Slags are crystalline to vitreous by-product materials generated in many high temperature industrial processes. This study presents a general technique for the identification of the phases present in petroleum coke gasification slags. documents the phase assemblages and textures, and finally determines the dissolution of vanadium from these slags as part of the considerations of potential resource reclamation. The general identification procedure utilizes (1) recognition of separate phases using optical microscopy and scanning electron microscopy; (2) electron probe microanalysis (EPM) of chemical compositions of individual phases; (3) statistical analysis of the EPM data to eliminate spurious data; (4) estimation of valence states of transition metals using thermodynamic and computational methods; (5) derivation of chemical formulae for the phases using computational methods and chemistry of ionic substitutions; (6) verification of phase identity using X-ray diffraction analysis. More than twenty phases were determined in petroleum coke slags including oxides, silicates. vanadates, sulfate. sulfides and alloys. The reduced slags are rich in V₂>0₃ with silicates and minor amounts of sulfides and native metals whereas the oxidized slags are composed of V₂>0₄, nickel aluminum spinels. various vanadates and glass. Textural analysis provided information on the crystallization process, reaction with gasifier refractory lining materials, sulfide exsolution processes, glass devitrification. and the development of chemical zonation in some spinels. This information offers some perspectives on the potential of resource reclamation. Resource reclamation for petroleum coke slags is best assessed with a knowledge of phases, phase assemblages, textures and dissolution behavior of the material. The dissolution of vanadium. the most significant element. was examined using long term dissolution experiments. These demonstrate that vanadium concentrations are pH dependent ranging from 1500 ppm to 5000 ppm with a minimum concentration near pH 6. Vanadium dissolution rates range from L28xlO⁴ mol m² sec⁻¹ to 3.08xlO^-6 mol m² sec⁻¹. In view of the strategic nature of vanadium and the fact that the concentration of vanadium in slags is almost two orders of magnitude higher than the current mining grades, petroleum coke slags offer significant potential to serve as resources for vanadium. / Ph. D.

This thesis investigates the use of the Stagnation-Point Reverse-Flow (SPRF) combustor geometry for burning low-grade solid fuels that are attractive for specific industrial applications because of their low cost and on-site availability. These fuels are in general, hard to burn, either because of high moisture and impurity-content, e.g. biomass, or their low-volatiles content, e.g., petroleum-coke. This results in various challenges to the combustor designer, for example reduced flame stability and poor combustion efficiency. Conventional solutions include preheating the incoming flow as well as co-firing with high-grade fuels. The SPRF combustor geometry has been chosen because it was demonstrated to operate stably on standard gaseous and liquid-fuels corresponding to ultra fuel-lean conditions and power densities at atmospheric-pressure around 20-25 MW/m3. Previous studies on the SPRF combustor have proven that the unique, reverse flow-geometry allows entrainment of near-adiabatic products into the incoming reactants, thereby enhancing the reactivity of the mixture. Further, the presence of the stagnation-end created a region of low mean velocities and high levels of unsteadiness and mixing-rates that supported the reaction-zones. In this study, we examine the performance of the SPRF geometry on a specific low grade solid fuel, petroleum coke. There are three main goals of this thesis. The first goal is the design of a SPRF combustor to operate on solid-fuels based on a design-scaling methodology, as well as demonstration of successful operation corresponding to a baseline condition. The second goal involves understanding the mode of operation of the SPRF combustor on solid-fuels based on visualization studies. The third goal of this thesis is developing and using reduced-order models to better understand and predict the ignition and quasi-steady burning behavior of dispersed-phase particles in the SPRF combustor. The SPRF combustor has been demonstrated to operate stably on pure-oxygen and a slurry made from water and petroleum-coke, both at the baseline conditions (125 kW, 18 g/s, ~25 µm particles) and higher power-densities and powder sizes. For an overall combustor length less than a meter, combustion is not complete (global combustion efficiency less than 70%). Luminance imaging results indicate the incoming reactant jet ignites and exhibits intense burning at the mid-combustor region, around 15 jet diameters downstream of the inlet, most likely due to enhanced mixing as a result of the highly unsteady velocity field. This roughly corresponds to the location of the reaction zones in the previous SPRF combustors operating on gas and liquid fuels. Planar laser visualization of the reacting flow-field using particle-scattering reveals that ignition of a significant amount of the reactants occurs only after the incoming jet has broken into reactant packets. Post-ignition, these burning packets burn out slowly as they reverse direction and exit the combustor on either side of the central injector. This is unlike the behavior in liquid and gas-fueled operation where the incoming reactants burned across a highly corrugated, thin-flame front. Based on these findings, as well as the results of previous SPRF studies, an idealized model of combustor operation based on a plug flow reactor has been developed. The predictions suggest that fuel-conversion efficiency is enhanced by the combustor operating pressure and lowered by the heat-losses. Overall, this effort has shown the SPRF geometry is a promising compact-combustor concept for self-sustained operation on low-grade solid-fuels for typical high-pressure applications such as direct steam-generation. Based on these findings, it is recommended that future designs for the specific application previously mentioned have a shorter base-combustor with lower heat-losses and a longer steam-generation section for injection of water.

No description available.

Petroleum coke-derived activated carbons were prepared and used for the adsorptive removal of a single-ring naphthenic acid (NA) from synthetic oil sands tailings pond water (TPW). The overall adsorption process was found to be intra-particle diffusion-controlled. The Weber-Morris intra-particle diffusion rate constants decreased from 7.43 to 1.23 mg/g min0.5 after activated carbon was post-oxidized with oxygen, suggesting a hindering effect of oxygen surface groups. The Freundlich model fit of the equilibrium adsorption isotherms and the small negative ΔHo pointed to a physisorption-dominated process and the importance of specific surface area. It was estimated that about 2.7 g/L of basic CO2-activated carbon is needed to reduce NA concentration from 120 mg/L to 2.5 mg/L (~98% removal) in synthetic TPW. However, equilibrium adsorption capacity was found to vary significantly after oxygen or nitrogen groups were introduced onto the surface. Therefore, there is a potential for enhanced adsorption by chemical functionalization of carbon.

Petroleum coke-derived activated carbons were prepared and used for the adsorptive removal of a single-ring naphthenic acid (NA) from synthetic oil sands tailings pond water (TPW). The overall adsorption process was found to be intra-particle diffusion-controlled. The Weber-Morris intra-particle diffusion rate constants decreased from 7.43 to 1.23 mg/g min0.5 after activated carbon was post-oxidized with oxygen, suggesting a hindering effect of oxygen surface groups. The Freundlich model fit of the equilibrium adsorption isotherms and the small negative ΔHo pointed to a physisorption-dominated process and the importance of specific surface area. It was estimated that about 2.7 g/L of basic CO2-activated carbon is needed to reduce NA concentration from 120 mg/L to 2.5 mg/L (~98% removal) in synthetic TPW. However, equilibrium adsorption capacity was found to vary significantly after oxygen or nitrogen groups were introduced onto the surface. Therefore, there is a potential for enhanced adsorption by chemical functionalization of carbon.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2017-04-12T16:58:50Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação_Ulysses.pdf: 2292611 bytes, checksum: 94f0d93357c24023b30a73414786b32e (MD5) / Made available in DSpace on 2017-04-12T16:58:50Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação_Ulysses.pdf: 2292611 bytes, checksum: 94f0d93357c24023b30a73414786b32e (MD5) Previous issue date: 2016-01-29 / CAPES / O processo de obtenção do gesso beta, que consiste na desidratação do minério da gipsita a uma temperatura entre 125 °C e 160°C, é realizado em fornos rotativos através de queima direta ou indireta. Os principais combustíveis utilizados neste processo no Polo Gesseiro do Araripe são a lenha, o coque de petróleo, o óleo BPF e gás natural. Esta dissertação estuda a modelagem matemática de um sistema de calcinação com aquecimento indireto utilizando dois combustíveis sólidos diferentes: a lenha e o coque de petróleo. A modelagem é feita por meio do Método dos Volumes Finitos em um modelo bidimensional de coordenadas cilíndricas. Através da simulação numérica é possível prever o perfil de temperatura em uma seção transversal do forno, tal como suas taxas de aquecimento. São observadas as influências de parâmetros como vazão mássica do combustível, percentual de excesso de ar na combustão e teor de umidade da lenha. Também é realizada uma comparação entre os processos utilizando a lenha e o coque com relação ao custo e à emissão de dióxido de enxofre (SO2). / The process of obtaining the beta plaster, which consists of dehydration of the gypsum ore under a temperature between 100°C and 160 °C, is performed in rotary kilns through direct or indirect burn. The main fuels utilized in this process at Araripe Gypsum District are firewood, petroleum coke, heavy fuel oil and natural gas. This dissertation studies the mathematical modeling of a calcination system with indirect heating using two different solid fuels: firewood and petroleum coke. The modeling is made by using the Finite Volume Method in a two-dimensional model of cylindrical coordinates. Through the simulation is possible to predict the temperature behavior in a cross section of the kiln, as well as its heating rates. It was analyzed the influence of parameter such as mass flow rate, percent excess combustion air and moisture content of the firewood. A comparison between the processes using firewood and coke is also conducted, concerning the cost and the sulfur dioxide (SO2) emission.

This work produced the retrofit of an air-fired, 150 kW reactor for oxy-combustion which was then used in three oxy-combustion studies: strategic oxy-combustion design, oxy-combustion of petroleum coke, and air versus oxy-combustion radiative heat flux measurements. The oxy-combustion retrofit was accomplished using a system of mass flow controllers and automated pressure switches which allowed safe and convenient operation. The system was used successfully in the three studies reported here and was also used in an unrelated study. A study was completed where a novel high oxygen participation burner was investigated for performance while burning coal related to flame stability, NO, and burnout using a burner supplied by Air Liquide. Parameters investigated included oxygen (O2) injection location, burner swirl number and secondary carbon dioxide (CO2) flow rate. The data showed swirl can be used to stabilize the flame while reducing NO and improving burnout. Center O2 injection helped to stabilize the flame but increased NO formation and decreased burnout by reducing particle residence time. Additional CO2 flow lifted the flame and increased NO but was beneficial for burnout. High O2 concentrations up to 100% in the secondary were accomplished without damage to the burner. Petroleum coke was successfully burned using the Air Liquide burner. Swirl of the secondary air and O2 injection into the center tube of the burner were needed to stabilize the flame. Trends in the data similar to those reported for the coal study are apparent. Axial total radiant intensity profiles were obtained for air combustion and three oxy-combustion operating conditions that used hot recycled flue gas in the secondary stream. The oxygen concentration of the oxidizer stream was increased from 25 to 35% O2 by decreasing the flow rate of recycled flue gas. The decrease in secondary flow rate decreased the secondary velocity, overall swirl, and mixing which elongated the flame. Changing from air to neat CO2 as the coal carrier gas also decreased premixing which elongated the flame. Flame elongation caused increased total heat transfer from the flame. The air flame was short and had a higher intensity near the burner, while high O2 concentration conditions produced lower intensities near the burner but higher intensities and temperatures farther downstream. It was shown that oxycombustion can change flame shape, temperature and soot concentration all influencing heat transfer. Differences in gas emission appear negligible in comparison to changes in particle emission.

The price and accessibility of fossil fuels, especially crude oil, are subject to considerable fluctuations due to growing demand on energy, limited resources, and energy security concerns. In addition, climate change caused by burning of fossil fuels is a challenge that energy sector is currently facing. These challenges incentivize development of alternative processes with no greenhouse gas emissions that can meet transportation fuels, chemical liquids, and electricity demands. Coal-based processes are of particular interest because coal price is both low and stable. However, these processes have a large environmental impact and are also less economically attractive than natural gas based plants due to the recent significant drop in natural gas price. However, even for natural gas plants, attempts to reduce CO2 emissions by using traditional CO2 capture and sequestration technologies not only decrease the thermal efficiency and profitability of the plant significantly but still release some CO2 to the atmosphere. The aim of this thesis is to develop, simulate and optimize an integrated polygeneration plant that uses multiple feedstocks and produces multiple products with low to zero CO2 emissions. Several process alternatives are investigated in this work to show the effect of each feedstock and product on the performance of the proposed plant. A comprehensive study is performed in each section, including process simulation in Aspen Plus software, development of custom models required for some units, as well as cost analysis by using Aspen Icarus software and empirical cost estimations from literature. Moreover, derivative free optimization techniques such as particle swarm optimization (PSO), genetic algorithm (GA) and simulated annealing (SA) are implemented to drive the design to economically optimum conditions as a function of the market price and carbon taxes. The final model will also introduce emerging technologies that can achieve higher efficiency and lower CO2 emissions compared to commercial systems, such as chemical looping gasification, chemical looping combustion, nuclear heat reforming, etc. By integrating multiple feedstocks and processes, the model can exploit certain synergies which are unavailable to traditional plants, resulting in significant efficiency improvements. In addition to power and liquid fuels, this polygeneration process offers benefits for petrochemical plants. Despite limited worldwide crude oil reserves, the demand for petrochemical products is still growing fast and it is highly important for petrochemical industry to find new resources as feedstock and diversify their supply chain network. By integration of the polygeneration plant in the same facility with novel processes that produce olefins (petrochemical feedstock) not from oil, but from syngas, it is possible to supply the required feed at lower cost than commercial steam cracking plants. / Thesis / Doctor of Philosophy (PhD)

Mémoire (M.Eng.)-- Université du Québec à Chicoutimi, 1993. / Document électronique également accessible en format PDF. CaQCU

Orientador: Antonio Carlos Luz Lisboa / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T17:26:02Z (GMT). No. of bitstreams: 1 Mendez_ManoelOrlandoAlvarez_M.pdf: 2603376 bytes, checksum: 0c8ee135799f28f8bda8e30c0023f76d (MD5) Previous issue date: 2005 / Resumo: Materiais Carbonosos Ativados (MCA), tais como Carvões Ativados (CA) e Peneiras Moleculares de Carbono (PMC), são caracterizados por apresentar elevada área superficial específica e um grande volume de poros em sua matriz carbonosa, sendo sua principal propriedade a de adsorver moléculas tanto na fase líquida quanto na gasosa. O Brasil importa em sua totalidade peneiras moleculares produzidas a partir de precursores carbonosos, empregando-os nas mais diversas áreas de ciência e tecnologia e em vários segmentos industriais. O coque de petróleo é um resíduo com alto teor de carbono fixo e baixo teor de cinzas, e em decorrência de sua estrutura praticamente amorfa, é um material de pouco valor comercial, sendo considerado um resíduo problemático, tanto em termos ambientais quanto comerciais. Desta forma, a utilização de coque de petróleo para a produção de CAs e de PMCs torna-se atrativa para a utilização deste resíduo. O presente trabalho teve como objetivo estudar a síntese de carvões ativados através das ativações física e química de coque de petróleo proveniente da unidade de coqueamento retardado da REPLAN - PETROBRÁS, buscando avaliar as influências dos parâmetros de processo na qualidade dos CAs, tais como: concentração de agente ativante, tempo de ativação, temperatura de ativação e granulometria do coque de petróleo. A ativação física apresentou resultados insatisfatórios devido a baixa reatividade do coque de petróleo com o dióxido de carbono. Contudo, o coque de petróleo apresentou uma maior reatividade com hidróxido de potássio, permitindo desenvolver uma metodologia adequada para a ativação química do coque de petróleo com KOH, de modo a obter carvões ativados de elevada área superficial. Os resultados obtidos indicam a possibilidade de produção de carvões ativados de elevada área superficial, superiores a 2000 m2.g-1 a partir do coque de petróleo / Abstract: Activated Carbon MateriaIs (ACM), such as Activated Carbons (AC) and Carbon Molecular Sieves (CMS), are characterized by a high specific surface area em high pore volume in their carbon matrix, being their principal property to adsorb molecules in liquid and gas phase. Brazil imports all its molecular sieves, using them in several areas of science and technology and industrial segments. Petroleum coke is a high carbon content residue with low ash content, and due to its amorphous structure have low comercial value, being considered an environmental and comercial problem. In this sense, the utilization of petroleum coke to produce AC and CMS becomes an atractive utilization of this residue. The objective of the present work was to study the synthesis of activated carbon by physical and chemical processes using as raw material the petroleum coke originated from the delayed coking unit from REPLAN PETROBRAS, evaluating the infiuence of process parameters, such as activating agent concentration, activation time, activation temperature and average particle size on the AC quality. The results of physical activation of petroleum coke was not satisfactory due to the low reactivity of the petroleum coke with the carbon dioxide. However, the petroleum coke presented higher reactivity with potassium hidroxide, given the possibility to develop an adequate methodology to chemically activate petroleum coke with KOH, in order to obtain activated carbon with high specific surface area. The results indicated the possibility to produce activated carbon materiaIs from petroleum coke with surface area higher than 2000 m2 .g-l / Mestrado / Engenharia de Processos / Mestre em Engenharia Química