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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
91

Desenvolvimento de procedimento analítico empregando multicomutação em fluxo para determinação fotométrica de cloreto em amostras de coque de petróleo / Development of analytical procedure employing multicommutation for photometric determination of chloride in petroleum coke

Andréia Cardoso Pereira 16 April 2010 (has links)
Neste trabalho foi desenvolvido um procedimento analítico empregando o processo de multicomutação para determinação de íons cloreto com detecção fotométrica para aplicação em amostras de coque de petróleo. O procedimento foi baseado no método espectrofotométrico descrito no Standard Methods, onde a reação entre tiocianato de mercúrio (II) e cloreto leva ao deslocamento dos íons tiocianato e à formação de um complexo de coloração vermelha com o Fe (III), que foi monitorado em 455 nm. Foram construídos dois módulos de análise empregando válvulas solenóide de três vias no primeiro e válvulas de estrangulamento no outro. Com os parâmetros analíticos otimizados para o primeiro módulo, obteve-se uma curva analítica linear para o intervalo de 0,25 a 4,0 mg L-1 de cloreto (R= 0,997), com um limite de detecção de 0,12 mg L-1 (3xbranco/inclinação); RSD de 1,7% (n=15) e uma freqüência de amostragem de 50 det h-1. O segundo módulo de análise foi proposto a fim de eliminar a etapa de acidificação das soluções de referência e amostras. Esta etapa era efetuada off line para liberar as bolhas formadas na reação. A curva analítica obtida para este módulo foi linear para o intervalo de 0,25 a 6,0 mg L-1 de cloreto (R= 0,999), com um limite de detecção de 0,04 mg L-1 (3xbranco/inclinação); RSD de 0,8% (n=15) e uma frequência de amostragem de 50 det h-1. O módulo foi aplicado em amostras de coque de petróleo e também no material de referência certificado. / In this work was developed an analytical procedure employing multicommutation for the photometric determination of chloride in petroleum coke. The procedure was based on the photometric method described on Stand Method, where the reaction between mercury(II) thyocyanate and chloride causes the displacement of the thyocyanate ions, which reacted with iron(III) forming a compound that monitored at 472 nm. Two analysis modules were designed employing three-way and pinch solenoid valves. After the optimizing of the analytical parameters related to analysis module that employed three-way solenoid valves, the analytical curve presented a linear response in the concentration range of 0.25 to 4.0 mg L-1 (R = 0.997). A detection limit of 0.12 mg L-1 chloride, a relative standard deviation of 1.7 % (n = 15) and a sampling frequency of 50 determination per hour were also achieved. The second analysis module was designed to avoid acidification step of sample and reference solutions that was carried out off line to prevent bubbled delivering. The analytical curve presented a linear response within the concentration range of 0.25 up to 6.0 mg L-1 chloride (R=0.999). Detection limit of 0.04 mg L-1, standard deviation of 0.8 % (n=15), and sampling frequency of 50 determination per hours were of achieved. The proposed system was used for the determination of chloride in petroleum coke and also in certified material.
92

Tratamento de despejo de coqueria via nitritação/desnitritação operando um sistema de lodo ativado em bateladas sequenciais. / Coke-oven wastewater treatment over nitritation/denitritation in an activated sludge sequencing batch reactor.

Luciano Matos Queiroz 19 June 2009 (has links)
A presente pesquisa objetivou estudar a remoção dos poluentes presentes em uma água residuária de coqueria, através do processo biológico de nitritação/desnitritação operando um reator de lodo ativado em bateladas seqüenciais em duas etapas sucessivas. Durante a primeira, o reator foi alimentado com um efluente sintético composto por dois poluentes abundantes em despejos de coqueria: nitrogênio amoniacal (500 mg N/L) e fenol (1.000 mg C6H5OH/L). Na segunda, o reator foi alimentado com o despejo gerado na unidade de coqueria de uma indústria siderúrgica integrada. Ao longo da primeira etapa, ao final da fase aeróbia dos 28 ciclos de tratamento, foi possível alcançar eficiências de remoção de N-NH3 superiores a 90% com predominância do N-NO2 - na massa líquida do reator evidenciado pelas relações N-NO2 -/ (N-NO2 - + N-NO3 -) superiores a 86%. O principal mecanismo de inibição das bactérias oxidantes de nitrito (BON) foram concentrações de amônia livre no conteúdo do reator entre 3,2 e 19,5 mg NH3/L. As taxas específicas de nitritação variaram entre 0,03 e 0,11 kg N-NH3/ kg SSV.dia, para temperaturas no conteúdo do reator entre 15 e 34°C. Durante a fase anóxica, o fenol mostrou-se adequado como fonte de carbono para a biomassa desnitritante, desde que as taxas de aplicação volumétricas fossem inferiores a 0,02 kg fenol/m³.hora. Respeitando essa condição, foi possível alcançar: eficiências de remoção de fenol entre 45 e 56%; taxas específicas de remoção de fenol entre 0,03 e 0,09 kg C6H5OH / kg SSV.dia; taxas específicas de desnitritação entre 0,03 e 0,06 kg N-NO2 -/ kg SSV.dia e eficiências de remoção de (N-NO2 - + N-NO3 -) superiores a 95%. Ao longo da fase anóxica foram retiradas amostras do conteúdo do reator para a realização de análises de nitrofenóis (NF). Os resultados acusaram a presença de 2 nitrofenol e 4 nitrofenol em concentrações proporcionais à taxa de aplicação volumétrica do fenol na massa líquida do reator. A presença desses compostos em concentrações inferiores a 0,5 mg/L não causou impacto sobre a desnitritação biológica. As análises realizadas em amostras coletadas ao final da reação anóxica, não acusaram a presença de 2 e 4 NF, demonstrando que esses compostos podem ser biodegradados por uma biomassa bem adaptada ao fenol. A concepção do sistema para tratamento da água residuária de coqueria via nitritação/desnitritação envolveu a operação de dois reatores (principal e reator de polimento) operados em bateladas seqüenciais. As condições de operação do reator principal eram manipuladas para viabilizar o acúmulo de NNO2 - ao final da fase aeróbia e promover a desnitritação durante a fase anóxica, utilizando como fonte de carbono a própria matéria orgânica presente no despejo. Como o sobrenadante do reator principal apresentava concentrações elevadas de N-NO2 -, esse efluente era aplicado no reator de polimento, juntamente com etanol como fonte de carbono para redução do NNO2 -. Ao final da fase aeróbia dos ciclos de tratamento conduzidos no reator principal alcançaram-se: relações NO2 -/ (N-NO2 - + N-NO3 -) superiores a 88%; eficiências de remoções de nitrogênio total superiores a 60%; remoções de N-NH3 superiores a 90%, para valores de pH na massa líquida do reator entre 7,8 e 8,5 e, temperatura entre 23 e 31°C. Tal qual ocorrido durante a primeira etapa da investigação, o principal mecanismo de inibição da atividade das bactérias oxidantes de nitrito foi a toxicidade conferida pelas concentrações de amônia livre (3,7 a 15,7 mg NH3/L) no conteúdo do reator. Durante a fase anóxica, as eficiências de remoção de (N-NO2 - foram limitadas pela disponibilidade de matéria orgânica biodegradável no despejo da coqueria, razões DBO/DQOafluente superiores a 80% resultaram em remoções de N-NO2 - próximas de 100%. Quanto ao reator de polimento, pode-se afirmar que o etanol teve um efeito positivo sobre a remoção de matéria orgânica da água residuária da coqueria, considerando a configuração (dois lodos) utilizada. / The present research aimed to study the coke-oven wastewater treatment over nitritation/denitritation in an activated sludge sequencing batch reactor in two successive phases. During the first one, the reactor was fed with a synthetic effluent composed by two abundant pollutants present in coke-oven wastewaters: total ammonia nitrogen (500 mg TAN.l-1) and phenol (1,000 mg C6H5OH.l-1). During the second phase, the reactor was fed with the wastewater produced in an integrated steel industrys coke-plant. The results of the first phase (28 cycles) showed that was possible to achieve TAN removal efficiencies higher than 90% with NO2 --N predominance in the reactor content, evidenced by the rates NO2 --N/ (NO2 --N + NO3 --N) higher than 86%. The main mechanism of the nitrite oxidizer bacteria (NOB) inhibition was free ammonia concentrations between 3.2 and 19.5 mg NH3.l-1. The specific nitritation rates varied between 0.03 and 0.11 kg TAN. kg VSS-1.d-1, for temperatures between 15 and 34oC. Phenol showed to be suitable as carbon source for denitrifying biomass, once the volumetric application rates were lower than 0.02 kg phenol.m-3.h-1. Obeying this condition, it was possible to achieve: phenol removal efficiencies between 45 and 56%; specific phenol removal rates between 0.03 and 0.09 kg C6H5OH. kg VSS-1.d-1; specific denitritation rates between 0.03 and 0.06 kg NO2 --N . kg VSS-1.d-1 and removal efficiencies of (NO2 --N + NO3 --N) higher than 95%. During the anoxic phase, samples were collected from the reactor content for nitrophenols analyses. The results showed the presence of 2- nitrophenol (2-NP) and 4-nitrophenol (4-NP) in concentrations proportional to phenol volumetric application rate in the reactor liquid mass. The presence of those compounds in concentrations lower than 0.5 mg/L does not cause impact over the biological denitritation. The analyses accomplished in samples collected at the end of the anoxic reaction do not show the presence of 2 and 4-NP, demonstrating that these compounds can be biodegraded by a well-adapted biomass. The arrangement of the system for the treatment of coke-oven wastewater (Phase 02) over nitritation/denitritation involved the operation of two sequencing batch reactors (the main reactor and the polishing one). The operational conditions of the main reactor were manipulated to make feasible the NO2 --N accumulation at the end of the aerobic stage and promote the denitritation using the own organic matter present in the cokeoven wastewater as carbon source. As the supernatant of the main reactor presented high nitrite concentrations, this effluent was conducted to a biological denitrifying polishing reactor with ethanol as carbon source. At the end of the aerobic stage of the treatment cycles conducted in the main reactor, it was achieved: NO2 --N/ (NO2 --N + NO3 --N) higher than 88%; total nitrogen removal efficiencies higher than 60%; ammonia nitrogen removal higher than 90%. As occurred during the first phase of the investigation, the main NOB activity inhibition was the toxicity of the free ammonia concentrations (3.7 to 15.7 mg NH3.l-1) in the reactor content. At the end of anoxic stage, the NO2 --N removal efficiencies were limited by the availability of the biodegradable organic matter in the coke-oven wastewater but BOD/CODinfluent higher than 80% resulted in NO2 --N removals next to 100%. Regarding to the polishing reactor, it can be stated that the ethanol had a positive effect over the organic matter removal of the coke-oven wastewater.
93

Avaliação da formação de eteno em catalisadores de Ni suportados em matrizes de Al2O3-aditivo(Ca, Ba, Sr) na reação de reforma a vapor do etanol / Evaluation of the ethene formation over Ni catalysts supported on Al2O3 modified (Ca, Ba, Sr) for ethanol steam reforming

Kariny Ferreira Monteiro Elias 12 September 2011 (has links)
No presente trabalho foi estudado o efeito da adição de cálcio, bário e estrôncio (0%-5% em massa) em catalisadores Ni/Al2O3, contendo 5% de níquel em massa, frente à reação de reforma a vapor do etanol com o objetivo de inibir a reação de desidratação do etanol, precursor do carbono. Os catalisadores foram preparados por dois métodos: impregnação (I) e co-precipitação (C). Inicialmente todos os catalisadores obtidos foram submetidos a analise de espectroscopia dispersiva em emissão de raios X (EDX), para confirmação de suas composições químicas, em seguida foram aplicados na reação de reforma a vapor do etanol, dentre os catalisadores estudados os que apresentaram a menor formação de eteno foram, 5%Ca-5%Ni/Al (I) e 5%Ca-5%Ni/Al (C) dentre os que continham cálcio; 0,5%Ba-5%Ni/Al (I) e 5%Ba-5%Ni/Al (C) dentre os que continham bário e 5%Sr-5%Ni/Al (I) e 5%Sr-5%Ni/Al (C) dentre os que continham estrôncio, sendo então submetidos as etapas de caracterização, difração de raios X (DRX), redução a temperatura programada (RTP), área superficial específica pelo método BET e reação de decomposição do isopropanol. O desempenho destes catalisadores foi comparado com o obtido para os catalisadores sem aditivos 5Ni/Al(I) e 5Ni/Al(C). O método da impregnação demonstrou ser mais eficiente do que o método da co-precipitação para o alcance dos objetivos do trabalho e o catalisador 5Ca-5Ni/Al (I) foi o mais efetivo na redução da acidez da alumina e consequentemente mostrou menor deposição de carbono. / Catalysts of Ni/Al2O3 containing 5wt% of nickel and modified by calcium, barium and strontium addition (0wt% - 5wt%) were tested in the ethanol steam reforming with the goal of reduce the reaction of dehydratation of ethanol, a carbon precursor. The catalysts were prepared by two methods: impregnation (I) and co-precipitation (C). Initially, all catalysts were subjected to analysis by Energy-dispersive X-ray spectroscopy (EDX), to confirm their chemical compositions, then they were applied in the steam reforming of ethanol, Among the catalysts studied those with lower ethene production were: 5%Ca-5%Ni/Al (I), 5%Ca-5%Ni/Al (C) among those containing calcium; 0,5%Ba-5%Ni/Al (I), 5%Ba-5%Ni/Al (C) among those containing barium and 5%Sr-5%Ni/Al (I), 5%Sr-5%Ni/Al (C) among those containing strontium, being submitted to the characterization by X-ray diffraction (XRD), temperature programmed reduction (TPR), specific surface area by BET method and reaction of isopropanol decomposition. The performance of these catalysts was compared to with the catalysts without additives 5(wt%)Ni/Al(I) and 5(wt%)Ni/Al(C). The impregnation method was more effective than the method co-precipitation for achieving the objectives of this work and the catalyst 5Ni-5Ca/Al (I) was the more effective in the reduction of alumina acidity and also showed the lower carbon deposition.
94

Estudo da influência de alguns combustíveis na sinterização de minério hematítico. / Effect of some fuel for iron ore sintering.

Cyro Takano 10 September 1970 (has links)
A sinterização de finos de minério de ferro é utilizada já há mais de 5 decênios , embora o maior impulso tenha-se verificado na década de 1950-1960. No Brasil, a Companhia Siderúrgica Belgo Mineira foi a pioneira nesses estudos, já em 1938. A literatura cita trabalhos analisando inúmeros fatores no estudo da sinterização, seja quanto aos tipos de equipamentos, às variáveis do processo, às variáveis da mistura a sinterizar, às variáveis do sínter produzido, até recente estudo sobre sinterização semi-redutora . Na presente tese o autor propõe-se a analisar o efeito das variações de algumas características dos combustíveis na sinterização de minério de ferro. Com o levantamento das curvas térmicas (curvas de evolução da temperatura com o tempo, num determinado ponto do interior da carga) o autor pretende analisar certos efeitos das matérias voláteis, da cinza e da reatividade dos combustíveis. Serão, também, verificados os efeitos de pequenas variações de unidade na sinterização, tendo em vista que, em unidades de operação contínua de sinterização, os recentes métodos adotados para controle da umidade da mistura a sinterizar (tais como por sonda de nêutrons e baseado na resistividade elétrica da carga) permitem avaliar o teor de umidade com sensibilidade dentro da faixa de 1%, isto é, com desvio de mais ou menos 0,5% (3), (4). Além do coque, que é o combustível normalmente empregado na sinterização, foram utilizados o carvão metalúrgico de Santa Catarina e o carvão vegetal (de eucalipto). Ênfase maior foi dada ao carvão metalúrgico, por razões que são justificadas logo adiante.O \"carvão metalúrgico\" de Santa Catarina, é o principal produto do beneficiamento do carvão mineral betuminoso das jazidas desse Estado, para emprego na produção de coque, geralmente em mistura com outro carvão importado da mesma categoria. Julgou-se que a possibilidade de aproveitamento desse carvão metalúrgico (não coqueificado) na sinterização, mormente com o encarecimento do carvão importado, ora verificado, poderá representar uma nova solução aos problemas siderúrgicos nacionais, tanto sob ponto de vista econômico, como estratégico e social. Além disso, o desvio de uma parcela do carvão metalúrgico nacional para a sinterização, dentro do critério da mistura com determinada quota de carvão importado, permitirá a operação dos altos fornos com coque de melhor qualidade. / Sem abstracts
95

The effect of diabietic acid on the coking of oxidised solvent-extracted coal

Ludere, Margaret Tshimangadzo 17 April 2008 (has links)
Refcoal is a refined carbon source obtained by extraction of coal with dimethylformamide (DMF). During the coking process, Refcoal goes through a mesophase (fluid) stage to form an anisotropic coke. In contrast, oxidised Refcoal does not undergo such a mesophase stage during the carbonisation process. Thus it does not yield an anisotropic coke, but forms an isotropic coke. The objective of this study is to produce an anisotropic coke from oxidised Refcoal. For this purpose, diabietic acid, a hydrogen donor, was considered as a suitable additive. Coking was performed in sealed glass capillary tubes as diabietic acid proved to be volatile at the carbonisation temperature of 500 °C. The resultant cokes were analysed using thermogravimetric analysis, Raman spectroscopy and optical microscopy. The results show that the degree of anisotropy increased with diabietic acid content (3, 5 and 10 mass %). / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / MSc / Unrestricted
96

Catalytic graphitisation of refcoal cokes

Nyathi, Mhlwazi Solomon 11 June 2008 (has links)
Synthetic graphite is an important industrial material, used in nuclear reactors, electrodes and many other applications. Graphitisation of coke is the solid-state transformation of the disordered carbon atoms into a well-ordered hexagonal graphite structure, requiring temperatures as high as 2 600 ºC. Catalytic graphitisation using metals or metal compounds allows the rearrangement of atoms to occur at lower temperatures. The extent of catalytic graphitisation is markedly dependent on the structural ordering of the parent coke, the catalyst concentration and the reaction conditions. Solvent extraction of coal using dimethylformamide (DMF) as a solvent yields a refined coal solution referred to as Refcoal solution. Cokes of solvent-refined Tshikondeni coal derivatives have been found to be graphitisable. The activity of acetylacetonate and hydroxyquinolinate complexes of Al, Ca, Cu, Fe and Zr for catalysing the graphitisation of Refcoal cokes at 1 600 and 2 000 ºC was investigated. The effect of residence time on the catalytic graphitisation of Refcoal cokes was investigated by heat-treating cokes for two and six hours at 1 600 °C. For iron(III)acetylacetonate, the effect of metal concentrations was studied. Samples were analysed using thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and optical microscope techniques. The results show that calcium(II)acetylacetonate catalyses the graphitisation of Refcoal cokes. The degree of graphitisation increases with an increase in the iron concentration. However, iron promotes localised graphitisation, probably in the vicinity of the catalyst particles. / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted
97

Study of the early stages of carbonisation of some pitch materials of different composition

Manabile, Segaule Isaac 29 November 2009 (has links)
The formation and development of mesophase from different pitches under carbonisation conditions was investigated. Members of the pyrolysis series were prepared from four pitches. A temperature range between 380 and 500°C was used to follow mesophase development for each pitch. As-received pitches and their green cokes were characterised by thermomechanical analysis (glass transition temperature and softening point temperature), elemental analysis, Fourier transform infrared spectroscopy, thermogravimetry or differential thermogravimetry, and optical microscopy (mesophase content). Additional data about the evolution of different volatile products and about possible chemical reactions occurring during thermal decomposition were obtained from thermogravimetric mass spectrometric analysis. The effect of heating rate on the behaviour and carbon yield was also studied. The results showed that the two anthracene oil pitches do not develop mesophase, whereas the medium-temperature and high-temperature pitches do. However, their textures are completely different. The medium-temperature pitch shows an improvement in texture from the mosaic to the coarse domain at 500°C, whereas the high-temperature pitch shows flow domains. It was further shown that the process of preparing mesophase, i.e. the heat-treatment process, increases the aromaticity and carbon yield. Thermogravimetric mass spectrometric analysis showed that the dominant reaction for all the pitches is the condensation reaction, which is accompanied by the evolution of H2 and CO. The heating rate affects the behaviour of the pyrolysing pitches in that a lower heating rate lowers the carbon yield. This study gave insight into the influence of the nature and composition of the precursor on the formation of mesophase. / Dissertation (MSc)--University of Pretoria, 2009. / Chemistry / unrestricted
98

Simulação da combustão de coque em regeneradores FCC usando fluidodinâmica computacional / Simulation of coke combustion in FCC regenerators using computational fluid dynamics

Prieto Jiménez, Natalia 18 August 2018 (has links)
Orientador: Milton Mori / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-18T19:12:31Z (GMT). No. of bitstreams: 1 PrietoJimenez_Natalia_M.pdf: 6938239 bytes, checksum: 6c44d3053179a676042ac55971eeb06b (MD5) Previous issue date: 2011 / Resumo: Craqueamento Catalítico Fluidizado (FCC) é um processo amplamente utilizado para converter frações de hidrocarbonetos de óleos brutos de petróleo com elevado ponto de ebulição, a produtos mais valiosos tais como gasolina e gases olefínicos (alcenos). Durante as reações de craqueamento, o catalisador é desativado rapidamente devido à deposição de coque na sua superfície. Em unidades industriais de FCC, o catalisador desativado é continuamente regenerado utilizando um regenerador, conectado ao reator riser. Além da regeneração do catalisador (combustão de coque pelo contato com o ar), o regenerador FCC fornece também a energia necessária para as reações de craqueamento endotérmicas. O objetivo deste trabalho de pesquisa é simular a combustão de coque em um regenerador tridimensional, analisado variáveis de saída como concentração de carbono, temperatura, velocidade axial e radial das fases sólida e gasosa, e fração volumétrica de sólidos, mediante a técnica de Fluidodinâmica Computacional (CFD). Para isto, são utilizadas duas configurações de regenerador com dimensões e condições de contorno tomadas da literatura. Para a modelagem matemática e numérica utilizaram-se os softwares comerciais ANSYS-CFX V11 e FLUENT V12, junto com sub-rotinas desenvolvidas durante a pesquisa. Foram comparados sistemas de reação homogênea e heterogênea utilizando o modelo cinético Finite-Rate laminar, no qual as taxas de reação são determinadas pelas expressões cinéticas de Arrhenius. Do desenvolvimento das simulações obtiveram-se resultados satisfatórios que serão úteis no entendimento do complexo processo da regeneração de catalisadores para processos de FCC / Abstract: Fluidized Catalytic Cracking (FCC) is a widely used process to convert hydrocarbon fractions of crude petroleum oils with high boiling point to more valuable products such as gasoline and olefin gases (alkenes). During the cracking reactions, the catalyst is quickly deactivated due to coke deposition on its surface. In FCC industrial units, deactivated catalyst is continuously regenerated using a regenerator, connected to the riser reactor. In addition to catalyst regeneration (coke combustion by contact with air), FCC regenerator also provides the necessary energy for endothermic cracking reactions. The aim of this research was to simulate the coke combustion in a three-dimensional regenerator, analyzing output variables as coke concentration, temperature, axial and radial velocity of solid and gaseous phases, and solid volume fraction through the technique of Computational Fluid Dynamics (CFD). For this purpose two configurations of regenerator were used with dimensions and boundary conditions taken from the literature. For mathematical and numerical modeling, the commercial software ANSYS-CFX V11 and FLUENT V12 were used, with subroutines developed during the research. Homogeneous and heterogeneous reaction systems were compared using the laminar Finite-Rate kinetic model, in which the reaction rates are determined by Arrhenius kinetic expressions. The simulation of this system produced satisfactory results that will be useful in understanding the complex process of catalyst regeneration for FCC processes / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química
99

The modification of Waxy Oil for preparing a potential feedstock for needle coke production

Clark, John Graham 01 February 2012 (has links)
This research study determines the potential to increase substantially the anisotropy of a coke from an aliphatic Waxy Oil produced by Sasol Synfuels at Secunda, South Africa. Experimental modifications included filtration, distillation and thermal treatment, followed by distillation with the aim of producing a carbonised product similar to needle coke. The substantial concentration of an iron oxide catalyst (up to 2%) in Waxy Oil is increased by an order of magnitude upon carbonisation and calcination due to low coke yield and reactivity factors. The catalyst also promotes oxidative polymerisation of the residue, acts as a barrier to mesophase formation and promotes multi-phase graphitisation. Filtration of Waxy Oil using a 0.5 ìm sintered metal filter reduces the ash content to 0.006% and increases the anisotropy of the carbonised product to 54% flow domains compared with 22% for the carbonised product of virgin Waxy Oil. Thermal treatment followed by distillation of Waxy Oil reduces the effect of organic reactivity promoters (mainly multi-alkylated aliphatics/aromatics and oxygenates), while increasing the concentration of thermally stable (C18 to C30) normal alkanes to 85% compared with 38% in the filtered Waxy Oil. Compared with the filtered Waxy Oil, thermally stabilised Waxy Oil reduces the amount of the pre-carbonisation residue (from 98.7 to 43.0%), while “static” carbonisation thereof increases the green coke yield (from 19.8 to 36.3%) and increases the anisotropicity (from 54 to 100% flow domains). The carbonisation mechanism of filtered and thermally treated Waxy Oil involves initial cracking of high molecular weight normal alkanes (C18 to C30), thus concentrating the molecular weight of normal alkanes (C18 to C22). This is followed by a slow cyclisation step involving both self condensation and cyclo addition reactions to form two- to six-ring cyclo-alkanes or hydro-aromatics. The hydro-aromatics are dehydrogenated rapidly to form methyl and di-methyl three- to six-ring substituted aromatics. Further thermal degradation dealkylates these molecules to form stable four- to six-ring “pre-mesogens”. The mesospheres are nucleated from the isotropic matrix and grow to more than 0.050 mm in diameter, with a volume of 2.61 x 10-3 mm3. Subsequent coalescence of the mesospheres produces mesospheres with diameters of over 0.200 mm and volumes of 41.82 x 10-3 mm3. The resultant microstructure of the solid carbon is composed of flow domains more than 400 ìm in length. Although needle cokes have historically been produced from aromatic residues, this research is the first to show that a coke with a similar microstructure can be produced from a totally aliphatic residue. The research thus provides potential for the development of a needle coke from a totally unique Waxy Oil residue with negligible sulphur (< 0.008%) and nitrogen (< 0.09%) contents. This is the first academic study of the chemistry of Waxy Oil. / Thesis (PhD)--University of Pretoria, 2011. / Chemical Engineering / unrestricted
100

In the Shadow of Steel: Leetonia, Ohio and Independent Iron Manufacturers in the Mahoning and Shenango Valleys, 1845-1920

Di Rocco, Samuel, II January 2012 (has links)
No description available.

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