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.

Desarrollo de circuitos electrónicos para la extracción y conversión en energía eléctrica de la vibración aplicada a materiales piezoeléctricos

xx,145 p.

Charge and spin transport in graphene devices

170 p.

Intuicionismo y formalismo en la filosofía de la matemática de I. Kant y H. Hilbert. Sobre función y significado de la intuición matemática

514 p.

La frontera, borders an transborders. Reflections of the borderlands in Chicana Literature (early 20th-21st c.)

421 p.

La crítica de Ortega y Gasset a la modernidad y su lugar en la filosofía contemporánea. Problemas onto-epistemológicos

361 p.

Zehaztasun handiko artikulazioen malgutasun analisia.

[EU]Azken urteetan argi geratu da gizakiak aurrera egiteko ezinbestekoa duela zehaztasuna. Teknologia berriak geroz eta bideratuagoak daude produktuen tamaina ahalik eta gehien murrizten edota produktu handien perdoiak nanometroetara hurbiltzeko ahaleginetan. Hau lortzeko bidean ezinbestekoa da elementu guztietan zehaztasuna limitera eramatea eta funtsean, honetan zentratuko da lan hau. Proiektu hau artikulazioen zehaztasuna hobetzeko tekniketan zentratuko da, gehiago zehaztuz, optika arloan lan egingo duen errobot baten artikulazioak analizatuko ditu. Artikulazioen zehaztasun optimoa lortzeko artikulazio hauek generazio berriko artikulazioak izatea pentsatu da, artikulazio flexible edo “flexible joints” izenekoak. Artikulazio hauek, orain artekoak ez bezala, ez dituzte bi elementu elkartuko, elementu bakarrez osatuta egongo dira eta bere buruarekiko errotazioz eta flexioz egingo dute lan honela, ohiko artikulazioek funtzionamendu egokirako behar duten lasaiera baztertu egingo da zehaztasun hobeak lortuz. Lan honetan zehar artikulazio flexible mota bat aukeratuko da eta geometriaren hainbat parametroren eta material ezberdinen aurrean edukiko duen jokaera analizatuko da. Aipatu beharra dago, artikulazio flexibleak azken hamarkadetan garatutako ideiak direnez beraiei buruzko informazioa oso pribatizatua dagoela eta ez dela lan erraza hau interneten edota liburutegietan topatzea. Ala ere, hauen analisirako aurkitu den informazio guztia eranskinetan dauden artikuluetan dago. Bertatik atera den informazio garrantzitsuena elementu finituen bitartezko analisian geometriak eduki beharreko baldintza batzuk eta ulermen eta aldaratze egokia lortzeko komeni diren datuak zehaztea izan da. Interesgarria da aipatzea analisiaren ondorioak konstante elastiko eta biratu dezaketen angelu maximoaren bitartez egin direla.

Control de almacén automatizado con dos ejes lineales.

[ES]El objetivo principal de este Trabajo Fin de Grado es automatizar un almacén con dos ejes lineales con la meta final de programar un panel de operador para que, ya sea un usuario u operario pueda introducir si desea depositar o recoger un palé, indicando la posición mediante un sistema de coordenadas las cuales dividen a las estanterías del almacén en filas y columnas. Para ello se cambiará parte del hardware de control, el cual incluye el antiguo módulo de posicionamiento (IP 246) que hasta ahora, controlaba el almacén. Esta tarjeta está limitada a un software ya desfasado, sin posibilidad de implementar un panel de operador con los requisitos demandados en la industria de hoy en día. También se ha utilizado una CPU S7-300, a diferencia de la SIMATIC S5 que se utilizaba con la antigua tarjeta.

La aplicación del principio de igualdad de oportunidades de mujeres y hombres al personal al servicio de la Administración de Justicia de la Comunidad Autónoma del País Vasco

611 p.

Spin squeezing, macrorealism and the heisenberg uncertainty principle

169 p.

Análisis del nivel de sedentarismo mediante acelerometría y cuestionario IPAQ en personas con hipertensión primaria y sobrepeso u obesidad

Antecedentes: La hipertensión arterial y el sobrepeso u obesidad son considerados factores de riesgo cardiovascular, asociados de forma clara con el sedentarismo en la población adulta. La valoración del sedentarismo se puede realizar a través de métodos objetivos y subjetivos. Objetivos: Analizar el nivel de sedentarismo, mediante el cuestionario internacional de actividad física (AF) (IPAQ, método subjetivo) y acelerometría (método objetivo) en personas con HTA primaria y sobrepeso u obesidad. Determinar si existen diferencias entre ambos métodos de valoración y entre sexos. Métodos: Se llevaron a cabo las dos pruebas de valoración a 48 participantes del estudio EXERDIET-HTA (edad 51,9 ± 8,1 años). 1) Cuestionario IPAQ en versión corta que mide la AF realizada durante los últimos siete días. Los datos se clasificaron en tiempo sedentario, ligero, moderado o intenso según las recomendaciones generales de la Organización Mundial de la Salud. 2) Acelerometría triaxial durante siete días portado en la muñeca no dominante. El tiempo dedicado a conductas sedentarias, así como las diferentes intensidades de AF (ligera, moderada, vigorosa y muy vigorosa), Kcal, METs y tiempo de sueño se calcularon para los días laborables y de fin de semana. Resultados: IPAQ presentó una media de 6 h/día en comportamientos sedentarios en ambos sexos. No se presentaron diferencias entre sexos. El 85,4% resulta sedentario. Acelerometría: Los participantes presentan 1,7±0,2 MET de media al día, considerado un valor metabólico de gasto calórico ligero. El tiempo de sueño diario fue de 6,6h. El gasto calórico diario se corresponde con comportamientos sedentarios entre semana para hombres y mujeres (2038,5±801,6 kcal) y sólo los hombres incrementan el gasto el fin de semana (P=0,036). Se observó que las mujeres realizan más minutos de AF a intensidad moderada que los hombres durante toda la semana (P=0,029). Se observaron diferencias de actividad entre los días entre semana y el fin de semana, con más tiempo de sedentarismo entre semana (P=0,040) y más AF ligera el fin de semana (P=0,003), resultando esta diferencia debida al cambio de actividad en los hombres pero no en las mujeres. Todos los participantes superan los 150 minutos de AF moderada que se recomienda en las guías mundiales según la acelerometría. Conclusiones: Las personas hipertensas y con sobrepeso u obesidad presentan en general conductas sedentarias. Los patrones de sueño podrían estar relacionados con la enfermedad. Sería necesario reducir las conductas sedentarias como prevención de la obesidad y del desarrollo prematuro de enfermedades cardiovasculares, fomentando la práctica regular de AF y mejorando los hábitos de alimentación.

Aireztapenen maiztasunaren neurketa bihotz biriketako berpiztean kapnografia erabiliz.

[EN]Hyperventilation, which is common both in-hospital and out-of-hospital cardiac arrest, decreases coronary and cerebral perfusion contributing to poorer survival rates in both animals and humans. Current resucitation guidelines recommend continuous monitoring of exhaled carbon dioxide (CO2) during cardiopulmonary resucitation (CPR) and emphasize good quality of CPR, including ventilations at 8-10 min1. Most of commercial monitors/de- brilators incorporate methods to compute the respiratory rate based on capnography since it shows uctuations caused by ventilations. Chest compressions may induce artifacts in this signal making the calculation of the respiratory rate di cult. Nevertheless, the accuracy of these methods during CPR has not been documented yet. The aim of this project is to analyze whether the capnogram is reliable to compute ventilation rate during CPR. A total of 91 episodes, 63 out-of-hospital cardiac arrest episodes ( rst database) and 28 in-hospital cardiac arrest episodes (second database) were used to develop an algorithm to detect ventilations in the capnogram, and the nal aim is to provide an accurate ventilation rate for feedback purposes during CPR. Two graphic user interfaces were developed to make the analysis easier and another two were adapted to carry out this project. The use of this interfaces facilitates the managment of the databases and the calculation of the algorithm accuracy. In the rst database, as gold standard every ventilation was marked by visual inspection of both the impedance, which shows uctuations with every ventilation, and the capnography signal. In the second database, volume of the respiratory ow signal was used as gold standard to mark ventilation instants since it is not a ected by chest compressions. The capnogram was preprocessed to remove high frequency noise, and the rst di erence was computed to de ne the onset of inspiration and expiration. Then, morphological features were extracted and a decission algorithm built based on the extracted features to detect ventilation instants. Finally, ventilation rate was calculated using the detected instants of ventilation. According to the results obtained in this project, the capnogram can be reliably used to give feedback ventilation rate, and therefore, on hyperventilation in a resucitation scenario.

Análisis de la desigualdad económica en los municipios del País Vasco

[ES]Este trabajo examina la evolución de la desigualdad económica en los municipios de País Vasco durante el periodo 1996-2010. Para ello se utilizan los datos del PIB per cápita municipal de la base de datos de UDALMAP. Mediante el análisis de curvas de Lorenz, que nos permiten realizar un estudio tanto estático como dinámico de la desigualdad, y el cálculo del índice de Gini y de Theil, llegamos a conclusiones con respecto a los efectos de la crisis en la evolución de la desigualdad económica. Además, mediante Theil se realiza un estudio más profundo descomponiendo la desigualdad por subgrupos de población (provincias) con el fin de detectar la principal fuente de la desigualdad del PIB per cápita entre los municipios del País Vasco. De este análisis se concluye que tanto a nivel del País Vasco como a nivel provincial la desigualdad económica aumenta hasta el año inicial a la crisis, disminuyendo a partir de ese punto hasta el último año analizado. Con la descomposición de Theil se observa que parte de la desigualdad del PIB per cápita proviene de la diferencia entre provincias, pero que su fuente principal radica en la diferencia entre municipios dentro de las provincias.

Exploring new labelling strategies for boronated compounds: towards fast development and efficient assessment of BNCT drug candidates

208 p.

Análisis Comparativo de las Estrategias Competitivas de dos Agencias de Viajes del País Vasco: Viajes Eroski y Loreak Bidaiak

[ES]El objeto del presente trabajo es analizar las estrategias competitivas que utilizan las empresas del sector de las agencias de viajes en el País Vasco. La decisión de estudiar las estrategias competitivas se tomó por la gran importancia que están adquiriendo las decisiones estratégicas en un mercado cada vez más competitivo. Para ello, he seleccionado dos empresas cuya sede principal está implantada en el País Vasco. Como bien he mencionado, ambas son del sector de las agencias de viajes, pero la diferencia principal que encontramos entre ambas es su expansión y tamaño. Para situarnos en el objeto de estudio, comenzaremos viendo la evolución histórica de la formulación e implantación de las estrategias por parte de la dirección de empresa. Posteriormente se seguirá con el análisis de los distintos niveles de estrategias, para continuar con el estudio más en profundidad de las estrategias competitivas según el modelo de Porter. Previo al estudio de las empresas seleccionadas se realizará un análisis sectorial y su situación en el País Vasco. Como el objeto de estudio se trata de las estrategias competitivas, en primer lugar he comenzado con una fundamentación teórica del objeto de estudio, es decir, de las estrategias competitivas. Posteriormente, en el apartado siguiente he pasado a la aplicación práctica a las dos empresas elegidas. En esta fase práctica del presente trabajo, una parte ha consistido en trabajo de campo, mediante el cual he obtenido parte de la información para poder realizar la investigación y poder llegar a la obtención de una serie de conclusiones. Las dos empresas seleccionadas son Viajes Eroski y Lorea Bidaiak. Por un lado, Viajes Eroski se trata de una empresa que abarca mayor ámbito geográfico, y por lo tanto mayor extensión. Por otro lado, la segunda empresa a analizar, es decir, Lorea Bidaiak, se trata de una empresa que solo actúa a nivel local, y por lo tanto, es de menor tamaño.