Optimization of the pyrolysis process for the production of a biomass derived reducing agent and hydrogen-rich gases

221 p.

Advanced Reaction Systems for Hydrogen Production

[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

Valorization of scrap tires pyrolysis oil (STPO) through a 2-stage hydrotreating-hydrocracking strategy. Process variables and kinetic modeling

232 p.

Nanocomposites de Poliuretanos Elastoméricos y Nanotubos de Carbono Multipared

218p. -- Tesis con mención "Doctor europeus" realizada en el periodo de Octubre 2005-Mayo 2010, en el Grupo "Materiales+Tecnologías" (GMT).

Serie Vídeos tutoriales para fonética (volumen 2). Video 3. Lectura en voz alta

Esta es una colección de 6 vídeos tutoriales que pueden ser empleados como material educativo en los cursos de fonética en el ámbito universitario. Tratan principalmente del cómo se puede obtener información desde las palabras aisladas, como se observa en las técnicas de los vídeos 1-2, pasando por datos obtenidos con participación del investigador, característica aún presente en los vídeos 3-4, hasta enunciados íntegros sin necesidad del investigador presente, tal como se ilustra en los vídeos 5-6. Se trata de establecer una reflexión entre la necesidad de identificar el grado de espontaneidad a la hora de brindar información por parte del hablante y la posibilidad (o la necesidad) de cuantificar los datos que se obtienen.

Modelización acústica del interior de un tren de alta velocidad.

[ES]El presente Trabajo de Fin de Grado titulado 'Modelización Acústica del Interior de un Tren de Alta Velocidad' tiene como tarea la realización de diversos análisis acústicos de un habitáculo de un coche ferroviario. El principal objetivo va a ser ofrecer una guía detallada a modo de manual de usuario para llevar a cabo dichos análisis sin necesitar información adicional. Las herramientas de ayuda a utilizar van a ser un programa CAD de diseño como Solid Edge ST6 o Catia V5 y un software de elementos finitos como Ansys.

Faltas de alta impedancia. Comportamiento y características.

[ES]El objetivo del presente trabajo es realizar un estado del arte sobre las faltas de alta impedancia en sistemas de distribución, sus características, causas y consecuencias. El estudio se acompaña con simulaciones software que se llevarán a cabo mediante el software Matlab a través de un modelo que represente su carácter no lineal y aleatorio.

Diseño de una junta esférica flexible para un manipulador de alta precisión.

ES]El Trabajo Fin de Grado que se presenta a continuación tiene como objetivo principal el diseño de una unión flexible que formará parte de las patas de un robot de cinemática paralela. Por la propia arquitectura de estos mecanismos, y para dotar a la plataforma de movimientos precisos, esta unión, ubicada en la parte superior de las patas, debe deformarse al ser sometida a esfuerzos de flexión y torsión. Se realiza un adecuado diseño que maximice las deformaciones de dicha unión a la par que se garantiza una adecuada duración de la misma para la aplicación requerida. A su vez, se comprueba que las tensiones a las que se verá sometida no superan el límite de fluencia del material elegido. Todo ello se realiza de forma computacional mediante el método de los elementos finitos.

Proceso de creación del “Competitor and Market Report” para cubrir las necesidades de información de la alta dirección de Zurich Insurance Ltd.

Proceso del Competitor and Market Report para cubrir las necesidades de información de la Alta Dirección de Zurich Insurance plc, para la unidad de negocio Global Corporate (GC) en la región de Europa Medio Oriente y África (EMEA) “ El Competitor and Market Report surge de la situación de desinformación en la que los altos directivos y los representantes de CD&M GCiEMEA de cada país se encuentran. Este trabajo consiste en estudiar todo el proceso de creación del Competitor and Market Report, empezando por la identificación del problema, búsqueda de soluciones e implementación y puesta en marcha de la solución. Este proceso nos obligara a inventariar y analizar los estudios que hasta el momento la empresa de seguros Zurich Insurance Ltd, recibía procedentes de fuentes externas o de distintos departamentos que rara vez estaban coordinados en la producción de estos informes. Analizaremos cuales son las áreas de información que estos informes no cubren. El proceso nos obligara a realizar un trabajo de campo. Haremos entrevistas que nos ayudaran a comprender mejor las necesidades de información de los altos directivos. A partir de los resultados anteriores se justificará la creación del Competitor and Market Report, y se estudiará todo el proceso de creación y puesta en marcha de un informe que cubra las necesidades anteriores.

Retórica y derecho en la Alta Edad Media: una defensa judicial del siglo IX

[ES] El objetivo de este artículo es Mostrar un aspecto particular de la Retórica en la Alta Edad Media, a saber, la vinculación de esta "Ars" con la práctica judicial y los estudios de Derecho. Para ello, hemoss analizado un documento relativamente "raro" en tanto que es casi el único de sus características en la Hispania del siglo IX: una defensa judicial incluída en el «Epistolario» de Álvaro de Córdoba (n.c. 800), uno de los mejores escritores en lengua latina de su época. La elección del citado documento tiene su razón de ser en la oscuridad e incertidumbre que rodean nuestro conocimiento de las fuentes y de los procedimientos jurídicos de dicha época.

Localización por imagen de alta resolución del sistema cannabinoide endógeno en la mitocondria del músculo estriado de roedor

96 p.

Diseño y PWHT de aceros avanzados de alta resistencia para cadenas de líneas de fondeo.

202 p. El contenido de los capítulos 3,4,5 y 6 está sujeto a confidencialidad

Efecto de la temperatura y la ración sobre el metabolismo de la carpa dorada (Carassius auratus)

[ES] Se llevan a cabo tres experimentos para estudiar el efecto de tres factores el metabolismo de Carassius auratus: temperatura de exposición, ración de alimento diario y tiempo transcurrido tras la exposición a las nuevas condiciones.

Máquinas de aprendizaje extremo para aplicaciones en ingeniería: implementaciones de alta velocidad sobre FPGAs

Los principales objetivos del presente trabajo son el estudio de las redes neuronales artificiales, los dispositivos reconfigurables de alta velocidad, como son las FPGAs, y su aplicación a un ejemplo concreto: el reconocimiento en tiempo real de diferentes tipos de suelo en imágenes de satélite. Con este fin se propone el diseño de una red neuronal y su implementación en un dispositivo de lógica programable usando el lenguaje de descripción del hardware VHDL (Very High Description Language). Otro de los objetivos del trabajo es conocer los entornos de desarrollo que los fabricantes de dispositivos de lógica programable ponen a disposición de los diseñadores y manejar herramientas de software matemático como Matlab.

Propiedades radiativas y ópticas de una herramienta de corte compuesta por nitruro de boro cúbico

Se ha medido la emisividad espectral (2,5-25 micras) normal de una herramienta de corte industrial, compuesta en un 55% por nitruro de boro cúbico (cBN), en el rango de temperaturas 200-1000 ºC. La emisividad medida muestra un comportamiento suavemente descendente al aumentar la longitud de onda, propio de metales, con un descenso pronunciado alrededor de 9 micras. Este valle se corresponde con la emisividad calculada para el cBN cúbico puro en la literatura, que sin embargo no exhibe el comportamiento metálico medido. Así mismo, se observa que la emisividad espectral es esencialmente independiente de la temperatura, aunque no así la emisividad total. Los resultados experimentales para el cBN puro indican que la reflectividad de dicho compuesto se puede explicar satisfactoriamente mediante un modelo de Lorentz para dieléctricos, mientras que el ajuste teórico de la reflectividad medida para la herramienta de corte necesita incluir una contribución del modelo de Drude para explicar el comportamiento metálico observado. Este modelo combinado se ajusta razonablemente bien a las medidas, y revela que la herramienta de corte se comporta como un semiconductor degenerado, con una alta densidad de portadores libres. Además, permite realizar una estimación teórica de sus constantes ópticas. Por último, se ha realizado un estudio sobre la medida y el control de la temperatura de la muestra, empleando distintos métodos de unión termopar.