京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22278号 / 理博第4592号 / 新制||理||1659(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 竹腰 清乃理, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Yes / In this work a simulation of detailed steady state model of an industrial fluid catalytic cracking (FCC) unit with a newly proposed six-lumped kinetic model which cracks gas oil into diesel, gasoline, liquefied petroleum gas (LPG), dry gas and coke. Frequency factors, activation energies and heats of reaction for the catalytic cracking kinetics and a number of model parameters were estimated using a model based parameter estimation technique along with data from an industrial FCC unit in Sudan. The estimated parameters were used to predict the major riser fractions; diesel as 0.1842 kg-lump/kg-feed with a 0.81% error while gasoline as 0.4863 kg-lump/kg-feed with a 2.71% error compared with the plant data. Thus, with good confidence, the developed kinetic model is able to simulate any type of FCC riser with six-lump model as catalyst-to-oil (C/O) ratios were varied and the results predicted the typical riser profiles.

No description available.

In this dissertation, simulation techniques are used to understand the role of surfaces and grain boundaries in the deformation response of metallic materials. This research utilizes atomistic scale modeling to study nanoscale deformation phenomena with time and spatial resolution not available in experimental testing. Molecular dynamics techniques are used to understand plastic deformation of grain boundaries and surfaces in metals under different configurations and loading procedures. Stress and strain localization phenomena are investigated at plastically deformed boundaries in axially strain thin film samples. Joint experimental and modelling work showed increased stress states at the intersections of slip planes and grain boundaries. This effect, as well as several other differences related to stress and strain localization are thoroughly examined in digital samples with two different grain boundary relaxation states. It is found that localized stress and strain is exacerbated by initial boundary disorder. Dislocation content in the randomly generated boundaries of these samples was quantified via the dislocation extraction algorithm. Significant numbers of lattice dislocations were present in both deformed and undeformed samples. Trends in dislocation content during straining were identified for individual samples and boundaries but were not consistent across all examples. The various contributions to dislocation content and the implications on material behavior are discussed. The effects of grain boundary hydrogen on the deformation response of a digital Ni polycrystalline thin film sample is reported. H content is found to change the structure of the boundaries and effect dislocation emission. The presence of dispersed hydrogen caused a slight increase in yield strength, followed by an increase in grain boundary dislocation emission and an increase in grain boundary crack formation and growth. An atomistic nano indenter is employed to study the nanoscale contact behavior of the indenter-surface interface during nano-indentation. Several indentation simulations are executed with different interatomic potentials and different indenter orientations. A surface structure is identified that forms consistently regardless of these variables. This structure is found to affect several atomic layers of the sample. The implications of this effect on the onset of plasticity are discussed. Finally, the implementation of an elastic/plastic continuum contact solution for use in mesoscale molecular dynamics simulations of solid spheres is discussed. The contact model improves on previous models for the forces response of colliding spheres by accounting for a plastic regime after the point of yield. The specifics of the model and its implementation are given in detail. Overall, the dissertation presents insights into basic plastic deformation phenomena using a combination of experiment and theory. Despite the limitations of atomistic techniques, current computational power allows meaningful comparison with experiments. / Ph. D.

The oil is of vital importance to society due to its derivatives with large employment in economic activities and especially its use as an energy source. The economic and social expansion of the country in recent decades, it requires significant development of our infrastructure, especially in the energy sector. The oil that is positioned as the energy source worldwide leader showed marked increase in the average international price over the past years. In this adverse scenario, improvements in the process of refining the oil representing the large-scale gains for society. The present research study is to evaluate the characteristics of efficiency of catalysis of zeolites ZSM-12 for use as additives for lowcost production of heterogeneous microporous catalysts for catalytic cracking of step (FCC), allowing further reductions in the cost of refining oil. The zeolites are crystalline aluminosilicates, which, in its acid form, playing the role of the main active component of FCC catalysts. In our study the zeolite ZSM-12 (zeolite Socony Mobil) a zeolite synthesized with high SiO2/Al2O3 ratio that presents a structure formed by pores dimensional elliptical opening 12 containing tetrahedral SiO4 (or AlO4) with diameter of 5.5 x 5.9 Å. The results were very promising for the SiO2/Al2O3 ratio assessed, with high conversion and selectivity (mainly the C1 and C3), pointing to ZSM-12 that potential low cost of zeolitic additive for FCC catalysts. / O Petróleo é de vital importância para a sociedade devido aos seus derivados com largo emprego nas atividades econômicas e principalmente sua utilização como fonte energética. A expansão econômica e social do país, nas últimas décadas, vem exigindo importante desenvolvimento da nossa infra-estrutura, notadamente no setor de energia. O petróleo que se posiciona como a fonte de energia líder mundial, apresentou acentuada oscilação do preço médio internacional ao longo dos últimos anos, atingindo no segundo semestre do ano de 2008 o maior preço já praticado desde os primórdios da indústria petrolífera. Neste cenário adverso, melhorias no processo de refino do petróleo representam ganhos em larga escala para sociedade. O presente trabalho de pesquisa teve como finalidade avaliar as características de eficiência de catálise de zeólitas ZSM-12 (Zeolite Socony Mobil) para serem utilizadas como aditivos de baixo custo para produção de catalisadores heterogêneos microporosos para a etapa de craqueamento catalítico (FCC), possibilitando futuras reduções no custo de refino do petróleo. As zeólitas são aluminossilicatos cristalinos, que, na sua forma ácida, desempenham o papel de principal componente ativo dos catalisadores de FCC. A zeólita ZSM-12 apresenta uma estrutura formada por poros unidimensionais de abertura elíptica contendo 12 tetraedros SiO4 (ou AlO4), com diâmetro de 5,5 x 5,9 Å. Nos experimentos foram utilizadas amostras de ZSM- 12 de razões SiO2/Al2O3 de 50, 80, 100 e 150, e foi possível observar que quanto maior a cristalinidade da amostra (verificada por difração de raios-X) maior a conversão durante o craqueamento. A região de máximo de conversão ocorre aproximadamente na razão SiO2/Al2O3 de 80 a 100 e intervalos de tempo entre 0 e 20 minutos. Os resultados mostraram-se bastante promissores para as razões SiO2/Al2O3 avaliadas, apresentando alta conversão e seletividade (principalmente ao C1 e C3), apontando a ZSM-12 como potencial aditivo zeolítico de baixo custo para catalisadores de FCC.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-04-15T15:07:33Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação CONTROLE DA INJEÇÃO DE CATALISADOR EM UMA UNIDADE PILOTO TIPO FCC A FRIO.pdf: 3413557 bytes, checksum: 5abbf7dd3a8cab8c21085e585d6282f6 (MD5) / Made available in DSpace on 2016-04-15T15:07:33Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação CONTROLE DA INJEÇÃO DE CATALISADOR EM UMA UNIDADE PILOTO TIPO FCC A FRIO.pdf: 3413557 bytes, checksum: 5abbf7dd3a8cab8c21085e585d6282f6 (MD5) Previous issue date: 2015-08-31 / CNPQ / O Craqueamento Catalítico Fluidizado (FCC) é largamente utilizado no processo de refino do petróleo para transformar hidrocarbonetos de baixo valor comercial em produtos de elevado valor agregado, como gasolina, diesel e GLP. A crescente demanda de combustíveis fósseis, que são recursos não renováveis, requer melhor compreensão do processo e da operação, desafios que tem atraído o interesse da indústria e da academia pelo FCC. Esse processo é bastante competitivo e está em continuo desenvolvimento tecnológico, cujas pesquisas estão divididas em duas grandes linhas: modelos fluidodinâmicos frios e modelos cinéticos. A combinação das informações obtidas nas linhas de pesquisas deve retornar ao processo industrial e garantir a competitividade. Com essa perspectiva, foi construída uma Unidade Piloto a Frio (UPF), no Departamento de Energia Nuclear da UFPE, para a investigação de parâmetros fluidodinâmicos no riser da unidade com auxílio das medidas de transmissão gama. A transmissão gama é requerida como método não intrusivo para medir a distribuição da concentração do catalisador no reator do FCC o riser. Com a operação da UPF realizam-se medidas em tempo real de pressão, vazão, intensidade da radiação, com a condição de que a automação garante que as variáveis do sistema estão sob controle. Este controle é necessário para realização das medidas porque as hipóteses dos modelos matemáticos para simular o escoamento bifásico ar–catalisador de FCC, assumem que o sistema é um leito fluidizado circulando em regime estacionário. Numa unidade piloto como no processo industrial, o controle da injeção de catalisador é um processo de extrema importância, pois a eficiência da reação de craqueamento dos hidrocarbonetos depende da concentração e da distribuição do catalisador no riser. No presente trabalho foi desenvolvido um novo tipo de injetor de sólidos, com desempenho avaliado em função da pressão, intensidade gama e da estabilidade do sistema sob controle automatizado. Os resultados apresentados demonstram que as variáveis do processo, medidas em tempo real, apresentaram a precisão requerida para a operação do sistema em regime estacionário. / The Fluid Catalyst Cracking FCC is a worldwide used process in petroleum refinery aiming to break fossils long carbohydrates chains into more commercial interesting products as gasoline, diesel, GLP. Increasing demand for renewable energy due to time limiting of the fossils sources and also for environmental reasons requires a continuous development and innovation of the FCC process. Such a demand brings technologic and academic efforts in order to keep FCC as a competitive commercial process. Therefore, the research follows two big lines: fluid dynamics and kinetic which for physical models are developed to simulate industrial plants for studying and return the obtained innovation. Looking for such a research perspective a cold model UPF was installed at Nuclear Energy Department of UFPE for fluid dynamic parameters investigation by means of gamma ray transmission measurements. The nuclear nonintrusive technique is required in the riser for the solid concentration distribution measurements. Online measurements of pressure, flow and gamma intensity are carried out during UPF automated operation that is keeping by control a stead state regime. Such operational conditions are assumed in the hypotheses of mathematical models that air-FCC catalyst flow can be simulated as a circulating fluidized bed in a stead state regime. As for a pilot unit in industrial plants the solid injection in riser is very important as the catalyst concentration distribution maps the cracking reactions, therefore, determining process efficiency. In this work a new solid injector was developed, its capability in keeping stable operational conditions was demonstrated by pressure and gamma intensity measurements under automation control.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The study about magnetic properties of strongly correlated electrons has been an problem of interest in physics by the great technological importance of various materials with this characteristic. A well-known theoretical approach, known as the Hubbard model, has been used in an attempt to describe such phenomena. This model considers the interactions and electron mobility in a simplified way for describing phenomena like itinerant magnetism and the metal-insulator transition. In this study were analyzed the thermodynamic clusters properties of structures with fcc lattice symmetry containing 4, 5, 6, 7 and 8 sites. An exact numerical diagonalization method was used, where the subspaces of the problem were separatly analyzed and put together on, which is a procedure that reduces the processing data time. In order to improve the diagram of quantum states also carried out a ground state analysis of the clusters, known in the literature and obtained from systems with 4, 5 and 6 sites. On this subject a new diagram was developed showing the quantum states transition using the Lanczos method, applied to clusters with 4 to 8 sites in this case. Finally, a comparison was made between the thermodynamic properties and the results found in the new quantum state diagram. The agreement between them is good. / O estudo de propriedades magnéticas de elétrons fortemente correlacionados tem sido um problema de interesse da física pela grande importância tecnológica de vários materiais com essa característica. Uma famosa abordagem teórica, conhecida como modelo de Hubbard, vem sendo utilizada na tentativa de descrever esse tipo fenômeno. Esse modelo considera interações e a mobilidade eletrônica descrevendo de forma simplificada fenômenos como magnetismo itinerante e transição metal-isolante. Neste trabalho foram analisadas propriedades termodinâmicas de clusters de estruturas com simetria da rede fcc contendo 4, 5, 6, 7 e 8 sítios. Foi utilizado um método de diagonalização numérica exata, onde os subespaços do problema foram analisados separadamente e reunidos posteriormente, procedimento que reduz o tempo de processamento dos dados. Foi também realizada uma análise do estado fundamental dos clusters com o intuito de aprimorar o diagrama de estados quânticos, conhecido na literatura, obtido a partir de sistemas com 4, 5 e 6 sítios. Sobre esse assunto, foi desenvolvido um novo diagrama que indica a transição de estados quânticos a partir da utilização do método de Lanczos, neste caso, aplicado a clusters de 4 a 8 sítios. Por fim, foi feita uma análise comparativa entre as propriedades termodinâmicas e os resultados encontrados no novo diagrama de estados quânticos que mostraram boa coerência entre si.

This paper discusses the search of an FeNi25-based alloy with a face-centered cubic crystal structure exhibiting a Curie point around room temperature, for magnetocaloric applications. Fe was substituted in various amounts with FCC-stabilising elements Mn and Co as these elements respectively decrease and increase the Curie Temperature, thus enabling to tune the Curie point. Three characterization methods were carried out on the samples: Magneto- thermo-gravimetry (MTG), X-ray diffraction (XRD) and finally, vibrating sample magnetometer (VSM) measurements were performed. All samples displayed several Curie points, each corresponding to various FCC phases. Also, the last sample, FeNi25Mn6Co2, had an FCC phase fraction of almost 99% and presented two Curie points in the continuity of one another one at -35°C and another at 91°C. Hence, at room temperature, the sample underwent a magnetic phase transition passing from its ferromagnetic state to a paramagnetic one. / Detta arbete består i att utröna möjligheterna att med utgångspunkt från den binära sammansättningen FeNi25 erhålla en ytcentrerad kubisk fas (fcc) med en Curie punkt vid rumstemperatur. Syftet är att använda dessa legeringar i magnetokaloriska tillämpningar. Strategin är att både Mn och Co är fcc stabliliserande grundämnen, och att Mn sänker och Co ökar Curie temperaturen. Tre olika karakteriseringsmetoder användes; röntgendiffraktometri (struktur), Magneto-Termo-Gravimetri (magnetisering vs temperatur) och konventionell magnetometri vid rumstemperatur (magnetisering vs magnetiskt fält, Vibrating Sample Magnetometry VSM). Resultaten visar att även om kristallstrukturen i det närmaste är fullständigt fcc, så ger de magnetiska mätningarna vid handen att flera olika faser är vid handen med avesvärt olika Curie temperaturer. Som en illustration av detta förhållande kan nämnas att sammansättningen FeNi25Mn6Co2 uppvisar en fcc-fraktion på i det närmaste 99%, men har vid en M(T) mätning ett förlopp som enklast förklaras med en Curie punkt vid ca -35C och en ytterligare vid ca 90°C. Denna observation signalerar att de magnetiska egenskaperna torde vara mer beroende av exakt distribution av de ingående atomslagen i fcc strukturen än vad de röntgendiffraktometriska undersökningarna kan detektera.

In dieser Arbeit adressieren wir die Schwierigkeit, Präzisionsvorhersagen mit dem kompletten Satz theoretischer Unsicherheiten in der perturbativen Quantenchromodynamik im Rahmen von Monte-Carlo-Simulationen zu treffen, angesichts der zunehmenden Komplexität der dazu nötigen Berechnungen. Die Anforderungen an die Rechenleistung können so groß sein, dass nicht in jeder Anwendung die bestmögliche Präzision erzielt wird. Wir präsentieren eine Reweighting-Methode für den Monte-Carlo-Ereignisgenerator SHERPA. Diese erstellt Variationen der nominellen Vorhersage mit vergleichsweise geringem zusätzlichen Zeitaufwand. Die Methode ist kompatibel mit aktuellen Multijet-Berechnungen nächsthöherer Ordnung, die mit Korrekturen von allen Ordnungen durch einen Partonschauer versehen sind. Zusätzlich diskutieren wir neue Entwicklungen für einen weiteren Reweighting-Ansatz, der auf QCD-Interpolationsgittern beruht. Diese ermöglichen noch schnellere Variationen für Berechnungen fester Ordnung. Solche Gitter können für Monte-Carlo-Simulationen automatisiert erstellt werden mithilfe von Interfaces wie MCgrid. Unsere Verbesserungen für MCgrid ermöglichen die Erstellung vielseitigerer Gitter, die eine größere Klasse von Berechnungen, Gitter-Implementierungen und Skalenvariationen unterstützen. Darüber hinaus diskutieren wir, auf welche Weise solche Gitter für die Unterstützung von Resummationseffekten erweitert werden müssten. Neben dem Reweighting studieren wir noch die Verwendung von Extrapolationsmethoden für die Vorhersage von Jet-Raten hoher Multiplizitäten, welche an zukünftigen Hochenergiebeschleunigern allgegenwärtig sein werden. Diese Methoden basieren auf dem Skalierungsverhalten der Jet-Raten. Eingebettet ist diese Studie in eine allgemeinere Diskussion der zu erwartenden Jet-Aktivität an einem Proton-Proton-Beschleuniger mit einer Schwerpunktsenergie von 100 TeV.

The Liquid Salt Cooled Reactor (LSCR) provides several potential benefits compared to pressurized water-cooled reactor systems. These include low operating pressure of the liquid salt coolant, the high burnup tolerance of the fuel, and the high operating temperatures which leads to increases in efficiency. However, due to inherently low heavy metal loading, the fuel cycle design presents specific challenges. In order to study options for optimizing the fuel design and fuel cycle, SCALE6.1 was used to create simplified models of the reactor and look at various parameters. The primary parameters of interest included packing factor and fuel enrichment. An economic analysis was performed on these results by developing a simple fuel cycle cost (FCC) model that could be used to compare the different options from an economic standpoint. The lithium enrichment of the FLiBe coolant was also investigated. The main focus was to understand the practical limitations associated with the Li-7 enrichment and whether it could be used for beneficial purposes. The main idea was to determine whether a lower-than-equilibrium enrichment could be used at reactor start up so that the Li-6 isotope acts as a burnable absorber. The results for the lithium enrichment study showed that the enrichment converges over time, but the amount of time required to reach steady state is much too long and the FLiBe coolant could not be utilized for reactivity control as a burnable absorber. The results found through this research provide reasonable guidelines for expected costs and narrow down the types of configurations that should be considered as fuel design options for the LSCR. Additionally, knowledge was gained on methods for modeling the system not only accurately but also efficiently to reduce the required computing power and time.