terms of COD removal efficiency. The biodegradability test was performed by BOD/COD ratio for checking the toxicity of the industrial wastewater as well as for the treated water. The BOD/COD ratio of treated water was significantly increased and signified that the toxicity of the organics was decreased while the biodegradability was increased, indicating the more amenability towards biological treatment.

Keywords: alumina based pt catalyst, BOD/COD ratio, catalytic wet air oxidation, COD removal efficiency, industrial organic raffinate

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Authors: Munoz A. Tatiana, Solano R. Brandon, Montes C. Juan, Cierco G. Javier

Abstract:

The hydrodynamic cavitation is a process in which the energy that the fluids have in the phase changes is used. From this energy, local temperatures greater than 5000 °C are obtained where thermal cracking of the fluid molecules takes place. The process applied to heavy oil affects variables such as viscosity, density, and composition, which constitutes an important improvement in the quality of crude oil. In this study, the need to design a software through mathematical integration models of mixing, cavitation, kinetics, and reactor, allows modeling changes in density, viscosity, and composition of a heavy oil crude, when the fluid passes through a hydrodynamic cavitation reactor. In order to evaluate the viability of this technique in the industry, a heavy oil of 18° API gravity, was simulated using naphtha as a hydrogen donor at concentrations of 1, 2 and 5% vol, where the simulation results showed an API gravity increase to 0.77, 1.21 and 1.93° respectively and a reduction viscosity by 9.9, 12.9 and 15.8%. The obtained results allow to have a favorable panorama on this technological development, an appropriate visualization on the generation of innovative knowledge of this technique and the technical-economic opportunity that benefits the development of the hydrocarbon sector related to heavy crude oil that includes the largest world oil production.

Keywords: hydrodynamic cavitation, thermal cracking, hydrogen donor, heavy oil upgrading, simulator

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Authors: Rakhshan Hakimelahi

Abstract:

In recent years, zinc oxid nano tubes have attracted much attention. The direct use of zinc oxid nano tubes modified by SiO2 as recoverable catalysts for organic reactions is very rare. The catalysts were characterized by XRD. The average particle size of ZnO catalysts is 57 nm and there are high density defects on nano tubes surfaces. A simple and efficient method for the quinazolin derivatives synthesis from the condensation isatoic anhydride and an aromatic aldehyde with ammonium acetate in the presence of a catalytic amount zinc oxid nano tubes modified by SiO2 is described. The reason proposed for higher catalytic activity of zinc oxid nano tubes modified by SiO2 is a combination effect of the small particle size and high-density surface defects. The practical and simple method led to excellent yields of the 2,3-Di hydro quinazolin-4(1H)-one derivatives under mild conditions and within short times.

Keywords: 2, 3-Dihydroquinazolin-4(1H)-one derivatives, reusable catalyst, SiO2, zinc oxid nanotubes

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Authors: Zhiqiang Xu, Hongfang Ma, Haitao Zhang, Weixin Qian, Weiyong Ying

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SSZ-13 materials with different Si/Al ratio were prepared by varying the composition of aluminosilicate precursor solutions upon hydrothermal treatment at 150 °C. The Si/Al ratio of the initial system was systematically changed from 12.5 to infinity in order to study the limits of Al composition in precursor solutions for constructing CHA structure. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, FESEM, and chemical analysis. NH₃-TPD was used to study the Brønsted acidity of SSZ-13 samples with different Si/Al ratios. The effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that Al species determine the nucleation rate and the number of nuclei, which is tied to the morphology and yield of SSZ-13. The size of SSZ-13 increased and the yield decreased as the Si/Al ratio was improved. Varying Si/Al ratio of the initial system is a facile, commercially viable method of tailoring SSZ-13 crystal size and morphology. Furthermore, SSZ-13 materials with different Si/Al ratio were tested as catalysts for the methanol to olefins (MTO) reaction at 350 °C. SSZ-13 with the Si/Al ratio of 35 shows the best MTO catalytic performance.

Keywords: crystallization, MTO, Si/Al ratio, SSZ-13

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Authors: Mona Lisa M. Oliveira, Nara A. Policarpo, Ana Luiza B. P. Barros, Carla A. Silva

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Selective catalytic reduction systems for nitrogen oxides reduction by ammonia has been the chosen technology by most of diesel vehicle (i.e. bus and truck) manufacturers in Brazil, as also in Europe. Furthermore, at some conditions, over-stoichiometric ammonia availability is also needed that increases the NH₃ slips even more. Ammonia (NH₃) by this vehicle exhaust aftertreatment system provides a maximum efficiency of NOx removal if a significant amount of NH₃ is stored on its catalyst surface. In the other words, the practice shows that slightly less than 100% of the NOx conversion is usually targeted, so that the aqueous urea solution hydrolyzes to NH₃ via other species formation, under relatively low temperatures. This paper presents a model based on neural networks integrated with a road vehicle simulator that allows to estimate NH₃-slip emission factors for different driving conditions and patterns. The proposed model generates high NH₃slips which are not also limited in Brazil, but more efforts needed to be made to elucidate the contribution of vehicle-emitted NH₃ to the urban atmosphere.

Keywords: ammonia slip, neural-network, vehicles emissions, SCR-NOx

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Authors: Wei-Jing Li, Ren-Xuan Yang, Kui-Hao Chuang, Ming-Yen Wey

Abstract:

Nowadays, plastic product and utilization are extensive and have greatly improved our life. Yet, plastic wastes are stable and non-biodegradable challenging issues to the environment. Waste-to-energy strategies emerge a promising way for waste management. This work investigated the co-production of hydrogen and carbon nanotubes from the syngas which was from the gasification of polypropylene. A nickel-silica core-shell catalyst was applied for syngas reaction from plastic waste gasification in a fixed-bed reactor. SiO2 were prepared through various synthesis solvents by Stöber process. Ni plays a role as modified SiO2 support, which were synthesized by deposition-precipitation method. Core-shell catalysts have strong interaction between active phase and support, in order to avoid catalyst sintering. Moreover, Fe or Co metal acts as promoter to enhance catalytic activity. The effects of calcined atmosphere, second metal addition, and reaction temperature on hydrogen production and carbon yield were examined. In this study, the catalytic activity and carbon yield results revealed that the Ni/SiO2 catalyst calcined under H2 atmosphere exhibited the best performance. Furthermore, Co promoted Ni/SiO2 catalyst produced 3 times more than Ni/SiO2 on carbon yield at long-term operation. The structure and morphological nature of the calcined and spent catalysts were examined using different characterization techniques including scanning electron microscopy, transmission electron microscopy, X-ray diffraction. In addition, the quality and thermal stability of the nano-carbon materials were also evaluated by Raman spectroscopy and thermogravimetric analysis.

Keywords: plastic wastes, hydrogen, carbon nanotube, core-shell catalysts

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Authors: Abdelmalk Brahma

Abstract:

Drying is a phenomenon that accompanies the hardening of hydraulic materials. It can, if it is not prevented, lead to significant spontaneous dimensional variations, which the cracking is one of events. In this context, cracking promotes the transport of aggressive agents in the material, which can affect the durability of concrete structures. Drying shrinkage develops over a long period almost 30 years although most occurred during the first three years. Drying shrinkage stabilizes when the material is water balance with the external environment. The drying shrinkage of cementitious materials is due to the formation of capillary tensions in the pores of the material, which has the consequences of bringing the solid walls of each other. Knowledge of the shrinkage characteristics of concrete is a necessary starting point in the design of structures for crack control. Such knowledge will enable the designer to estimate the probable shrinkage movement in reinforced or prestressed concrete and the appropriate steps can be taken in design to accommodate this movement. This study is concerned the modelling of drying shrinkage of the hydraulic materials and the prediction of the rate of spontaneous deformations of hydraulic materials during hardening. The model developed takes in consideration the main factors affecting drying shrinkage. There was agreement between drying shrinkage predicted by the developed model and experimental results. In last we show that developed model describe the evolution of the drying shrinkage of high performances concretes correctly.

Keywords: drying, hydraulic concretes, shrinkage, modeling, prediction

Procedia PDF Downloads 236

Authors: N. Marzban, J. K. Heydarzadeh M. Pourmohammadbagher, M. H. Hatami, A. Samia

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A nano-alumina-zirconia composite catalyst was synthesized by a simple aqueous sol-gel method using AlCl₃.6H₂O and ZrCl₄ as precursors. Thermal decomposition of the precursor and subsequent formation of γ-Al₂O₃ and t-Zr were investigated by thermal analysis. XRD analysis showed that γ-Al₂O₃ and t-ZrO₂ phases were formed at 700 °C. FT-IR analysis also indicated that the phase transition to γ-Al₂O₃ occurred in corroboration with X-ray studies. TEM analysis of the calcined powder revealed that spherical particles were in the range of 8-12 nm. The nano-alumina-zirconia composite particles were mesoporous and uniformly distributed in their crystalline phase. In order to measure the catalytic activity, esterification reaction was carried out. Biodiesel, as a renewable fuel, was formed in a continuous packed column reactor. Free fatty acid (FFA) was esterified with ethanol in a heterogeneous catalytic reactor. It was found that the synthesized γ-Al₂O₃/ZrO₂ composite had the potential to be used as a heterogeneous base catalyst for biodiesel production processes.

Keywords: nano alumina-zirconia, composite catalyst, thin film, biodiesel

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Authors: Ghada Diaa, Enas A. Khattab

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Ultra High Strength Concrete (UHSC) is a new advanced concrete that is being transferred from laboratory researches to practicable applications. In addition to its excellent durability properties, UHSC has high compressive and tensile strengths, and high modulus of elasticity. Despite of this low degree of hydration, ultra high strength values can be achieved by controlling the mixture proportions. In this research, an experimental program was carried out to investigate the shear behavior of ultra high strength concrete beams. A total of nine beams were tested to determine the effect of different parameters on the shear behavior of UHSC beams. The parameters include concrete strength, steel fiber volume, shear span to depth ratio, and web reinforcement ratio. The results demonstrated that nominal shear stress at cracking load and at ultimate load increased with the increase of concrete strength or the decrease in shear span-depth ratio. Using steel fibers or shear reinforcement increases the ultimate shear strength and makes the shear behavior more ductile. In this study, a simplified analytical model to calculate the shear strength of UHSC beams is introduced. Shear strength estimated according to the proposed method in this research is in good agreement with the experimental results.

Keywords: ultra high strength, shear strength, diagonal, cracking, steel fibers

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Authors: Farej Ahmed Emhmmed Alhegagi

Abstract:

Duplex stainless steels are attractive material for apparatus working with sea water, petroleum, refineries, chemical plants,vessels, and pipes operating at high temperatures and/or pressures. The role of austenite phase in duplex stainless steels performance was investigated. Zeron 100, stainless steels with 50/50 ferrite / austenite %, specimens were tested for strength, toughness, embrittlement susceptibility, and assisted environmental cracking (AEC) resistance. Specimens were heat treated at 475°C for different times and loaded to well- selected values of load. The load values were chosen to be within the range of higher / lower than the expected toughness. Sodium chloride solution 3.5wt% environment with polarity of -900mV / SCE was used to investigate the material susceptibility to (AEC). Results showed important effect of austenite on specimens overall mechanical properties. Strength was affected by the ductile nature of austenite phase leading to plastic deformation accommodated by austenite slip system. Austenite embrittlement, either by decomposition or nucleation and growth process, was not observed to take place during specimens heat treatment. Cracking due to (AEC) took place in the ferrite grains and avoided the austenite phase. Specimens showed the austenite to act as a crack arrestor during (AEC) of duplex stainless steels.

Keywords: austenite phase, mechanical properties, embrittlement susceptibility, duplex stainless steels

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

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The CO2 emitted from anthropic activities is perceived as a constraint in industrial activity due to taxes, stringent environmental regulations, impact on global warming… To limit these CO2 emissions, reuse of CO2 represents a promising alternative, with important applications in chemical industry and for power generation. However, CO2 valorization process requires a gas as pure as possible Oxyfuel-combustion that enables obtaining a CO2 rich stream, with water vapor (10%) is then interesting. Nevertheless to decrease the amount of the by-products found with the CO2 (especially CO and NOx which are harmful to the environment) a catalytic treatment must be applied. Nowadays three-way catalysts are well-developed material for simultaneous conversion of unburned hydrocarbons, carbon monoxide (CO) and nitrogen oxides (NOx). The use of Pd attracted considerable attention on the basis of economic factors (the high cost and scarcity of Pt and Rh). This explains the large number of studies concerning the CO-NO reaction on Pd in the recent years. In the present study, we will compare a series of Pd materials supported on different oxides for CO2 purification from the oxyfuel combustion system, by reducing NO with CO in an oxidizing environment containing CO2 rich stream and presence of 8.2% of water. Al2O3, CeO2, MgO, SiO2 and TiO2 were used as support materials of the catalysts. 1wt% Pd/Support catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2]. The obtained samples were subsequently characterized by H2 chemisorption, BET surface area and TEM. Finally, their catalytic performances were evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200mL.min−1, in the same GHSV. The catalytic performance of the Pd catalysts for CO2 purification revealed that: -The support material has a strong influence on the catalytic activity of 1wt.% Pd supported catalysts. depending of the nature of support, the Pd-based catalysts activity changes. -The highest reduction of NO with CO is obtained in the following ranking: TiO2>CeO2>Al2O3. -The supports SiO2 and MgO should be avoided for this reaction, -Total oxidation of CO occurred over different materials, -CO2 purification can reach 97%, -The presence of H2O has a positive effect on the NO reduction due to the production of the reductant H2 from WGS reaction H2O+CO → H2+CO2

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis, oxyfuel combustion

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Authors: V. Pérez-Herranz, C. González-Buch, E. M. Ortega, S. Mestre

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In this work new macroporous Ni electrodes modified with Au nanoparticles for hydrogen production have been developed. The supporting macroporous Ni electrodes have been obtained by means of the electrodeposition at high current densities. Then, the Au nanoparticles were synthesized and added to the electrode surface. The electrocatalytic behaviour of the developed electrocatalysts was studied by means of pseudo-steady-state polarization curves, electrochemical impedance spectroscopy (EIS) and hydrogen discharge curves. The size of the Au synthetized nanoparticles shows a monomodal distribution, with a very sharp band between 10 and 50 nm. The characteristic parameters d10, d50 and d90 were 14, 20 and 31 nm respectively. From Tafel polarization data has been concluded that the Au nanoparticles improve the catalytic activity of the developed electrodes towards the HER respect to the macroporous Ni electrodes. EIS permits to obtain the electrochemically active area by means of the roughness factor value. All the developed electrodes show roughness factor values in the same order of magnitude. From the activation energy results it can be concluded that the Au nanoparticles improve the intrinsic catalytic activity of the macroporous Ni electrodes.

Keywords: Au nano particles, hydrogen evolution reaction, porous Ni electrodes, electrochemical impedance spectroscopy

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Authors: Bipasa Dey, Varsha Panwar, Tanmay Dutta

Abstract:

Laccase, a multicopper oxidase (EC 1.10.3.2) have been at the forefront as a superior industrial biocatalyst. They are versatile in terms of bestowing sustainable and ecological catalytic reactions such as polymerisation, xenobiotic degradation and bioremediation of phenolic and non-phenolic compounds. Regardless of the wide biotechnological applications, the critical limiting factors viz. reusability, retrieval, and storage stability still prevail. This can cause an impediment in their applicability. Crosslinked enzyme aggregates (CLEAs) have emerged as a promising technique that rehabilitates these essential facets, albeit at the expense of their enzymatic activity. The carrier free crosslinking method prevails over the carrier-bound immobilisation in conferring high productivity, low production cost owing to the absence of additional carrier and circumvent any non-catalytic ballast which could dilute the volumetric activity. To the best of our knowledge, the ε-amino group of lysyl residue is speculated as the best choice for forming Schiff’s base with glutaraldehyde. Despite being most preferrable, excess glutaraldehyde can bring about disproportionate and undesirable crosslinking within the catalytic site and hence could deliver undesirable catalytic losses. Moreover, the surface distribution of lysine residues in Trametes versicolor laccase is significantly less. Thus, to mitigate the adverse effect of glutaraldehyde in conjunction with scaling down the degradation or catalytic loss of the enzyme, crosslinking with inert substances like gelatine, collagen, Bovine serum albumin (BSA) or excess lysine is practiced. Analogous to these molecules, sugars have been well known as a protein stabiliser. It helps to retain the structural integrity, specifically secondary structure of the protein during aggregation by changing the solvent properties. They are comprehended to avert protein denaturation or enzyme deactivation during precipitation. We prepared crosslinked enzyme aggregates (CLEAs) of laccase from T. versicolor with the aid of sugars. The sugar CLEAs were compared with the classic BSA and glutaraldehyde laccase CLEAs concerning physico-chemical properties. The activity recovery for the fructose CLEAs were found to be ~20% higher than the non-sugar CLEA. Moreover, the 𝐾𝑐𝑎𝑡𝐾𝑚⁄ values of the CLEAs were two and three-fold higher than BSA-CLEA and GACLEA, respectively. The half-life (t1/2) deciphered by sugar-CLEA was higher than the t1/2 of GA-CLEAs and free enzyme, portraying more thermal stability. Besides, it demonstrated extraordinarily high pH stability, which was analogous to BSA-CLEA. The promising attributes of increased storage stability and recyclability (>80%) gives more edge to the sugar-CLEAs over conventional CLEAs of their corresponding free enzyme. Thus, sugar-CLEA prevails in furnishing the rudimentary properties required for a biocatalyst and holds many prospects.

Keywords: cross-linked enzyme aggregates, laccase immobilization, enzyme reusability, enzyme stability

Procedia PDF Downloads 54

Authors: Abd El-Aziz Said

Abstract:

In this study, natural silica was used as an active, selective, reusable and eco-friendly catalyst for the liquid phase synthesis of iso-amyl, benzyl and cinnamyl esters. The original and calcined natural silica were characterized by TG-DTA, XRF, XRD, FTIR, SEM, and N2-sorption analysis. The surface acidity of the catalysts was determined using isopropanol dehydration and the strength of available acid sites was measured using chemisorption of pyridine (PY) and dimethyl pyridine (DMPY). The results of acidity specified that the acidic sites are of Brönsted type, while PY-TPD demonstrated that almost of the acidic sites over the surface of natural silica are of weak and intermediate strength. The catalytic activity of natural silica towards esterification of acetic acid with alcohols was extensively studied. The results revealed that natural silica had high catalytic activity with 100% selectivity to all targeted esters. In addition, the yields obtained in batch methods were 83, 81, and 80%, respectively, whereas these yields after simple distillation were improved 97, 99.5, and 90%, respectively.

Keywords: liquid-phase esterification, natural silica, acidity esters, characterization

Procedia PDF Downloads 100

Authors: Devesh Motwani, Ranjana S. Baruah

Abstract:

The prime incentive behind up gradation of heavy oil is to increase its API gravity for ease of transportation to refineries, thus expanding the market access of bitumen-based crude to the refineries. There has always been a demand for an integrated approach that aims at simplifying the upgrading scheme, making it adaptable to the production site in terms of economics, environment, and personnel safety. Recent advances in nanotechnology have facilitated the development of two lines of heavy oil upgrading processes that make use of nano-catalysts for producing upgraded oil: In Situ Upgrading and Field Upgrading. The In-Situ upgrading scheme makes use of Hot Fluid Injection (HFI) technique where heavy fractions separated from produced oil are injected into the formations to reintroduce heat into the reservoir along with suspended nano-catalysts and hydrogen. In the presence of hydrogen, catalytic exothermic hydro-processing reactions occur that produce light gases and volatile hydrocarbons which contribute to increased oil detachment from the rock resulting in enhanced recovery. In this way the process is a combination of enhanced heavy oil recovery along with up gradation that effectively handles the heat load within the reservoirs, reduces hydrocarbon waste generation and minimizes the need for diluents. By eliminating most of the residual oil, the Synthetic Crude Oil (SCO) is much easier to transport and more amenable for processing in refineries. For heavy oil reservoirs seriously impacted by the presence of aquifers, the nano-catalytic technology can still be implemented on field though with some additional investments and reduced synergies; however still significantly serving the purpose of production of transportable oil with substantial benefits with respect to both large scale upgrading, and known commercial field upgrading technologies currently on the market. The paper aims to delve deeper into the technology discussed, and the future compatibility.

Keywords: upgrading, synthetic crude oil, nano-catalytic technology, compatibility

Procedia PDF Downloads 380

Authors: Bedarnia Ishak

Abstract:

In the recent years, the dry reforming of methane has received considerable attention from an environmental view point because it consumes and eliminates two gases (CH4 and CO2) responsible for global warming by greenhouse effect. Many catalysts containing noble metal (Rh, Ru, Pd, Pt and Ir) or transition metal (Ni, Co and Fe) have been reported to be active in this reaction. Compared to noble metals, Ni-materials are cheap but very easily deactivated by coking. Ni-based mixed oxides structurally well-defined like perovskites and spinels are being studied because they possibly make solid solutions and allow to vary the composition and thus the performances properties. In this work, nano-sized nickel ferrite oxides are synthesized using three different methods: Co-precipitation (CP), hydrothermal (HT) and sol gel (SG) methods and characterized by XRD, Raman, XPS, BET, TPR, SEM-EDX and TEM-EDX. XRD patterns of all synthesized oxides showed the presence of NiFe2O4 spinel, confirmed by Raman spectroscopy. Hematite was present only in CP sample. Depending on the synthesis method, the surface area, particle size, as well as the surface Ni/Fe atomic ratio (XPS) and the behavior upon reduction varied. The materials were tested in methane dry reforming with CO2 at 1 atm and 650-800 °C. The catalytic activity of the spinel samples was not very high (XCH4 = 5-20 mol% and XCO2 = 25-40 mol %) when no pre-reduction step was carried out. A significant contribution of RWGS explained the low values of H2/CO ratio obtained. The reoxidation step of the catalyst carried out after reaction showed little amounts of coke deposition. The reducing pretreatment was particularly efficient in the case of SG (XCH4 = 80 mol% and XCO2 = 92 mol%, at 800 °C), with H2/CO > 1. In conclusion, the influence of preparation was strong for most samples and the catalytic behavior could be interpreted by considering the distribution of cations among octahedral (Oh) and tetrahedral (Td) sites as in (Ni2+1-xFe3+x) Td (Ni2+xFe3+2-x) OhO2-4 influenced the reducibility of materials and thus their catalytic performance.

Keywords: NiFe2O4, dry reforming of methane, spinel oxide, oxide zenc

Procedia PDF Downloads 255

Authors: Noor S. Nasri, Eric C. A. Tatt, Usman D. Hamza, Jibril Mohammed, Husna M. Zain

Abstract:

Climate change has becoming a global environmental issue that may trigger irreversible changes in the environment with catastrophic consequences for human, animals and plants on our planet. Methane, carbon dioxide and nitrous oxide are the greenhouse gases (GHG) and as the main factor that significantly contributes to the global warming. Mainly carbon dioxide be produced and released to atmosphere by thermal industrial and power generation sectors. Methane is dominant component of natural gas releases significant of thermal heat, and the gaseous pollutants when homogeneous thermal combustion takes place at high temperature. Heterogeneous catalytic Combustion (HCC) principle is promising technologies towards environmental friendly energy production should be developed to ensure higher yields with lower pollutants gaseous emissions and perform complete combustion oxidation at moderate temperature condition as comparing to homogeneous high thermal combustion. Hence the principle has become a very interesting alternative total oxidation for the treatment of pollutants gaseous emission especially NOX product formation. Noble metals are dispersed on a support-porous HCC such as γ- Al2O3, TiO2 and ThO2 to increase thermal stability of catalyst and to increase to effectiveness of catalytic combustion. Support-porous HCC material to be selected based on factors of the surface area, porosity, thermal stability, thermal conductivity, reactivity with reactants or products, chemical stability, catalytic activity, and catalyst life. γ- Al2O3 with high catalytic activity and can last longer life of catalyst, is commonly used as the support for Pd catalyst at low temperatures. Sustainable and renewable support-material of bio-mass char was derived from agro-industrial waste material and used to compare with those the conventional support-porous material. The abundant of biomass wastes generated in palm oil industries is one potential source to convert the wastes into sustainable material as replacement of support material for catalysts. Objective of this study was to compare the kinetic rate of reaction the combustion of methane on Palladium (Pd) based catalyst with Al2O3 support and bio-char (Bc) support derived from shell kernel. The 2wt% Pd was prepared using incipient wetness impregnation method and the HCC performance was accomplished using tubular quartz reactor with gas mixture ratio of 3% methane and 97% air. Material characterization was determined using TGA, SEM, and BET surface area. The methane porous-HCC conversion was carried out by online gas analyzer connected to the reactor that performed porous-HCC. BET surface area for prepared 2 wt% Pd/Bc is smaller than prepared 2wt% Pd/ Al2O3 due to its low porosity between particles. The order of catalyst activity based on kinetic rate on reaction of catalysts in low temperature is prepared 2wt% Pd/Bc > calcined 2wt% Pd/ Al2O3 > prepared 2wt% Pd/ Al2O3 > calcined 2wt% Pd/Bc. Hence the usage of agro-industrial bio-mass waste material can enhance the sustainability principle.

Keywords: catalytic-combustion, environmental, support-bio-char material, sustainable and renewable material

Procedia PDF Downloads 370

Authors: Bouhenni Mohamed Saif El Islam

Abstract:

In the recent years, the dry reforming of methane has received considerable attention from an environmental view point because it consumes and eliminates two gases (CH4 and CO2) responsible for global warming by greenhouse effect. Many catalysts containing noble metal (Rh, Ru, Pd, Pt and Ir) or transition metal (Ni, Co and Fe) have been reported to be active in this reaction. Compared to noble metals, Ni-materials are cheap but very easily deactivated by coking. Ni-based mixed oxides structurally well-defined like perovskites and spinels are being studied because they possibly make solid solutions and allow to vary the composition and thus the performances properties. In this work, nano-sized nickel ferrite oxides are synthesized using three different methods: Co-precipitation (CP), hydrothermal (HT) and sol gel (SG) methods and characterized by XRD, Raman, XPS, BET, TPR, SEM-EDX and TEM-EDX. XRD patterns of all synthesized oxides showed the presence of NiFe2O4 spinel, confirmed by Raman spectroscopy. Hematite was present only in CP sample. Depending on the synthesis method, the surface area, particle size, as well as the surface Ni/Fe atomic ratio (XPS) and the behavior upon reduction varied. The materials were tested in methane dry reforming with CO2 at 1 atm and 650-800 °C. The catalytic activity of the spinel samples was not very high (XCH4 = 5-20 mol% and XCO2 = 25-40 mol %) when no pre-reduction step was carried out. A significant contribution of RWGS explained the low values of H2/CO ratio obtained. The reoxidation step of the catalyst carried out after reaction showed little amounts of coke deposition. The reducing pretreatment was particularly efficient in the case of SG (XCH4 = 80 mol% and XCO2 = 92 mol%, at 800 °C), with H2/CO > 1. In conclusion, the influence of preparation was strong for most samples and the catalytic behavior could be interpreted by considering the distribution of cations among octahedral (Oh) and tetrahedral (Td) sites as in (Ni2+1-xFe3+x)Td (Ni2+xFe3+2-x)OhO2-4 influenced the reducibility of materials and thus their catalytic performance.

Keywords: NiFe2O4, dry reforming of methane, spinel oxide, XCO2

Procedia PDF Downloads 347

Authors: A. Feliczak Guzik, I. Nowak

Abstract:

Zeolites, classified as microporous materials, are a large group of crystalline aluminosilicate materials commonly used in the chemical industry. These materials are characterized by large specific surface area, high adsorption capacity, hydrothermal and thermal stability. However, the micropores present in them impose strong mass transfer limitations, resulting in low catalytic performance. Consequently, mesoporous (hierarchical) zeolites have attracted considerable attention from researchers. These materials possess additional porosity in the mesopore size region (2-50 nm according to IUPAC). Mesoporous zeolites, based on commercial MFI-type zeolites modified with silver, were synthesized as follows: 0.5 g of zeolite was dispersed in a mixture containing CTABr (template), water, ethanol, and ammonia under ultrasound for 30 min at 65°C. The silicon source, which was tetraethyl orthosilicate, was then added and stirred for 4 h. After this time, silver(I) nitrate was added. In a further step, the whole mixture was filtered and washed with water: ethanol mixture. The template was removed by calcination at 550°C for 5h. All the materials obtained were characterized by the following techniques: X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption/desorption isotherms, FTIR spectroscopy. X-ray diffraction and low-temperature nitrogen adsorption/desorption isotherms revealed additional secondary porosity. Moreover, the structure of the commercial zeolite was preserved during most of the material syntheses. The aforementioned materials were used in the epoxidation reaction of cyclohexene using conventional heating and microwave radiation heating. The composition of the reaction mixture was analyzed every 1 h by gas chromatography. As a result, about 60% conversion of cyclohexene and high selectivity to the desired reaction products i.e., 1,2-epoxy cyclohexane and 1,2-cyclohexane diol, were obtained.

Keywords: catalytic application, characterization, epoxidation, hierarchical zeolites, synthesis

Procedia PDF Downloads 62