Orientadores: Rubens Maciel Filho, André Luiz Jardini Munhoz, Betânia Hoss Lunelli / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-26T10:23:37Z (GMT). No. of bitstreams: 1 Peres_AnaPaulaGimenez_D.pdf: 3966242 bytes, checksum: a5d9efcc4a345b82183bab53e34a3ebd (MD5) Previous issue date: 2014 / Resumo: Dentre as rotas alternativas e novas fontes sustentáveis de energia, a biomassa vem se tornando uma opção com potencial para atender a crescente demanda por energia e combustíveis. Como exemplo de fonte renovável, podemos citar o biodiesel, uma das fontes de energia limpa e alternativa mais promissora, cuja produção mundial vem crescendo anualmente. Neste contexto, a geração de hidrogênio e gás de síntese a partir da glicerina bruta tem sido considerada. O principal objetivo desta Tese foi projetar, fabricar e testar um microrreator para produção de hidrogênio a partir da pirólise da glicerina utilizando Laser de CO2 como fonte de energia. Para o cumprimento deste objetivo, quatro etapas principais foram desenvolvidas. A primeira delas foi a realização de estudos fluidodinâmicos do microrreator para a escolha da geometria mais favorável à distribuição do fluxo entre os microcanais. Nesta etapa foi possível quantificar o fluxo do gás nos microcanais e escolher a geometria de acordo com o menor valor no desvio padrão relativo apresentado pela geometria do microrreator. Contudo, neste trabalho, o modelo de microrreator com microcanais internos apresentado não será aplicado, pois de acordo com o objetivo principal da Tese - produção de hidrogênio e gás de síntese a partir da pirólise da glicerina aplicando o laser de CO2 - a radiação do laser deverá atingir diretamente a superfície da amostra (glicerina). Na segunda etapa, através da tecnologia de prototipagem rápida/impressão 3D foi fabricado o protótipo do microrreator e a partir desse protótipo foi fabricado o microrreator a partir do método convencional de usinagem. Na terceira etapa, os parâmetros do laser de CO2, tais como potência, velocidade de varredura e tempo de incidência foram avaliados, através de simulações computacionais. A partir da variável de resposta - geração de calor na amostra - foi possível identificar que a potência do laser de CO2 é a variável com maior influência na geração de calor. Na etapa final, experimentos de pirólise da glicerina foram realizados no microrreator com laser de CO2. Os resultados mostraram significantes conversões para a produção de hidrogênio e gás de síntese. A potência do laser de CO2 foi a variável operacional mais importante. Uma conversão na faixa de 54 a 66 % foi obtida quando uma potência de 60 W foi aplicada / Abstract : Motivated to solve the problems caused by the use of non-renewable fuels, scientists around the world seek ways to develop renewable energy that can reduce these impacts in Earth's atmosphere. Among the alternative routes and new sustainable energy sources, biomass is becoming a potential with option to meet the growing demand for energy and fuel. As a renewable source of one example, biodiesel, one of the sources of clean energy and more promising alternative, whose world production is increasing annually. In this context, the generation of hydrogen and syngas from crude glycerol has been considered. Therefore, the objective of this thesis was to design, fabricate and test a microreactor for hydrogen production from glycerol pyrolysis using CO2 laser as a source of energy. To achieve this objective, four main steps were developed. Firstly, studies of the fluid dynamic behavior of microreactor was conducted for choosing the most favorable geometry to flow distribution among microchannels. At this point it was possible to quantify the internal gas flow in the microchannels and to select the geometry with the lowest value in the relative standard deviation. However, in this thesis, the model of microreactor with internal microchannels presented will not be applied, because according to the main objective of the thesis - the production of hydrogen and synthesis gas from pyrolysis of the glycerol applying the CO2 laser - laser radiation should directly reach the surface of the sample (glycerol). In the second step, by rapid prototyping technology/3D printing was made the microreactor of the prototype and from the prototype that was manufactured the microreactor from conventional machining method. In the third step, the CO2 laser parameters such as power, sweep rate and incidence of time were evaluated through computer simulations. From the response variable - heat generation in the sample - we found that the power of the CO2 laser is the variable with the greatest influence on the generation of heat. In the final step, glycerol pyrolysis experiments were performed in the microreactor with CO2 laser. The results showed significant conversions for the production of hydrogen and synthesis gas. The power of the CO2 laser is the most important operational variable. A conversion in the range 54-66% was obtained when an output of 60 W was applied / Doutorado / Engenharia Química / Doutora em Engenharia Quimica

Orientadores: Maria Regina Wolf Maciel, Rubens Maciel Filho / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-28T02:11:55Z (GMT). No. of bitstreams: 1 Miranda_JulioCesardeCarvalho_D.pdf: 11420052 bytes, checksum: 1d66d50744b41020ecf572a3b96b2561 (MD5) Previous issue date: 2015 / Resumo: O gás de síntese (syngas) é conhecido principalmente pelo seu uso na produção de amônia (Processo Harber-Bosch) e hidrocarbonetos (Processo Fischer-Tropsch). No entano, uma rota menos explorada para a produção de produtos químicos, entre eles alcoóis e outros oxigenados, a partir do gás de síntese, vem ganhando atenção nos últimos anos. Nessa rota, a matéria-prima inicial, como a biomassa é inicialmente gaseificada ao syngas, o qual é reformado, limpo, comprimido e finalmente convertido cataliticamente em uma mistura de alcoóis e produtos oxigenados que, após os passos de separação, atingem a pureza necessária para sua comercialização. Nesse trabalho, a rota termoquímica, como é conhecida, é utilizada com o objetivo de se produzir etanol a partir do syngas. Utilizando o simulador comercial ASPEN Plus v7.3, foram propostos 9 casos de estudo utilizando 3 categorias diferentes de catalisador em 4 diferentes layouts de processo. Todos os casos de estudo foram avaliados quanto à sua produtividade, ao seu consumo de energia e aspectos de importância econômica. Foi possível concluir a partir das análises feitas que cada uma das categorias de catalisador possui vantagens e desvantagens dependendo do contexto econômico, podendo-se citar a diferenciada produção de hidrocarbonetos e outros oxigenados além do etanol, a geração de água, o número de unidades de separação e o consumo de energia / Abstract: Synthesis gas (syngas) is mostly known by its use on ammonia (Harber-Bosch process) and hydrocarbons (Fischer-Tropsch process) production processes. However, a less explored route to produce chemical products, among them alcohols and other oxygenates, from syngas is gaining attention over the last few years. In this route, an initial feedstock as biomass is firstly gasified to synthesis gas, which is reformed, cleaned, compressed and finally catalytically converted in a mixture of alcohols and oxygenated products that after separation steps attain sufficient purity to be sold. In this work, the thermochemical route, as it is known, is used aiming ethanol production from syngas. Using the commercial simulator ASPEN Plus v7.3, 9 case studies were proposed using 3 different categories of catalysts in 4 different process layouts. All the cases were evaluated regarding their productivity, their energy consumption, and aspects of economic importance. It was possible to conclude from the analysis that each of the catalyst categories has advantages and disadvantages depending on the economic context, among them the different proportion of hydrocarbons and other oxygenated products besides ethanol, water generation, number of separation unities and energy consumption / Doutorado / Engenharia Química / Doutor em Engenharia Química

En este trabajo de tesis doctoral, se realiza un estudio comparativo teórico y experimental entre dos tipos de tecnologías de gasificación de biomasa, determinando su viabilidad técnica, económica y ambiental para la producción de energía eléctrica en aplicaciones de baja potencia (inferiores a 100 kW). Los tipos de tecnologías seleccionadas están entre los de mayor interés en el campo de la gasificación de biomasa: lecho fijo downdraft y lecho fluido burbujeante. La mayoría de los resultados presentados en este trabajo, comparando las dos tecnologías, fueron obtenidos de manera experimental. Aunque más costosos, los experimentos proporcionan datos de diseño más fiables que los que se pueden obtener a través de la modelización o simulación, esto sin tener en cuenta que las reacciones que se llevan a cabo en el reactor son complejas y difíciles de modelar, sobretodo en la fase de conversión de sólido a gas, además, la mayoría de los modelos se enfocan en la producción y composición del gas sin tener en cuenta tanto la generación de alquitranes y residuos sólidos como su separación del gas, tan esenciales como el propio proceso de generación del gas. Todos estos hechos han obligado a centrar el estudio comparativo en la verificación experimental del comportamiento de ambos tipos de gasificadores, para lo cual se diseñó, construyó y puso en operación un prototipo con una potencia eléctrica del orden de 10 kW para cada una de las dos configuraciones a estudiar. También se aborda en el presente trabajo el problema de limpieza del gas y la separación de los residuos, especialmente alquitranes, generados en el proceso de gasificación. Para cada uno de los dos tipos de tecnologías estudiadas se ha definido y probado un tipo de sistema de limpieza de gases diferente, utilizando en ambos casos lavadores húmedos de gases y filtrado por medio de astillas, aunque con modos de operación diferentes. El estudio experimental permitió determinar la configuración óptima con la cual se obtiene un gas adecuado para ser quemado en un motor de combustión interna, éste es uno de los problemas más importantes a considerar en una planta de gasificación, debido al coste y el consumo de energía adicional que conllevan estos sistemas. En el aspecto de viabilidad económica se determinó, a partir de los gastos de construcción de los prototipos, que las plantas de generación de energía mediante la gasificación de biomasa con potencias inferiores a 50 kW no son económicamente rentables en España, salvo en condiciones muy restrictivas de bajo coste de la biomasa (inferior a 0,03 ¿/kg) y/o elevada subvención que permitiese un precio de venta superior a 0,2 ¿/kWh. Descartando la conexión a red de una planta de gasificación de baja potencia, se consideró su utilización en zonas no interconectadas, comparando los costes de generación de energía en dicha planta con los de las plantas que operan con gas natural o gasoil, se ha determinado que es más rentable la planta de gasificación, por lo tanto sería una alternativa para la generación de energía eléctrica en zonas rurales donde es costoso llevarla utilizando los métodos convencionales. / Vargas Salgado, CA. (2012). Estudio comparativo de la utilización de las tecnologías de gasificación Downdraft y lecho fluidizado burbujeante para la generación de energía eléctrica en aplicaciones de baja potencia [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/16379 / Palancia

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The following chapters deal with the chemistry, catalytic poisoning, newer catalyst technologies, and possible future solutions to increase the efficiency of creating high-value products by thermochemically converting gasified biomass (producer gas). Chapter 1 puts emphasis on multifunctional catalysts containing transition metals that are used for renewable fuel production. High-value products such as gasoline-range hydrocarbons, dimethyl ether (DME), aldehydes, isobutane, isobutene and other olefins can be produced with gasified biomass due to the gas containing syngas (H2 + CO). The chemistry and production of these chemicals is discussed in the review. Chapter 2 describes the reactor design of a bench scale system and results after using a Mo/HZSM- 5 catalyst for aromatic hydrocarbon creation. This chapter also discusses issues that came with trying to control the temperature without any reactor intercooling. Chapter 3 shows the feasibility of using a particular multifunctional catalyst with a lab scale system and also shows the importance of certain process variables including temperature, space velocity, gas ratios, and pressure. The subject of the importance of the cleanliness of the producer gas is also discussed so that maximum high-value product yield can be achieved with the greatest efficiency. Chapter 4 discusses the implementation of a bench scale and pilot scale reactor design (both with intercooling) and the results of scale-up when using the catalyst mentioned in Chapter 3. Chapter 5 involves the modelling of an industrialized system with Aspen Plus. The economics of industrial plants to produce hydrocarbons from coal or wood feedstocks at scales of 5, 50 and 5000 tons per day were modeled using CAPCOST.

Dry reforming of methane is an important reaction to generate syngas from two greenhouse gases. The syngas can be used in Fishcher-Tropsch synthesis to produce valueded chemicals. Chapter I reviews the catalytic conversion of methane and carbon dioxide to syngas, including DRM reaction chemistry, catalysts used in this process, catalyst deactivation, and the kinetics of DRM reaction. Chapter II discusses the development of bimodal pore NiCeMgAl catalysts for DRM reaction. Bimodal pore NiCeMgAl catalysts were synthesized via the refluxed co-precipitation method and systematically investigated the influence of active metal loading, calcination temperature, reduction temperature and gas hourly space velocity (GHSV) on the catalytic performance of DRM reaction. The Ni15CeMgAl sample with 15 wt% NiO loading was found to be active enough at 750 °C with a high CH4 conversion of 96.5%. The proper reduction temperature for the NiCeMgAl catalyst is either 550–650 °C or 850 °C. Higher calcination temperature favors the formation of NiAl2O4 and MgAl2O4 spinel structures. Compared with non-bimodal pore NiCeMgAl catalyst, bimodal pore NiCeMgAl catalyst has a longer stability in the feed gas without dilution. In chapter III, the kinetic behavior of bimodal pore NiCeMgAl catalyst for DRM reaction was investigated after the elimination of external and internal diffusion effects in a fixed-bed reactor as a function of temperature and partial pressures of reactants and products. A Langmuir-Hinshelwood model was developed assuming that the carbon deposition is ignorable but the RWGS reaction is non-ignorable and the removal of adsorbed carbon intermediate is the rate-determining step. A nonlinear least-square method was applied to solve the kinetic parameters. The derived kinetic expression fits the experimental data very well with a R2 above 0.97, and predicts the products flow rate satisfactorily. Chapter IV documents the results of in situ XRD study on the NiMgAl catalyst for DRM reaction. The phase evolution of a NiMgAl oxide catalyst at the reduction stage was qualitatively analysed and quantitatively determined by employing the continuous changes in XRD intensity and TPR information. The stable crystallite size of both active metal and spinel support is responsible for the long stability of NiMgAl catalyst without carbon deposition during the DRM reaction.

Since bio-gasification is a potentially more efficient way to utilize bio-energy, the economic feasibility becomes one of the greatest issues when we apply this new technology. Evaluation of economic feasibility of a bio-gasification facility needs understanding of its production unit cost under different capacities and different working shift modes. The objectives of this study were to evaluate the unit cost of bio-syngas and biouel products at different capacities by using economic modeling method. Result showed that economic feasibility of a power facility was significantly affected by its production capacity and operating mode (one shift, two shifts, or three shifts mode). Economic feasibility could be improved by increasing production capacity or by changing operating mode to two or three shifts from one shift. The economic evaluation model and cost analysis software developed in this study could be a good tool for economic analysis of bio-syngasand biouel products from biomass gasification.

Recently, work in ethanol production is exploring the fermentation of syngas (primarily CO, CO2, and H2) following gasification of cellulosic biomass. The syngas fermentation by clostridium microbes utilizes the Wood-Ljungdahl metabolic pathway. Along this pathway, the intermediate Acetyl-CoA typically diverges to produce ethanol, acetic acid, and/or cell mass. To develop strategies for process optimization, a thermodynamic analysis was conducted that provided a detailed understanding of the favorability of the reactions along the metabolic pathway. Thermodynamic analysis provided identification of potentially limiting steps. Once these limiting reactions were identified, further thermodynamic analysis provided additional insights into the ways in which reaction conditions could be adjusted to improve product yield as well as minimize the effect of such bottlenecks. In this way, strategies to enhance product formation were effectively formed. A thermodynamic analysis regarding electron utilization suggested that it would be unlikely that H2 is utilized in favor of CO for electron production when both species are present. Therefore, CO conversion efficiency to products will be sacrificed during syngas fermentation since some of the CO will make electrons at the expense of product and cell mass formation. Furthermore, the analysis showed the thermodynamic difference of ethanol production, acetate production, and acetate to ethanol conversion, at varying reaction conditions, such as at different pH and redox potential levels. These differences were then incorporated into a strategy to optimize production of desired product, improve bioreactor design, and decrease the amount of by-product formed. Based on the thermodynamics analysis, experiments with varying experimental conditions were performed. The results showed that sulfide concentration in the media changed. In order to assess the effects of experimental conditions on syngas fermentation and decrease the experimental variability, experiments with controlled sulfide, redox potential, and pH were designed and the results indicated that these factors play key roles on cell growth, product formation and product distribution. Furthermore, experimental conditions had different effects on fermentation during different phases. For example, cell growth is much better at pH=5.8 than pH=4.5. However, the ethanol production rate at pH=4.5 is better than pH=5.8. A strategy involving controlling the pH and redox potential at different phases was effectively applied to improve ethanol production. This work provided significant insights on how varying experimental conditions can affect the syngas fermentation process.