Prudentia Iuris, 2003, n° 57 (número completo)

Contenido: Editorial – Respuestas institucionales y políticas ante la macrocriminalidad: La naturaleza económica de la criminalidad organizada / Andrea Castaldo – Blanqueo de capitales : desde la represión del delito a la prevención / María José Meinke – Globalización y derecho penal / Luis Flávio Gomes – La nueva política criminal intimidatoria e inocuizadora : el caso de la seguridad ciudadana en Perú / Percy García Cavero – La respuesta al terrorismo político en Italia / Mauricio Landi – Réplica francesa al terrorismo y al crimen organizado / Serge Leteur – El debate sobre la constitucionalidad de las leyes 23.492 y 23.521 / Miguel M. Padilla – Derechos fundamentales y constitucionalismo penal / Carlos Alberto Mahiques – El estatuto de Roma y el principio de legalidad en el Derecho Penal internacional / Juan Manuel Gramajo – Actualizaciones en Derecho Penal: Acerca de la responsabilidad de la persona jurídica en el Derecho Italiano / Mauro Ronco – La Corte suprema y la morosidad del proceso penal / Francisco D’Albora – El secreto profesional médico / Fernando Mario Caunedo ; Manuel Gorostiaga – La Legislación Argentina ante los delitos complejos / Luis Enrique Velasco – In Memoriam -- Recensiones

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.

Agua, poder y sociedad en el mundo urbano alavés bajomedieval y moderno

561 p.

Dibujantes del Museo de la Plata: Carlos Andrés Tremouilles

En esta colección de la Serie Documentos presentamos a los dibujantes y artistas que pasaron por nuestra institución, lo que representa una tarea nada fácil. Sin embargo, con las imperfecciones del caso, iniciamos este trabajo esperando que, en un futuro próximo, esta iniciativa sea continuada dentro de las diferentes Divisiones que conforman la estructura de nuestro Museo. En este segundo artículo mostramos algunas de las imágenes que pudimos rescatar de Carlos Andrés Tremouilles, formado en la Escuela Superior de Bellas Artes y perteneciente a una dinastía de dibujantes del Museo de La Plata. Su padre Carlos Hipólito y su hijo Carlos también fueron dibujantes de esa institución. Colaboró con Emiliano Mac Donagh y con Raúl A. Ringuelet para ilustrar trabajos sobre nuestra ictiofauna. En 1959 fue reconocido por las autoridades del Primer Congreso Sudamericano de Zoología desarrollado en el Museo de La Plata. Realizó restauraciones de obras pictóricas, guardas y vitrales. Su versatilidad, le permitió realizar también tareas en vitrinas de exhibición, montaje del laboratorio de C14 y reparación de instrumental en base a sus conocimientos de electrónica. Aquí presentamos una pequeña parte de su numerosa obra obtenida de acuarelas y dibujos de peces de los archivos de la División Zoología Vertebrados y los incorporados a las obras Peces marinos de la República Argentina de R. A. Ringuelet y R. H. Arámburu (1960) y Los peces argentinos de agua dulce de R. A. Ringuelet, R. H. Arámburu y A. A. de Arámburu (1967)

Dibujantes del Museo de la Plata: Carlos Andrés Tremouilles.

En esta colección de la Serie Documentos presentamos a los dibujantes y artistas que pasaron por nuestra institución, lo que representa una tarea nada fácil. Sin embargo, con las imperfecciones del caso, iniciamos este trabajo esperando que, en un futuro próximo, esta iniciativa sea continuada dentro de las diferentes Divisiones que conforman la estructura de nuestro Museo. En este segundo artículo mostramos algunas de las imágenes que pudimos rescatar de Carlos Andrés Tremouilles, formado en la Escuela Superior de Bellas Artes y perteneciente a una dinastía de dibujantes del Museo de La Plata. Su padre Carlos Hipólito y su hijo Carlos también fueron dibujantes de esa institución. Colaboró con Emiliano Mac Donagh y con Raúl A. Ringuelet para ilustrar trabajos sobre nuestra ictiofauna. En 1959 fue reconocido por las autoridades del Primer Congreso Sudamericano de Zoología desarrollado en el Museo de La Plata. Realizó restauraciones de obras pictóricas, guardas y vitrales. Su versatilidad, le permitió realizar también tareas en vitrinas de exhibición, montaje del laboratorio de C14 y reparación de instrumental en base a sus conocimientos de electrónica. Aquí presentamos una pequeña parte de su numerosa obra obtenida de acuarelas y dibujos de peces de los archivos de la División Zoología Vertebrados y los incorporados a las obras Peces marinos de la República Argentina de R. A. Ringuelet y R. H. Arámburu (1960) y Los peces argentinos de agua dulce de R. A. Ringuelet, R. H. Arámburu y A. A. de Arámburu (1967).

Fuentes azufradas en cultivos de grano de la Región Pampeana

La presente tesis tuvo como objetivos: i. Evaluar la incidencia de la solubilidad y forma química de fuentes azufradas (azufre elemental y una fuente sulfatada soluble) en las respuestas en el rendimiento de trigo y soja de primera. ii. Analizar la residualidad de la aplicación de las fuentes azufradas en el trigo en el rendimiento de la soja de segunda. Asimismo, como objetivo secundario se planteó evaluar la influencia de variables edáficas y climáticas en las respuestas observadas. Se plantearon dos hipótesis: i. La necesidad de oxidación del azufre elemental (AE) reduce la respuesta y eficiencia de uso del S (EUS) en el cultivo de trigo, comparado con el sulfato de amonio (SA). Por el contrario, ese efecto es de menor magnitud en soja de primera, debido a las condiciones termo - hídricas más favorables. ii. La residualidad de la fertilización del trigo sobre el rendimiento de la soja de segunda, es mayor con el AE micronizado que con el SA. Se realizaron ocho ensayos de campo en trigo/soja 2da y nueve en soja de 1ra, durante dos años consecutivos en sitios ubicados en la Región Pampeana. Los tratamientos fueron: i. testigo (sin agregado de S), ii. fertilización con azufre elemental (AE) micronizado (0-0- 0+95 por ciento de S) en dos niveles de dosis, iii. fertilización con sulfato de amonio granulado (SA, 21-0-0+ 24 por ciento S), también en dos niveles de dosis. Las dosis evaluadas fueron 10 y 30 kg ha-1 de S (año 1) y 15 y 30 kg ha-1 (año 2). La fertilización azufrada afectó significativamente (p menor 0,05) los rendimientos del trigo en cuatro de cinco sitios en el primer año y en todos los sitios durante el segundo año. Las respuestas se ubicaron en el rango de 231 a 857 kg ha-1 en el primer año y entre 702 y 2119 kg ha-1 en el segundo año. No se observaron diferencias en respuesta entre fuentes azufradas (i.e. similar efectividad) o en la eficiencia agronómica del S aplicado (kg de grano kg de S aplicado- 1) en la mayoría de los sitios. Para el conjunto de experimentos, ambos fertilizantes fueron adecuados para proveer SO4 2-al cultivo. Estos resultados permitieron rechazar la hipótesis planteada. Tampoco se detectó efecto significativo de dosis o interacción fuente x dosis en la mayoría de los sitios (p mayor 0,05). La dosis más baja fue suficiente para cubrir la demanda de S del cultivo. Se observó una asociación positiva entre las respuestas y el contenido de MO del suelo y las precipitaciones (macollaje y total del ciclo) e inversa con la disponibilidad de S-SO4 2- a la siembra, aunque con bajo ajuste (R2 medio=0,18). No se detectó asociación entre las respuestas y la temperatura en macollaje o en el ciclo. En los experimentos con soja de 1ra, se observó una baja frecuencia de sitios con respuesta a la fertilización azufrada. En estos sitios, las respuestas fueron de 377-982 kg ha-1 (año 1) y de 151-361 kg ha-1 (año 2) y no se evidenció correlación significativa entre las respuestas y variables climáticas o edáficas en el primer año de evaluación. En el segundo año, las respuestas se correlacionaron en forma inversa con el contenido de S-SO42- inicial (R2=0,63). La eficiencia agronómica del S aplicado fue similar entre las fuentes azufradas durante el primer año y se observó efecto significativo de dosis. La dosis más alta fue más eficiente en proveer S al cultivo. En el segundo año, dependiendo de la localidad, se observaron algunas diferencias de efectividad entre las fuentes azufradas relacionadas con la influencia de variables de sitio. Los efectos residuales en la soja de 2da se observaron en pocos sitios experimentales. Las respuestas fueron de 58-689 (año 1) y de 186-512 kg ha-1 (año 2) y se pudieron asociar en forma inversa con el contenido de S-SO4 2- estimados al inicio del cultivo (R2=0,33). En los sitios con residualidad significativa (p manor 0,05) y con la menor dosis de S aplicada en el trigo antecesor, no se observaron diferencias significativas (p mayor 0,05) en eficiencia agronómica entre fuentes. Por el contrario, con la dosis mas elevada, la eficiencia del S aplicado como AE fue mayor que con SA. Por ello, la hipótesis planteada en el tema de residualidad se acepta, pero parcialmente. Los resultados obtenidos no permitieron determinar un patrón claro de residualidad de las fuentes azufradas en los sitios experimentales.

Resolución No. 073. Por medio de la cual se decide un recurso de reposición y se concede el de apelación

Servicios registrales

Visita a la Santísima y Purísima Inmaculada Virgen María Nuestra Señora del Pueblito, consuelo y delicia de los queretanos y patrona de la provincia de religiosos franciscanos de Michoacán...

UANL

Elogio funebre del señor don Pedro Ramón Romero de Terreros, Trebuestos, Davalos, Ochoa, y Castilla, conde de Santa María de Regla, que con asistencia del tribunal dixo el día 27 de noviembre de 1809 en la iglesia del convento imperial, de N.P. Santo Domingo.

UANL

Solucion del gran problema acerca de la poblacion de las Americas : en que sobre el fundamento de los Libros santos se descubre facil camino á la transmigracion de los hombres del uno al otro continente, ycomo pudieron pasar al nuevo mundo, no salamente las bestias de servicio, sino tambien las fieras, y nocivas.

UANL

Leyendas y tradiciones : Toledo, Córdoba, Granada.

UANL

Granada, Jaen, Málaga y Almería

UANL

La Thebayda en poblado, el convento de la Concepcion Capuchina, en la imperial Toledo, su fundacion, y progressos, y las vidas de sus anacoretas religiosas que con su santidad le han ilustrado

UANL

Dios, la naturaleza y la humanidad estudios críticos sobrelos principales problemas del materialismo y positivismo experimental para demostrar que entre la religión católica yla ciencia empírica no pueden existir conflictos

UANL

Décima carta pastoral que el Obispo de Linares dirige a sus diócesanos con motivo del decreto, fecha 5 de marzo, expedido por el Supremo Gobierno de Nuevo León y Coahuila que despoja a la Iglesia de los capitales de capellanías, cofrades y legados piadosos

UANL