Production of hydrogen is primarily achieved via catalytic steam reforming, partial oxidation,and auto-thermal reforming of natural gas. Although these processes are mature technologies, they are somewhat complex and CO is formed as a by-product, therefore requiring a separation process if a pure or hydrogen-rich stream is needed. As an alternative method, supported metal catalysts can be used to catalytically decompose hydrocarbons to produce hydrogen. The process is known as catalytic cracking of hydrocarbons. Methane, the hydrocarbon containing the highest percentage of hydrogen, can be used in such a process to produce a hydrogen-rich stream. The decomposition of methane occurs on the surface of the active metal to produce hydrogen and filamentous carbon. As a result, only hydrogen is produced as a gaseous product, which eliminates the need of further separation processes to separate CO2 or CO. Nickel is commonly used in research as a catalyst for methane cracking in the 500-700C temperature range. To conduct methane catalytic cracking in a continuous manner, regeneration of the deactivated catalyst is required and circulation of the catalysts between cracking and regeneration cycles must be achieved. Different reactor designs have been successfully used in cyclic operation, such as a set of parallel fixed-bed reactors alternating between cracking and regeneration, but catalyst agglomeration due to carbon deposition may lead to blockage of the reactor and elevated pressure drop through the fixed bed. Also poor heat transfer in the fixed bed may lead to elevated temperature during the regeneration step when carbon is burned in air, which may cause catalyst sintering. A fluidized bed reactor appears as a viable option for methane catalytic cracking, since it would permit cyclic operation by moving the catalyst between a cracker and a regenerator. In addition, there is the possibility of using fine catalyst particles, which improves catalyst effectiveness. The aims of this project were 1) to develop and characterize a suitable nickel-based catalyst and 2) to develop a model for thermal catalytic decomposition of methane in a fluidized bed.

This thesis reports a research of the corrosion mechanism and corrosion rate of steel reinforcement in concrete. Experimental results are presented to compare the corrosion behaviours of steel reinforcement in two blended-cement concretes in seawater. The experimental program included a study of the influence of crack width on macrocell corrosion, an investigation of the procedure for the determination of polarisation curves of steel in concrete and, an evaluation of the corrosion rate of steel in concrete and the influence of crack width as determined by a new polarisation curve analysis. A mechanism is proposed to interpret the different influences, in both the short and long term, of concrete crack width on the macrocell corrosion rate. This mechanism is based on the finding that the corrosion-spread phenomenon is caused by polarisation effects. An oxygen-depletion mechanism is also proposed to explain the much lower macrocell corrosion rate in the slag cement concrete than that in the flyash cement concrete. The procedure for polarisation testing of steel in concrete is found to be critical to obtaining correct polarisation curves. A twotest procedure is verified to be an appropriate procedure and used in this investigation. Experimental polarisation curves of steel in concrete are found to be very different to those expressed by the kinetic Butler-Volmer equation and, this is considered to be a result of the influence of the passive film on the steel surface in concrete. An empirical polarisation formula is developed and its interpretation is based on the postulation of two parallel kinetic processes occurring at the steel/passive-film/concrete interface; one is the active corrosion process and the other is the film growth/dissolution process. The formula is used to model experimental polarisation curves of steel in concrete through curvefitting analyses. Good curve-fitting results are obtained between the polarisation test curves and model curves. The results are used for evaluation of the corrosion rate and Tafel behaviours of steel in the two concretes and for assessment of the influence of crack width on the corrosion rate within the crack zone.

Steam reforming is the most economical and widely-used route for the conversion of light hydrocarbon (such as natural gas) to various valued-added products. This process is commonly carried out over a low-cost alumina-supported nickel catalyst, which often suffers from carbon deposition resulting in loss of active sites, flow and thermal maldistribution, as well as excessive pressure drop. A bimetallic catalyst with improved anti-coking properties was formulated by incorporating the nickel-based system (15% loading) with cobalt metal (5% loading). Two-level factorial design was employed to investigate the effect of major preparation variables, namely impregnation pH value (2-8), calcination temperature (873-973 K), heating rate (5-20 K min-1) and time (1-5 h). The catalysts prepared were subjected to various characterisation techniques to determine key physicochemical properties (i.e. BET area, H2-chemisorption and NH3- TPD acidity). X-ray diffraction revealed that NiO, Co3O4, NiCo2O4 and a proportion of Ni(Co)Al2O4 aluminates were transformed during H2-reduction to active Co and Ni crystallites. TEM images showed an egg yolk profile in the low-pH catalyst suggesting that main deposition site was located in the particle centre, while metal deposition occurred primarily around the particle exterior for the high-pH catalyst. Temperature programmed experiments were carried out to examine the extent of conversion, type of surface species and solid-state kinetics (using the Avrami-Erofeev model) involved during various stages in catalyst life-cycle (calcination, reduction, oxidation and regeneration). Steam reforming analysis suggested that enhanced catalyst activity may be due to synergism in the Co-Ni catalyst. Specifically, the low-pH catalyst exhibited better resistance towards carbon-induced deactivation than the high-pH formulation. The study also provided the first attempt to develop a quantitative relation between catalyst preparation conditions and its performance (activity, product selectivity and deactivation) for steam reforming reaction. Deactivation and reforming kinetic coefficients were simultaneously evaluated from propane reforming conversion-time data under steam-to-carbon ratios of 0.8-1.6 and reaction temperatures between 773-873 K. The time-dependent optimum operational policy derived based on these rate parameters gave better conversion stability despite the heavy carbon deposit. Thermal runs further showed that the catalysts regenerated via two-stage reductive-oxidative coke burn-off exhibited superior surface properties compared to those rejuvenated by a single-step oxidation.

Password cracking based on dictionary attacks have been confined only to the use of dictionary strings which make sense to both humans and the computer or are usually alphanumeric keyboard patterns. But here we also try to extend the dictionary attacks to homophones which the millennials tend to use more often. The word LOVE is used as LUV, LAV. Based on the pronunciation of a word there can be many spellings to it. Phoneme to Grapheme Correspondences have a great amount of significance here. So here in this research we try to incorporate all such words in the attacking dictionary with the highest possible probabilities to see if it has any impact on the password cracking efficiency. We use the probabilistic context-free grammar password cracker to see what our test results yield.

abstract: The main objective of this study is to investigate drying properties and plastic shrinkage cracking resistance of fresh cement-based pastes reinforced with fibers and textiles. Naturally occurring mineral wollastonite has been studied independently as well as in combination with AR-glass textile. A series of blended mixes with Portland cement and wollastonite nano-fibers were developed and tested under low vacuum conditions to simulate severe evaporation conditions and expedite the drying process causing plastic shrinkage cracks. Cumulative moisture loss, evaporation rates, and diffusivity were analyzed by means of a 2-stage diffusion simulation approach, developed previously in Arizona State University. Effect of fiber-matrix interaction on the transport properties of the composite were evaluated using the existing approach. Morphology of the cracked surface was investigated by the means of image analysis wherein length, width, area and density of the cracks were computed to help characterize the contribution of fiber and textile in the cracking phenomenon. Additionally, correlation between cumulative moisture loss and crack propagation was attempted. The testing procedures and associated analytical methods were applied to evaluate effectiveness of four wollastonite fiber sizes and also a hybrid reinforcement system with alkali-resistant glass (ARG) textile in improving shrinkage cracking related parameters. Furthermore, the experimental and analytical approach was extended to magnified version of the existing shrinkage testing set-up to study the size effect of these composites when subjected to matching drying conditions. Different restraining mechanisms were used to study the simulation of the cracking phenomena on a larger specimen. Paste and mortar formulations were developed to investigate size effect on shrinkage resistance of cementitious composites. / Dissertation/Thesis / Masters Thesis Civil Engineering 2014

Orientador: Antonio Carlos Luz Lisboa / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-12T15:53:08Z (GMT). No. of bitstreams: 1 Silva_GermanGonzalez_M.pdf: 1967268 bytes, checksum: fb1da8c45ce0a2b393f58ef9ab9d72d0 (MD5) Previous issue date: 2008 / Resumo: Os reatores de leito fluidizado são uma das mais importantes tecnologias atuais para processos heterogêneos gás-sólido, tanto catalíticos como não catalíticos. As aplicações industriais mais importantes incluem o craqueamento catalítico na indústria petroquímica, a combustão e/ou gaseificação de carvão, biomassa e resíduos sólidos. Estes são importantes processos para a geração de energia, produção de combustíveis e gás de síntese. Um dos tipos de reatores de leito fluidizado mais relevante é o reator de fluxo ascendente conhecido como riser. Este reator consiste de uma coluna tubular na qual o sólido e o gás escoam co-correntes de forma ascendente. Em comparação com outras tecnologias, o reator riser tem uma importante desvantagem: uma distribuição de tempos de residência variada no reator que reduz a conversão e a seletividade. Recentemente cresceu o interesse por outro tipo de reator gás-sólido circulante que possui melhor desempenho que o reator riser. Neste tipo de reator, conhecido como downer, por oposição ao riser, o escoamento co-corrente gás-sólido ocorre de forma descendente, o que lhe outorga características fluidodinâmicas que se assemelham mais ao escoamento tipo pistão e permitem um melhor controle da conversão, da seletividade e da desativação. O objetivo deste trabalho é estudar a simulação de reatores gás-sólido tipo downer, incorporando modelos fluidodinâmicos com modelos de engenharia das reações químicas e catalíticas. Desenvolve-se, de forma geral, a modelagem dos diferentes fenômenos fluidodinâmicos, físico-químicos e catalíticos que ocorrem no reator e são propostos algoritmos de solução para diferentes situações. Posteriormente, aplica-se o modelo proposto do reator downer ao estudo de um caso industrial: o craqueamento catalítico. Os resultados mostram um enfoque geral aplicável para a modelagem e simulação de sistemas de reações gás-sólido em fluxo descendente. As simulações do processo industrial de craqueamento catalítico revelam que o reator tipo downer apresenta características de desempenho que o fazem superior ao reator tipo riser convencional. / Abstract: The fluidized bed reactor is one of the most important technologies for gas-solid heterogeneous operations, considering catalytic or non catalytic processes. The most important industrial applications include catalytic cracking, coal combustion and biomass combustion. The most relevant fluidized bed reactor is the ascendant flow reactor, which is known as riser. The riser reactor consist of a tubular column in which the solid and the gas flow cocurrently upward. The riser reactor has as main disadvantage a wide residence time distribution, which reduce the conversion and the selectivity. Recently, it has grown the interest in a new type of gas-solid circulating reactor with a better performance than the riser which is known as downer. In this reactor the gas and the solid flow cocurrently downward, creating hydrodynamic features comparable to a plug flow reactor and allowing a better control over the conversion, the selectivity and the deactivation. This work regarded it had been studied the simulation of the gas-solid downer reactor, including hydrodynamic models and models from the chemical reaction engineering. It was developed in a general way the modelling of the hydrodynamic, physical chemical and catalytic phenomena occurring in the reactor. Algorithms were proposed to solve of different simulation cases. The proposed model of the downer reactor was used in the studying of one industrial case: the catalytic cracking. The results show a general approach which is applicable for modelling and simulation of gas-solid reactive system with descendent flow. The simulations of the catalytic cracking show that the downer reactor has features that make it perform better than the conventional riser reactor. / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

This study investigated localized corrosion behavior of austenitic stainless steels under stressed and unstressed conditions, as well as corrosion of metallic thin films. While austenitic stainless steels are widely used in corrosive environments, they are vulnerable to pitting and stress corrosion cracking (SCC), particularly in chloride-containing environments. The corrosion resistance of austenitic stainless steels is closely tied to the alloying elements chromium, nickel, and molybdenum. Polarization curves were measured for five commercially available austenitic stainless steels of varying chromium, nickel, and molybdenum content in 3.5 wt.% and 25 wt.% NaCl solutions. The alloys were also tested in tension at slow strain rates in air and in a chloride environment under different polarization conditions to explore the relationship between the extent of pitting corrosion and SCC over a range of alloy content and environment. The influence of alloy composition on corrosion resistance was found to be consistent with the pitting resistance equivalent number (PREN) under some conditions, but there were also conditions under which the model did not hold for certain commercial alloy compositions. Monotonic loading was used to generate SCC in in 300 series stainless steels, and it was possible to control the failure mode through adjusting environmental and polarization conditions. Metallic thin film systems of thickness 10-200 nm are being investigated for use as corrosion sensors and protective coatings, however the corrosion properties of ferrous thin films have not been widely studied. The effects of film thickness and substrate conductivity were examined using potentiodynamic polarization and scanning vibrating electrode technique (SVET) on iron thin films. Thicker films undergo more corrosion than thinner films in the same environment, though the corrosion mechanism is the same. Conductive substrates encourage general corrosion, similar to that of bulk iron, while insulating substrates supported only localized corrosion.

The interactions between engineering materials and their environment which give rise to stress corrosion cracking are reviewed and industrial examples from the petrochemical industry are described. In one of the examples, cracking took place in carbon steel exposed to pressurised gas containing carbon monoxide, carbon dioxide and water. The crack morphology in this system was studied by metallography of samples from industrial gas processing plants and the crack growth rates were determined using precracked specimens. Constant extension rate tests, U-bend specimens and potentiodynamic studies were used to evaluate alternative materials and inhibitor additions in CO-C02-H20 environments. Electrochemical noise was accessed as a technique to monitor sec on line. It was found that the CO-C02-H20 system was characterised by a time dependent adsorption of carbon monoxide at anodic and cathodic sites. The adsorption produced a critical balance between crack tip corrosion rate and the repassivation process comparable to the behaviour at the active-passive transition zone in more conventional systems. The anodic passivation exhibited a breakdown potential near to -400 mV (Ag/ AgCI) that defined the zone of sec susceptibility. Inhibition by CO and hence sec was virtually independent of CO partial pressure provided there was a sufficient reservoir of CO. The addition of commercial film forming inhibitors did not greatly influence the system and sec was still observed in CO-C02-H20 environments to which inhibitors had been added. Steels containing alloy additions of more than 9 % chromium were found to be resistant to sec but austenitic-ferritic weld joints cracked. A low alloy 3% nickel steel performed well in the constant extension rate tests but was not wholly resistant to sec. The morphology of stress corrosion cracks in CO-C02-H20 mixtures was influenced by carbon monoxide partial pressure. More corrosion was observed on the crack walls at low carbon monoxide partial pressure and widened cracks resembling •mesa• corrosion were common. This increased corrosion was probably due to difficulty in maintaining passivity in the crevice formed by the growing crack. Similarly, crevicing in precracked specimens appeared to inhibit sec and no crack extension was observed. Electrochemical noise proved to be a useful tool for monitoring. / Thesis (PhD)--University of Pretoria, 1994. / gm2013 / Materials Science and Metallurgical Engineering / PhD

Please read the abstract in the section front of this document / Dissertation (MEng(Metallurgical Engineering))--University of Pretoria, 2006. / Materials Science and Metallurgical Engineering / unrestricted

The objective of this work was the development of structured zeolite catalysts by growing of ZSM-5 and Y zeolites layers on the pre-treated FeCrAlloy wires, which could now offer technical advantage in catalytic application. The advantages of implementation of zeolitic coatings in industrial applications are that they have; lower pressure drop, high heat and mass transfer rates compared to standard pelleted or extruded catalysts. The key focus of this research was the generation of thin films of zeolite ZSM–5 and Y zeolite catalysts on the surface of a FeCrAlloy metal substrate. Using in-situ hydrothermal synthesis, the influence of the synthesis parameters such as substrate oxidation and crystallisation time on the zeolite crystallisation process in both the bulk phase (powder) and on the structured zeolite was studied and optimised. Then powder and structured Na-ZSM-5 and Na-Y were treated by calcination and ion exchange in post-synthesis treatment. Further post-synthesis modification was required in the zeolite Y case to improve the catalytic properties. The post synthetic modification of zeolite Y was carried out using acidified ammonium nitrate which was optimised to produce dealuminated zeolite Y with good crystallinity and a Si/Al = 8. Characterisation was performed after each stage of this work to optimise catalyst development using XRD, SEM, EDAX, BET, MAS-NMR, and TGA. Once the optimised zeolite Y and ZSM-5 structured catalysts prepared, cracking of n-heptane was carried out to assess the in catalytic performance compared with Y and ZSM-5 pellets in a fixed-bed reactor under the same operation conditions. The cracking of n–heptane over the pellets and structured catalysts for both ZSM–5 and Y zeolite showed very similar product selectivities for similar amounts of catalyst with apparent activation energy of around 60 kJ mol-1. This research demonstrates that structured catalysts can be manufactured with excellent zeolite adherence and when suitably activated/modified give comparable cracking results to the pelleted powder forms. These structured catalysts will improve temperature distribution in highly exothermic and endothermic catalysed processes.