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Desenvolvimento de modelo matemático do sistema reacional de uma unidade industrial de reforma catalítica de nafta com leito móvel. / Development of mathematical model of a reaction system of an industrial unit of nafta catalytic reforming with mobile bed.Carolina May Rodrigues 26 March 2014 (has links)
Reforma catalítica de nafta é um dos processos mais importantes para a produção de gasolina de alta octanagem, hidrocarbonetos aromáticos e hidrogênio na indústria de petróleo e petroquímica. Para predizer os rendimentos e as propriedades dos produtos ou mesmo melhorar as condições de processo é recomendado descrever o processo matematicamente em termos de modelos cinéticos. A nafta tem um grande número de compostos com número de carbonos variando de cinco a doze, assim, um modelo considerando todos os componentes e reações, é complexo. Modelos baseados em lumps costumam agrupar os compostos em isômeros de mesma natureza. Neste trabalho, é proposto um modelo cinético de uma unidade comercial de reforma catalítica com regeneração contínua de catalisador (CCR Continuous Catalyst Regeneration) capaz de predizer o perfil de temperatura e a de composição dos produtos ao longo do reator. O modelo é baseado na análise de hidrocarbonetos parafínicos, naftênicos e aromáticos e na temperatura de carga. A cinética envolve 24 reações modeladas como de pseudo-primeira ordem e 19 componentes. Os parâmetros cinéticos foram estimados usando dados de uma unidade da Petrobras, localizada em Cubatão-SP. O modelo proposto descreve a operação de quatro reatores com fluxo radial representando-os como um reator de fluxo pistonado (PFR Plug Flow Reactor), pois nas condições de operação os efeitos de dispersão radial e axial são assumidos desprezíveis. Os resultados mostram que o modelo pode ser usado para prever os rendimentos de benzeno, tolueno, xileno e hidrogênio. Para os demais compostos os resultados demonstram a necessidade de sofisticação da abordagem. O modelo representa de forma adequada a variação da concentração dos compostos e da temperatura ao longo do inventário de catalisador. / Naphtha catalytic reforming is one of the most important processes for producing high octane gasoline, aromatic products and hydrogen in petroleum and petrochemical industries. To predict yield and properties of the products or even improve the process conditions it is recommended to mathematically describe the process in terms of kinetic models. The naphtha feedstock has a large number of compounds with carbon number ranging from five to twelve. Thus, a detailed kinetic model considering all the components and reactions is complex. Lumping models are used to group the compounds in terms of isomers of the same nature. A kinetic and reactor model of a commercial naphtha continuous catalytic reforming process is proposed to predict temperature profile and products composition. The model is based on paraffins, naphthenes and aromatics analysis and reformer inlet temperature. Kinetics involves 24 pseudo-first-order rate reactions with 19 compounds. All parameters were estimated from industrial data of a Petrobras Refinery at Cubatão-SP. The reactor model describes four radial flow reactors represented by a PFR, due to the fact that under typical reformer operating conditions, radial and axial dispersion effects were found to be negligible. Simulation results demonstrate good agreements between model predictions and actual plant data for benzene, toluene, xylenes and hydrogen. For the remaining compounds, the model output suggests the need for approach sophistication. Nevertheless, the model adequately represents
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Molecular characterisation and modelling for refining processesLiu, Luyi January 2015 (has links)
The highly competitive market in the oil refining industry forces refiners look for more detailed information of both feedstocks and products to achieve the optimal economic performance. Due to stricter environmental legislations, the molecular level characterisation has been investigated by various researchers and shows promising advantages in modern refinery design and operation. Although various molecular characterisation methods have been developed, there is an unavoidable trade-off between keeping astronomical molecule details and practicality in industrial applications. In the meantime, many of these methodologies have different characteristics and different focuses according to a particular application purpose. Our aim is hence to tackle the problems of developing manageable and practical technical solutions for molecular characterisation of petroleum fractions for vary refinery processes. A pseudo-component based approach is developed within a modified MTHS (Molecular Type Homologous Series) matrix framework (Peng, 1999) to represent the molecular information of a particular refining stream. This proposed methodology incorporates both molecular type and pseudo-component information by the conjunction of homologous series and boiling points in the matrix framework. To increase the usability of this method, a 3-parameter gamma distribution function is introduced to describe the composition of each structural molecular type. Typical PIONA (paraffin, iso-paraffin, olefin, naphthene, aromatic) analysis, ratios between each homologous types and the percentage of particular carbon type are considered as well as the distillation curve and the density of a stream. More strict product specifications and environmental legislations make strong restriction to the benzene and aromatics content in gasoline products, which motivate refiners to understand, characterise and simulate gasoline catalytic reforming on molecular-level. In this work, kinetic and reactor model of naphtha catalytic reforming is developed based on the proposed MTHS method. The naphtha feedstock composition is represented by the MTHS matrix, and a kinetic network is constructed according to conversions among matrix elements. A process model proposed by Wu (2010) is employed for reforming modelling. The proposed model is then applied to a bench-scale semi-regenerative catalytic reforming unit, which contains 3 fixed-bed reactors, for validation. The influences of essential operating conditions, such as reactor inlet temperature, pressure and weight hourly space velocity (WHSV), on the product distribution and quality are explored. The developed characterisation is also applied in gasoline blending modelling. A molecular-level nonlinear gasoline blending model is developed based on proposed MTHS method with validation. Key properties such as Octane Numbers (ONs) and RVP are blended by molecular matrix elements, and the influence of molecular composition on bulk properties is obvious. A case of recipe optimisation is studied to show the applicability of the proposed method. The implementation of the developed MTHS method for catalytic reforming and gasoline blending demonstrates the compatibility when characterising different petroleum streams, and provides a common platform to simulate and optimise refining operations on the same molecular basis.
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Catalytic Dry Reforming of Methane: Paving the Road to a Carbon Neutral Industrial Scale Blue Hydrogen Production Process Technology via Monolithic Catalyst-Based Reformer Bolstered by a Techno-Economic AssessmentAlkhani, Anas Farkad January 2022 (has links)
Dry Reforming of Methane (DRM) is a relatively new process technology that provides economic and environmental incentives for several industries that rely heavily on Hydrogen (H₂) and syngas (H₂ and Carbon Monoxide (CO)) utilization. The process utilizes Carbon Dioxide (CO₂) and Natural Gas, containing mainly Methane (CH₄), as a feedstock to produce H₂ and CO. Hydrogen intensive applications and syngas processing facilities benefit mostly by generating new revenue streams as well as achieving a reduced overall carbon footprint of their operations, since CH₄ and CO₂ are both powerful greenhouse gases. This process can be considered on a reactive basis to treat flue gases and emitted streams rich in CO₂, and it also can be a proactive approach to eliminating CO₂ emissions before they occur. The focus in this work is on the latter approach, where DRM, deposited on a low-pressure monolith, is being studied as a relatively new process to produce a pure H₂ gas stream (+99.9% purity) while maintaining carbon neutrality and prove its superiority to the dominating technology today; Steam Methane Reforming (SMR) which utilizes steam (H₂O) as a reactant instead of CO₂, and reacts with Natural Gas to produce H₂ and CO, however, they are accompanied by a large generation of CO₂ emissions.
A comprehensive life cycle assessment (LCA) analysis was conducted to compare both technologies, DRM and SMR, and has demonstrated the feasibility of DRM in almost all environmental impact categories with a significant reduction in CO₂ equivalent emissions. This study assessed the performance of SMR and DRM in various indicators, including energy consumption, air emissions, global warming potential, water consumption, wastewater production, solid catalyst utilization and solid waste production. Although DRM requires higher energy in the reformer, its overall energy consumption is lower than SMR since steam generation needed is only roughly one third that of SMR. Harmful components released by DRM in air emissions are lower in all categories which reduces global warming potential to a large extent and in particular, CO₂ is reduced by approximately 61% when compared with SMR. Since SMR relies heavily on steam input and cooling purposes, water consumption and wastewater generation indicators are more adverse compared to DRM. This outcome acts as a strong driver to invest more in this research field and accelerate commercialization of this process technology.
The research focus around DRM has been studied for over 20 years focusing on landfill gas (CO₂:CH₄ with a ratio of 0.8) and only few commercial testing facilities exist as of today due to major catalyst stability drawback, due to excess CH₄ causing coking issues. While most of the research body is considering DRM to process landfill gas, this research work has found out that by moving to a coke-free regime, the catalyst retains excellent initial stability properties. Thermodynamic analysis demonstrated that ratios of CO₂:CH₄ equal to and greater than 1.5, solid carbon no longer thermodynamically forms, and indeed, the experimental studies have confirmed the same conclusion evident by stable catalyst performance. Both Nickle (Ni) and Rhodium (Rh) in powder forms exhibited excellent activity and stability levels under a CO₂:CH₄ ratio of 1.5. This was the first and most important stepping stone in constructing a solid argument supporting DRM as a stable process with great potential for commercialization. This ratio is possible when separate sources of CO₂ and CH₄ are available and thus ratios can be adjusted unlike in landfills where CH₄ is always in excess. The work continued in performing several parametric experiments and screening multiple catalysts with different metal loadings. Three active metals were tested, Ni, Rh, and Ruthenium (Ru), and the results concluded that the most promising formulations are 10% Ni on Alumina (Al2O3) and 1% Rh on Al₂O₃. Those were further investigated in details for artificially aging by intentionally forming coke and successfully regenerated by steam gasification. The catalysts were coked and regenerated to essentially fresh activity.
Commercial SMR is operated with a packed-bed reactor design and utilizing catalysts (most commonly Ni on alpha Al₂O₃.) in the form of pellets and rings, which lead to large pressure drops and ultimately large reactor design and increased energy requirements. To help overcome the design challenges, this research work has considered monolithic catalysts for testing and scale-up purposes. Monoliths, with their high open frontal areas and large geometric surface areas, overcome the challenges of high pressure drop, experienced in pellets, exhibit solid mechanical strength and provide large geometric surface areas of catalysts (washcoat) contact for reactions to take place, and hence, significantly reduce reactor sizes and eventually, overall capital and operating costs. The monolithic catalysts were prepared by washcoating 10% Ni and separately 1% Rh, both on gamma Al₂O₃. on their walls. The same parametric studies conducted for powders were tested for monolithic catalysts, and the results were positively surprising. Monolithic catalysts possessed extremely high activities, far better than all powders tested even at higher loadings. Moreover, their excellent stability results provide a possible road to a more compact reactor design. One conclusion; monolithic catalysts, or washcoated structured reactors as known in industry, are strong competitors that have the potential to deliver superior results when compared to packed-bed reactors. Therefore, this research is proposing the use of monolithic catalysts working under the favorable thermodynamic environment, as a potential solution to accelerate DRM advanced testing for H₂ production.
To further support the thesis argument, a basic process design of the DRM was carried out to understand the various compositions of streams and the material and energy requirements for a feasible commercial plant. The design resembled very closely that of an SMR plant with the major difference in the main reactor, known as the “Reformer”. With this data on hand, a financial modelling was constructed to preliminarily prove the feasibility of this technology when compared to competitors in the market. Consequently, when compared to SMR with and without carbon capture (CC), DRM achieved relatively low H₂ prices in the range of 1.07-1.32 $/kg in the case of a Methanator design case and up to 1.91 $/kg for the CC design case, while SMR exceeded 2.1 $/kg for sustainable H₂ production; indicating that DRM, on preliminary basis, is a very profitable process technology. In conclusion, the laboratory research work combined with process design and financial feasibility, strongly supports the grounds of recommending DRM as a viable H2 production technology for a future pilot plant testing and advancement for commercialization. A more detailed engineering design and financial assessment would provide more accurate results after the successful pilot plant testing.
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Effect of compressibility factor on the hydrodynamics of naphtha catalytic‑reforming reactorsZakari, A.Y., John, Yakubu M., Aderemi, B.O., Patel, Rajnikant, Mujtaba, Iqbal 04 July 2022 (has links)
Yes / A detailed steady-state catalytic-reforming unit (CRU) reactor process model is simulated in this work, and for the first time, different compressibility Z factor correlations have been applied using gPROMS software. The CRU has been modeled and simulated with the assumption that the gas phase behaves like an ideal gas. This is assumed for the four reactors in series and for different conditions of hydrogen–hydrocarbon ratio (HHR), operating temperature, and pressure. The results show that the Z factor varies at every point along the height of the reactors depending on reaction operating pressure, temperature, and HHR ratio. It also shows that the magnitude of deviation from ideal gas behaviour can be measured over the reactor height. The Z factor correlation of Mahmoud (J Energy Resour Technol Trans ASME 136:012903, 2014) is found to be suitable for predicting the Z factor distribution in the reactors.
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Efeito da concentração de irídio sobre as propriedades de catalisadores do tipo Pt-Ge-Ir/Al2O3Barreto, Rubens Santos January 2008 (has links)
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Previous issue date: 2008 / Neste trabalho, foi estudado o efeito do conteúdo de irídio na atividade, seletividade e estabilidade de catalisadores de platina, irídio e germânio suportados em alumina, destinados à reforma catalítica de nafta de petróleo. As amostras foram preparadas por impregnação dos sais metálicos (ácido hexacloroplatínico, ácido hexacloroirídico e cloreto de germânio) na g-alumina, de modo a obter 0,3 % de platina e de germânio e teores vairados de irídio (0,03; 0,06; 0,09 e 0,15 %). Os sólidos obtidos foram caracterizados por redução termoprogramada, espectroscopia no infravermelho com transformada de Fourier de monóxido de carbono adsorvido, dessorção à temperatura programada de piridina, desidrogenação de cicloexano e isomerização de npentano, usadas para avaliar as funções metálica e ácida, respectivamente. O desempenho foi avaliado na reforma de n-octano. Os catalisadores usados nessa reação foram analisados por oxidação termoprogramada. Os resultados mostraram que o irídio catalisa a redução da platina, enquanto o germânio exerce um efeito inibidor; esses efeitos dependem da quantidade de irídio nos sólidos, devido às diferentes interações entre os metais e com o suporte. Ambos os metais modificam eletronicamente a platina, tornando-a mais rica (irídio) ou mais deficiente (germânio) em elétrons. Entretanto, nos catalisadores trimetálicos, o efeito do germânio sobre a platina só se torna significativo em concentrações mais elevadas de irídio (0,15 %), que promove a redução do germânio, gerando sólidos com espécies de platina em diferentes estados eletrônicos. A presença do germânio diminui a concentração de sítios ácidos fracos e aumenta aqueles de acidez moderada e forte, enquanto o irídio provoca alterações na concentração de sítios de diferentes forças ácidas, dependendo do seu teor nos sólidos. A atividade catalítica dos sítios metálicos na desidrogenação do cicloexano diminui devido ao germânio enquanto o irídio (em teores superiores a 0,03 %) causa um aumento, devido à sua atividade dedidrogenante; este efeito aumenta com o teor de irídio nos sólidos. Nos catalisadores trimetálicos a atividade dos sítios metálicos é mais baixa que no sistema monometálico de platina, devido ao efeito simultâneo dos dois metais, que podem estar formando ligas com a platina e/ou encobrindo seus sítios ativos diminuindo sua atividade de desidrogenação. A adição de irídio e de germânio a catalisadores de platina suportada em alumina aumenta a sua atividade na isomerização do n-pentano e diminui a atividade de hidrogenólise. Nos catalisadores trimetálicos, a seletividade a compostos aromáticos é inferior àquela dos sistemas bimetálicos e o orto-xileno é o isômero mais favorecido. O germânio aumenta a estabilidade dos catalisadores enquanto o irídio exerce um efeito inverso. A produção de compostos aromáticos diminui com o aumento do teor de irídio no catalisador, enquanto um comportamento inverso é observado com relação à seletividade a produtos isômeros. A razão entre as seletividades a compostos isômeros e aromáticos cresce com o conteúdo de irídio, de modo que se um reformado mais rico em compostos aromáticos é desejado, deve-se usar um catalisador com baixos teores de irídio. Por outro lado, uma composição com concentração de irídio mais alta produz um reformado mais rico em compostos isômeros e, portanto, mais adequado ao uso como combustível. / Salvador
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Dehydrogenation mechanisms of methyl-cyclohexane on γ-alumina supported platinum subnanometric-clusters : DFT coupled with experimental kinetics and kinetic modelling / Mécanismes de déshydrogénation du méthyl-cyclohexane catalysée par des agrégats sub-nanométriques de platine supportés sur alumine gamma : études couplées DFT, cinétique expérimentale et modélisation cinétiqueZhao, Wei 09 November 2017 (has links)
Le reformage catalytique vise à transformer les naphtas en aromatiques à haut indice d'octane et à produire simultanément du dihydrogène. Le catalyseur utilisé est composé d’agrégats sub-nanométriques à base de platine hautement dispersées sur un support d’alumine-gamma dont le comportement en réaction pose de nombreuses questions. Nous étudions expérimentalement et théoriquement une réaction modèle qui sonde les sites métalliques, la déshydrogénation du methyl-cyclohexane en toluène. Une compréhension détaillée à l'échelle atomique des mécanismes impliqués et des paramètres cinétiques est nécessaire. Nous avons mise en œuvre des calculs DFT (PBE et PBE-dDsC) sur un modèle pertinent Pt13/alumine-gamma, afin de déterminer les intermédiaires, les états de transition et leurs enthalpies libres. Le mécanisme a été exploré via des étapes séquentielles de rupture des liaisons C-H. Une reconstruction des agrégats se produit le long du chemin réactionnel, mettant en évidence sa fluctionalité (confirmée par dynamique moléculaire). Les enthalpies libres d’activation de la rupture C-H, de migration d’hydrogène et de reconstruction de l’agrégat ont été systématiquement déterminées à T=625 K. L'enthalpie libre la plus élevée (ΔrG‡=95 kJ/mol) est trouvée pour la troisième rupture de liaison C-H sur le methyl-cyclohexène. L'intermédiaire le plus stable est le produit adsorbé {toluène+H2}. Cependant, d’autres étapes de rupture C-H ou de désorption du toluène sont compétitives. Les constantes de vitesse des étapes élémentaires obtenues par DFT sont introduites dans 8 modèles cinétiques différents de type Langmuir-Hinshelwood (LH). La nature de l'étape déterminante de la vitesse a été choisie en fonction des constantes de vitesse de chaque étape élémentaire individuelle, ou de la prise en compte de séquences d’étapes limitantes, grâce à une analyse de type « energetic span ». Nous avons finalement expérimentalement réalisé des tests catalytiques sur Pt/γ-alumine (0.3 wt% Pt) à différentes températures, temps de contact, pressions partielles d’hydrogène et de méthylcyclohexane, pour obtenir des données cinétiques expérimentales. L'enthalpie d'activation apparente de 196 kJ/mol calculée par l’un des meilleurs modèles LH (3ème rupture C-H limitante) est proche de l’expérience (195 kJ/mol). De plus, l’évolution des vitesses de réaction en fonction des pressions partielles d'hydrogène et de méthylcyclohexane est discutée au regard de l’expérience et des modèles. Même si les tendances sont recouvrées par les modèles, des écarts théorie-expérience sont mis au jour, ce qui ouvre des perspectives vers une modélisation microcinétique future. / Catalytic reforming aims at transforming naphta into high octane aromatics and producing simultaneously dihydrogen. The catalyst used is composed of platinum-based sub-nanometric clusters highly dispersed on a gamma-alumina support which behavior under reaction conditions is the subject of numerous questions. We investigate experimentally and theoretically one model reaction probing the metal sites, the dehydrogenation of methyl-cyclohexane into toluene. A detailed atomic scale understanding of the mechanisms involved, and their related kinetic parameters, is required. We undertook DFT calculations with PBE and PBE-dDsC functionals on a relevant Pt13/γ-alumina model, in order to determine the intermediates, transition states and their free energies. The reaction mechanism was explored by assuming sequential C-H breaking steps. Reconstructions of the cluster and hydrogen migrations occur along the reaction pathway, highlighting its high fluctionality (also confirmed by molecular dynamics). Free energies of activation for C-H bond breaking, H migration and cluster’s reconstruction were systematically determined at T=625 K. The highest activation Gibbs free energy (ΔrG‡=95 kJ/mol) is found for the third C-H bond breaking on methyl-cyclohexene, while the most stable intermediate is the {toluene+H2} adsorbed product. However, other C-H bond breaking steps and eventually toluene desorption may compete. A comparison with the Pt (111) surface is also given. Rate constants of elementary steps estimated by DFT are introduced in 8 Langmuir-Hinshelwood (LH) kinetic models based on a single rate determining step (RDS) concept, or on a limiting steps sequence deduced from an energetic span analysis. We finally carried out experimental tests on Pt/γ-alumina catalysts (0.3 wt% Pt) at various temperatures, space times, hydrogen and methyl-cyclohexane partial pressures, to provide experimental kinetic data. The calculated apparent activation enthalpy is predicted to be 196 kJ/mol in close agreement with the experimental one (195 kJ/mol) for the best LH model (third C-H bond breaking as RDS). Moreover, the dependence of reaction rates on hydrogen and methyl-cyclohexane partial pressures are discussed with respect to experimental trends and models. Although the main trends are recovered by the kinetic model, some discrepancies are revealed. This work paves the way for a future microkinetic modeling.
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Procédé propre de production de chaleur et d'électricité à partir d'un biogaz produit à l'échelle domestique : exemples de matériaux catalytiques de reformage du méthane / Clean process for production of heat and electricity from biogas produced at domestic scale : examples of catalytic materials for methane reformingBassil, Siréna 10 April 2014 (has links)
Le reformage catalytique du méthane en hydrogène, vecteur d'énergie pour les piles à combustibles de type Solid Oxide Fuel Cell (SOFC), a été étudié sur des matériaux d'anode à base de métaux supportés (NiO/CeO2, NiO-Y2O3-ZrO2) et également sur des catalyseurs de structure définie (La0,8Sr0,2TiO3+δ). La première famille de catalyseurs a été synthétisée par deux méthodes de préparation : la technique d'imprégnation en milieu aqueux et en milieu organique sur des supports du commerce CeO2 et Y2O3-ZrO2 ou préparés au laboratoire, et par le procédé sol-gel. Le titanate de lanthane dopé au strontium a été préparé par la méthode de co-précipitation et également par la méthode sol-gel. La méthode de préparation a un effet important sur les propriétés physico-chimiques des catalyseurs synthétisés et par conséquent affecte à la fois leur activité catalytique en reformage du méthane et leur résistance à l'empoisonnement par le dépôt de carbone. Les catalyseurs à base de nickel supporté sur cérine ont été par la suite dopés avec l'oxyde de magnésium (formation d'une solution solide MgO-NiO) ainsi qu'avec l'oxyde de lanthane (La2O3-NiO) en vue de limiter la formation de carbone sur la surface catalytique et augmenter ainsi la durée de vie des catalyseurs lors du reformage du méthane. Les résultats obtenus montrent que l'effet de promotion de la phase active NiO par MgO ou La2O3 diminue à la fois le dépôt de carbone mais également les performances catalytiques. Les propriétés physico-chimiques et les performances catalytiques de NiO-Y2O3-ZrO2 préparé par le procédé sol-gel ont été comparées à celles de matériaux commerciaux (Aldrich & Jülich) de même composition. Les résultats expérimentaux montrent que les matériaux synthétisés par la méthode sol-gel sont plus actifs en vaporeformage du méthane que ceux du commerce (dans le domaine de fonctionnement d'une pile SOFC) alors qu'ils présentent une activité similaire à ces derniers en reformage à sec du méthane. La quantité de carbone graphitique formée, quoique supérieure à celle observée dans le cas des catalyseurs commerciaux, demeure faible (< 2%). Ce dépôt de carbone ne provoque qu'une légère diminution des performances catalytiques en reformage à sec du méthane. Ceci est probablement lié à la diminution des sites actifs / The catalytic reforming of methane into hydrogen, for direct operation of Solid Oxide Fuel Cells (SOFCs) on methane, was studied on anode materials such as NiO/CeO2, NiO-Y2O3-ZrO2 and La0.8Sr0.2TiO3+δ. The first group of catalysts was synthesized by two methods: the impregnation technique both in aqueous and organic media (commercial and laboratory made CeO2 and Y2O3-ZrO2), and also using sol-gel process. Lanthanumtitanium oxide host structure doped with strontium was prepared both by co-precipitation and sol-gel process. The method of preparation has an important effect on the physico-chemical properties of the synthesized catalysts and affects consequently both their catalytic performances in methane reforming and their resistance to poisoning by carbon deposition. In order to limit carbon formation on the catalytic surface and to increase the lifetime of catalysts during the catalytic reforming of methane, ceria supported nickel based-catalysts were doped with magnesium oxide (forming MgO-NiO solid solution) as well as with lanthanum oxide (La2O3-NiO). The obtained results show that the effect of promotion of NiO active phase by MgO and La2O3 decreases carbon deposition but also the catalytic performances. Physico-chemical properties and catalytic performances of NiO-Y2O3-ZrO2 (Ni-YSZ) prepared by the sol-gel process were compared with those of commercial (Aldrich and Jülich) materials having the same composition. The experimental results showed that materials synthesized by the sol gel method are more active in methane steam reforming than commercial catalysts while sol gel and commercial samples show similar performances in methane dry reforming. Amounts of graphitic carbon, although being higher for sol gel samples compared to commercial ones, remain low (< 2%). This carbon deposit provokes only a slight decrease of catalytic performances of sol gel prepared materials in methane dry reforming, probably by decreasing the number of active sites
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Méthodologie pour tenir compte de l'impact environnemental d'un procédé lors de sa conception / Development of a methodology for process eco designPortha, Jean-François 04 November 2008 (has links)
L'impact environnemental d'un procédé est déterminé par des méthodes d'évaluation comme l'analyse de cycle de vie (ACV). Une méthode complémentaire a été développée afin de caractériser l'impact environnemental d'un procédé lors de la phase de dimensionnement, en lui appliquant un bilan thermodynamique restreint à ses frontières avec une fonction ad hoc. La fonction choisie, l'exergie, est basée sur l'état physico-chimique de l'environnement et quantifie l'irréversibilité d'une transformation. L'existence d'irréversibilités dans un procédé signifie qu'une partie de l'énergie fournie est dégradée augmentant simultanément les émissions polluantes. L'intérêt de l'exergie réside également dans l'allocation des coproduits. L'étude se focalise sur l'impact changement climatique dû aux émissions de gaz à effet de serre (GES). Cette méthode couplant ACV et analyse exergétique a été appliquée à un procédé représentatif du raffinage du pétrole: le reformage catalytique du naphta. Les émissions de GES y sont d'origine directe (régénération du catalyseur) et indirecte (utilités). Le procédé et les réacteurs ont été modélisés respectivement avec le simulateur de procédés ProII et avec un sous-programme codé en langage Fortran interfacé avec le simulateur pour tenir compte des transformations chimiques. La méthodologie, qui ne peut s'affranchir de données ACV, a permis de lier, pour le procédé, les émissions de GES respectivement à un indicateur thermodynamique Ip et à la variation d'exergie chimique. La méthode a été étendue pour comparer deux procédés ayant une même fonction en quantifiant, notamment, la qualité des produits formés et l'appauvrissement des ressources / The environmental impact of a process is assessed by evaluation methods such as life cycle assessment (LCA). A complementary method has been developed in order to characterize the environmental impact at the preliminary design stage by application of a thermodynamic balance on the process boundaries. The chosen thermodynamic function is exergy which takes into account irreversibilities and is linked to the mean environment temperature, pressure and composition. Existence of irreversibility in a process means that a part of the provided energy is wasted increasing simultaneously pollutant emissions. Exergy is also a tool for co-products allocation. The study focuses on climate change that implies greenhouse gas (GHG) emissions. To illustrate the potential of coupling LCA and exergy analysis in the petroleum industry, a naphtha catalytic reforming process has been selected and evaluated in terms of climate change. In this process, GHG emissions have two origins: direct (due to catalyst regeneration) and indirect (due to utilities) emissions. The process and the reactors have been respectively modelled with the process simulator ProII and with a Fortran subroutine to take into account chemical transformations. The method, which cannot avoid LCA data, has underlined, for the process, a positive relationship between GHG emissions and respectively a thermodynamic parameter Ip and the variation of chemical exergy. The method has been extended to compare two processes having the same function and to take into account co-products quality and resource depletion
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Influência dos parâmetros reacionais e da composição dos transportadores de oxigênio, aplicáveis aos processos de combustão e reforma do metano, com recirculação química / Influence of the reaction parameters and composition of oxygen carriers, applicable to the processes of chemical looping combustion and chemical looping reforming of methaneRenato Dias Barbosa 10 December 2014 (has links)
Impulsionados pela busca de fontes limpas de energia, surgem os processos de combustao com recirculacao quimica (CLC), e reforma com recirculacao quimica (CLR). CLC e CLR sao processos quimicos para oxidacao de hidrocarbonetos gasosos. E utilizada a acao de transportadores de oxigenio (TO), para transferir oxigenio do ar para o combustivel (neste caso o metano), evitando-se o contato direto entre ar atmosferico e metano por diversos motivos. Os TOs, compostos por oxidos metalicos na forma de po fino, circulam continuamente entre dois reatores de leito fluidizado (reator de ar e de combustivel), sofrendo sucessivos ciclos de reducao e oxidacao. Os processos se diferenciam com relacao aos produtos, em CLC objetiva-se a geracao de energia, atraves da oxidacao completa do combustivel, resultando em uma mistura de CO2 e H2O, podendo ser facilmente separada por condensacao. No caso do CLR a oxidacao ocorre de maneira parcial, dando origem a uma mistura de gas de sintese (H2 + CO). O CLC apresenta vantagens com relacao aos processos tradicionais de captura de CO2, pois nao se faz necessaria a utilizacao de processos secundarios para separacao gasosa, economizando assim energia, alem do fato de nao gerar gases do tipo NOx. O presente trabalho apresenta a preparacao de duas series de materiais, via impregnacao seca, uma com composicao 2, 4 e 8% m/m de oxido de niquel e outra com os mesmo teores de oxido de niobio, suportados sobre alumina comercial de alta area superficial especifica. Os materiais foram caracterizados pelas tecnicas de picnometria a helio, volumetria de nitrogenio, porosimetria por intrusao de mercurio, DRX, MEV, TPR 5%H2/N2 analisado com TCD em ChemBet, TPR 5%CH4/Ar e TPO 5%O2/Ar sendo a variacao de massa analisada em termobalanca (TGA/DSC), alem de se utilizar de espectrometria de massas para analise dos gases gerados. Os diferentes transportadores de oxigenio foram testados em reator de leito fixo, sendo avaliados em diferentes condicoes experimentais tais como: temperaturas de operacao, vazoes de reagentes gasosos, concentracoes de metano, adicao de CO2 e H2O ao combustivel. Os produtos da reacao no reator de leito fixo foram analisados por cromatografia gasosa e espectrometria de massa. Os resultados mostraram que; o deposito de carbono sobre o catalisador pode ser drasticamente reduzido com a adicao de mistura oxidante junto ao combustivel e que estes oxidos estudados tem potencial aplicacao industrial, mostrando-se seletivos para reforma do metano com consecutiva producao de gas de sintese. / Driven by the demand for clean energy sources, arise chemical-looping combustion - CLC, and chemical-looping reforming - CLR. CLC and CLR are chemical processes for oxidation of gaseous hydrocarbons. Both of them use the action of catalysts, here called oxygen carriers (OC), which transfers oxygen from the air to the fuel (in this case methane), avoiding the direct contact between the two gases for various reasons. The OC\'s are composed of metal oxides in the form of fine power, circle continuously between two fluidized bed reactors (fuel reactor and air reactor), suffering successive cycles of reduction and oxidation. The two processes differ in relation to the products; the aim of CLC is generation of energy (heat), through the complete oxidation of the fuel, resulting in a mixture of CO2 and H2O, which can be easily separated by condensation. In the case of CLR, the oxidation occurs partially, resulting in synthesis gas, a mixture of H2 and CO. The CLC processes shows advantages when compared to other traditional processes for capture of CO2, because it is not necessary to use secondary processes for gas separation, saving energy, besides the fact of no NOx is generated. This work describes the preparation of two series of materials via dry impregnation, which are composed of 2, 4 and 8% w/w niobium oxide or nickel oxide, supported on commercial alumina, with high specific surface area. The materials were characterized by the techniques of helium pycnometry, nitrogen volumetry, mercury intrusion porosimetry, DRX, MEV, TPR 5% H2/N2 analyzed with TCD in ChemBet, TPR 5% CH4/Ar and TPO 5% O2/Ar, being the changes in mass and heat analyzed in a thermogravimetric balance (TGA/DSC) coupled to a mass spectrometer permitting the analysis of the generated gases. The different oxygen carriers were tested in a fixed bed reactor, evaluated in different experimental conditions, such as operation temperature, flow rate of gaseous reactants, methane concentrations, addition of CO2 and H2O to the fuel. The products of the reaction in the fixed bed reactor were analyzed by gas chromatography and mass spectrometry. The results show that: the carbon deposits over the catalysts can be drastically reduced by addition of oxidizing mixture together to the fuel and these studied oxides have a potential industrial application, showing selectivity to reforming of methane with consecutive synthesis gas production.
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Influência dos parâmetros reacionais e da composição dos transportadores de oxigênio, aplicáveis aos processos de combustão e reforma do metano, com recirculação química / Influence of the reaction parameters and composition of oxygen carriers, applicable to the processes of chemical looping combustion and chemical looping reforming of methaneBarbosa, Renato Dias 10 December 2014 (has links)
Impulsionados pela busca de fontes limpas de energia, surgem os processos de combustao com recirculacao quimica (CLC), e reforma com recirculacao quimica (CLR). CLC e CLR sao processos quimicos para oxidacao de hidrocarbonetos gasosos. E utilizada a acao de transportadores de oxigenio (TO), para transferir oxigenio do ar para o combustivel (neste caso o metano), evitando-se o contato direto entre ar atmosferico e metano por diversos motivos. Os TOs, compostos por oxidos metalicos na forma de po fino, circulam continuamente entre dois reatores de leito fluidizado (reator de ar e de combustivel), sofrendo sucessivos ciclos de reducao e oxidacao. Os processos se diferenciam com relacao aos produtos, em CLC objetiva-se a geracao de energia, atraves da oxidacao completa do combustivel, resultando em uma mistura de CO2 e H2O, podendo ser facilmente separada por condensacao. No caso do CLR a oxidacao ocorre de maneira parcial, dando origem a uma mistura de gas de sintese (H2 + CO). O CLC apresenta vantagens com relacao aos processos tradicionais de captura de CO2, pois nao se faz necessaria a utilizacao de processos secundarios para separacao gasosa, economizando assim energia, alem do fato de nao gerar gases do tipo NOx. O presente trabalho apresenta a preparacao de duas series de materiais, via impregnacao seca, uma com composicao 2, 4 e 8% m/m de oxido de niquel e outra com os mesmo teores de oxido de niobio, suportados sobre alumina comercial de alta area superficial especifica. Os materiais foram caracterizados pelas tecnicas de picnometria a helio, volumetria de nitrogenio, porosimetria por intrusao de mercurio, DRX, MEV, TPR 5%H2/N2 analisado com TCD em ChemBet, TPR 5%CH4/Ar e TPO 5%O2/Ar sendo a variacao de massa analisada em termobalanca (TGA/DSC), alem de se utilizar de espectrometria de massas para analise dos gases gerados. Os diferentes transportadores de oxigenio foram testados em reator de leito fixo, sendo avaliados em diferentes condicoes experimentais tais como: temperaturas de operacao, vazoes de reagentes gasosos, concentracoes de metano, adicao de CO2 e H2O ao combustivel. Os produtos da reacao no reator de leito fixo foram analisados por cromatografia gasosa e espectrometria de massa. Os resultados mostraram que; o deposito de carbono sobre o catalisador pode ser drasticamente reduzido com a adicao de mistura oxidante junto ao combustivel e que estes oxidos estudados tem potencial aplicacao industrial, mostrando-se seletivos para reforma do metano com consecutiva producao de gas de sintese. / Driven by the demand for clean energy sources, arise chemical-looping combustion - CLC, and chemical-looping reforming - CLR. CLC and CLR are chemical processes for oxidation of gaseous hydrocarbons. Both of them use the action of catalysts, here called oxygen carriers (OC), which transfers oxygen from the air to the fuel (in this case methane), avoiding the direct contact between the two gases for various reasons. The OC\'s are composed of metal oxides in the form of fine power, circle continuously between two fluidized bed reactors (fuel reactor and air reactor), suffering successive cycles of reduction and oxidation. The two processes differ in relation to the products; the aim of CLC is generation of energy (heat), through the complete oxidation of the fuel, resulting in a mixture of CO2 and H2O, which can be easily separated by condensation. In the case of CLR, the oxidation occurs partially, resulting in synthesis gas, a mixture of H2 and CO. The CLC processes shows advantages when compared to other traditional processes for capture of CO2, because it is not necessary to use secondary processes for gas separation, saving energy, besides the fact of no NOx is generated. This work describes the preparation of two series of materials via dry impregnation, which are composed of 2, 4 and 8% w/w niobium oxide or nickel oxide, supported on commercial alumina, with high specific surface area. The materials were characterized by the techniques of helium pycnometry, nitrogen volumetry, mercury intrusion porosimetry, DRX, MEV, TPR 5% H2/N2 analyzed with TCD in ChemBet, TPR 5% CH4/Ar and TPO 5% O2/Ar, being the changes in mass and heat analyzed in a thermogravimetric balance (TGA/DSC) coupled to a mass spectrometer permitting the analysis of the generated gases. The different oxygen carriers were tested in a fixed bed reactor, evaluated in different experimental conditions, such as operation temperature, flow rate of gaseous reactants, methane concentrations, addition of CO2 and H2O to the fuel. The products of the reaction in the fixed bed reactor were analyzed by gas chromatography and mass spectrometry. The results show that: the carbon deposits over the catalysts can be drastically reduced by addition of oxidizing mixture together to the fuel and these studied oxides have a potential industrial application, showing selectivity to reforming of methane with consecutive synthesis gas production.
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