Glycerol oxidehydration to acrylic acid on complex mixed-metal oxides

The project of this Ph.D. thesis is based on a co-supervised collaboration between Università di Bologna, ALMA MATER STUDIORUM (Italy) and Instituto de Tecnología Química, Universitat Politècnica de València ITQ-UPV (Spain). This Ph.D. thesis is about the synthesis, characterization and catalytic testing of complex mixed-oxide catalysts mainly related to the family of Hexagonal Tungsten Bronzes (HTBs). These materials have been little explored as catalysts, although they have a great potential as multifunctional materials. Their peculiar acid properties can be coupled to other functionalities (e.g. redox sites) by isomorphous substitution of tungsten atoms with other transition metals such as vanadium, niobium and molybdenum. In this PhD thesis, it was demonstrated how it is possible to prepare substituted-HTBs by hydrothermal synthesis; these mixed-oxide were fully characterize by a number of physicochemical techniques such as XPS, HR-TEM, XAS etc. They were also used as catalysts for the one-pot glycerol oxidehydration to acrylic acid; this reaction might represent a viable chemical route to solve the important issue related to the co-production of glycerin along the biodiesel production chain. Acrylic acid yields as high as 51% were obtained and important structure-reactivity correlations were proved to govern the catalytic performance; only fine tuning of acid and redox properties as well as the in-framework presence of vanadium are fundamental to achieve noteworthy yields into the acid monomer. The overall results reported herein might represent an important contribution for future applications of HTBs in catalysis as well as a general guideline for a multifaceted approach for their physicochemical characterization.

Selección y estimación de parámetros genéticos en bovinos lecheros

La estimación de parámetros genéticos en bovinos lecheros requiere ajustar modelos estadísticos para datos longitudinales (modelos de regresión aleatoria y/o medidas repetidas). Es esencial en regresión aleatoria determinar el orden correcto de los polinomios que describen los coeficientes aleatorios en el tiempo. Tradicionalmente, esta tarea se desarrolló empleando criterios de selección como AIC o BIC, que no siempre logran dilucidar claramente el modelo apropiado. Esta tesis introduce el criterio PAL para la selección del orden del polinomio en modelos de regresión aleatoria, empleando una penalización adaptativa de la función de verosimilitud. Comparativamente, PAL presentó un desempeño superior a AIC y BIC, y su aplicación a datos de producción produjo un modelo parsimonioso, con buena bondad de ajuste y habilidad de predicción. Se abordó además el problema de estimar parámetros genéticos bajo un modelo de medidas repetidas para caracteres que muestran distribución asimétrica. Para evitar desvíos del supuesto de normalidad de los errores, se presentó un modelo alternativo basado en asumir una distribución Normal asimétrica. Se implementó un enfoque bayesiano con muestreo de Gibbs en datos de intervalos entre partos. Incluyendo un parámetro adicional, se obtuvieron estimaciones más precisas de los parámetros genéticos. Estos desarrollos metodológicos estuvieron motivados por los desafíos que enfrenta actualmente el programa de mejoramiento genético de la raza Holstein en Colombia. Entre ellos, figura también el impacto de introducir toros extranjeros provenientes del programa de selección genómica norteamericana. En este marco, se estimó el progreso genético esperado en la población comercial colombiana. Los cálculos reflejaron que utilizar toros genómicos jóvenes se traducirá en una respuesta genética acelerada y en una disminución de la diferencia genética entre el hato comercial y el núcleo del cual provienen.

Hydrochemical Atlas of the Arctic Ocean

Introduction: Chemical composition of water determines its physical properties and character of processes proceeding in it: freezing temperature, volume of evaporation, density, color, transparency, filtration capacity, etc. Presence of chemical elements in water solution confers waters special physical properties exerting significant influence on their circulation, creates necessary conditions for development and inhabitance of flora and fauna, and imparts to the ocean waters some chemical features that radically differ them from the land waters (Alekin & Liakhin, 1984). Hydrochemical information helps to determine elements of water circulation, convection depth, makes it easier to distinguish water masses and gives additional knowledge of climatic variability of ocean conditions. Hydrochemical information is a necessary part of biological research. Water chemical composition can be the governing characteristics determining possibility and limits of use of marine objects, both stationary and moving in sea water. Subject of investigation of hydrochemistry is study of dynamics of chemical composition, i.e. processes of its formation and hydrochemical conditions of water bodies (Alekin & Liakhin 1984). The hydrochemical processes in the Arctic Ocean are the least known. Some information on these processes can be obtained in odd publications. A generalizing study of hydrochemical conditions in the Arctic Ocean based on expeditions conducted in the years 1948-1975 has been carried out by Rusanov et al. (1979). The "Atlas of the World Ocean: the Arctic Ocean" contains a special section "Hydrochemistry" (Gorshkov, 1980). Typical vertical profiles, transects and maps for different depths - 0, 100, 300, 500, 1000, 2000, 3000 m are given in this section for the following parameters: dissolved oxygen, phosphate, silicate, pH and alkaline-chlorine coefficient. The maps were constructed using the data of expeditions conducted in the years 1948-1975. The illustrations reflect main features of distribution of the hydrochemical elements for multi-year period and represent a static image of hydrochemical conditions. Distribution of the hydrochemical elements on the ocean surface is given for two seasons - winter and summer, for the other depths are given mean annual fields. Aim of the present Atlas is description of hydrochemical conditions in the Arctic Ocean on the basis of a greater body of hydrochemical information for the years 1948-2000 and using the up-to-date methods of analysis and electronic forms of presentation of hydrochemical information. The most wide-spread characteristics determined in water samples were used as hydrochemical indices. They are: dissolved oxygen, phosphate, silicate, pH, total alkalinity, nitrite and nitrate. An important characteristics of water salt composition - "salinity" has been considered in the Oceanographic Atlas of the Arctic Ocean (1997, 1998). Presentation of the hydrochemical characteristics in this Hydrochemical Atlas is wider if compared with that of the former Atlas (Gorshkov, 1980). Maps of climatic distribution of the hydrochemical elements were constructed for all the standard depths, and seasonal variability of the hydrochemical parameters is given not only for the surface, but also for the underlying standard depths up to 400 m and including. Statistical characteristics of the hydrochemical elements are given for the first time. Detailed accuracy estimates of initial data and map construction are also given in the Atlas. Calculated values of mean-root deviations, maximum and minimum values of the parameters demonstrate limits of their variability for the analyzed period of observations. Therefore, not only investigations of chemical statics are summarized in the Atlas, but also some elements of chemical dynamics are demonstrated. Digital arrays of the hydrochemical elements obtained in nodes of a regular grid are the new form of characteristics presentation in the Atlas. It should be mentioned that the same grid and the same boxes were used in the Atlas, as those that had been used by creation of the US-Russian climatic Oceanographic Atlas. It allows to combine hydrochemical and oceanographic information of these Atlases. The first block of the digital arrays contains climatic characteristics calculated using direct observational data. These climatic characteristics were not calculated in the regions without observations, and the information arrays for these regions have gaps. The other block of climatic information in a gridded form was obtained with the help of objective analysis of observational data. Procedure of the objective analysis allowed us to obtain climatic estimates of the hydrochemical characteristics for the whole water area of the Arctic Ocean including the regions not covered by observations. Data of the objective analysis can be widely used, in particular, in hydrobiological investigations and in modeling of hydrochemical conditions of the Arctic Ocean. Array of initial measurements is a separate block. It includes all the available materials of hydrochemical observations in the form, as they were presented in different sources. While keeping in mind that this array contains some amount of perverted information, the authors of the Atlas assumed it necessary to store this information in its primary form. Methods of data quality control can be developed in future in the process of hydrochemical information accumulation. It can be supposed that attitude can vary in future to the data that were rejected according to the procedure accepted in the Atlas. The hydrochemical Atlas of the Arctic Ocean is the first specialized and electronic generalization of hydrochemical observations in the Arctic Ocean and finishes the program of joint efforts of Russian and US specialists in preparation of a number of atlases for the Arctic. The published Oceanographic Atlas (1997, 1998), Atlas of Arctic Meteorology and Climate (2000), Ice Atlas of the Arctic Ocean prepared for publication and Hydrochemical Atlas of the Arctic Ocean represent a united series of fundamental generalizations of empirical knowledge of Arctic Ocean nature at climatic level. The Hydrochemical Atlas of the Arctic Ocean was elaborated in the result of joint efforts of the SRC of the RF AARI and IARC. Dr. Ye. Nikiforov was scientific supervisor of the Atlas, Dr. R. Colony was manager on behalf of the USA and Dr. L. Timokhov - on behalf of Russia.

Análisis estructural de cúpulas tabicadas: la cúpula interior de la Basílica de la Virgen de los Desamparados en Valencia

La Basílica de la Virgen de los Desamparados, construida entre 1652 y 1667, es el edificio valenciano más importante del siglo XVII (Bérchez 1995). Su elemento más notables es la gran cúpula oval que, en planta, aparece inscrita en un trapezoide. Esta disposición fue muy popular en el Barroco y tiene su origen en los proyectos de Vignola para Sant Andrea in Via Flaminia (1550) y Sant= Anna dei Palafraneri (1572), véase Lotz (1955). En España se construyeron varias cúpulas ovales hacia 1600 (Rodríguez G. de Ceballos 1983); la más grande es la del convento de las Recoletas Bernardas in Alcalá de Henares, 1617-1626, con ejes de 25 x 18 m, y una altura de 11 m (según levantamiento de Schubert 1908). Treinta y tres años tras su terminación, hacia 1700, se construyó una nueva cúpula interior, encajada dentro de la original, para servir de soporte a un enorme fresco del pintor Antonio Palomino en honor de la Virgen de los Desamparados. Esta cúpula es extraordinariamente delgada y presenta algunas disposiciones que la convierten en un caso de excepcional interés en la historia de las cúpulas de fábrica. La estructura y construcción de la Basílica de los Desamparados fue estudiada exhaustivamente en los años 1990 con vistas a elaborar posteriormente un proyecto de restauración. Los trabajos y el proyecto fueron dirigidos por el arquitecto Ignacio Bosch Reig. Algunos estudios fueron publicados en 1999 (Roig y Bosch 1999), y toda la información referente a los estudios y posterior restauración fue compilada y publicada en un libro (Bosch 2006). En este caso se dispone, por tanto, de una enorme cantidad de información sobre la estructura, construcción y forma del edificio. En lo que sigue trataremos sólo la construcción y comportamiento estructural de la doble cúpula de la Basílica.

Simulación de maniobras de buques con sistemas de propulsión no convencional en aguas poco profundas

Los requisitos cada vez más exigentes en cuanto a misiones, limitaciones operacionales y ambientales así como nuevas tecnologías, imponen permanentemente retos a los arquitectos navales para generar alternativas de buques y valorar su bondad en las primeras etapas del proyecto. Este es el caso de los Buques Patrulleros de Apoyo Fluvial Pesados PAF-P, que por requerimiento de la Armada Nacional de Colombia ha diseñado y construido COTECMAR. Los PAF-P, son buques fluviales cuya relación Manga-Calado excede la mayoría de los buques existentes (B/T=9,5), debido principalmente a las restricciones en el calado a consecuencia de la escasa profundidad de los ríos. Estos buques están equipados con sistemas de propulsión acimutales tipo “Pum-Jet”. Las particularidades del buque y del ambiente operacional, caracterizado por ríos tropicales con una variabilidad de profundidad dependiente del régimen de lluvias y sequía, así como la falta de canalización y la corriente, hacen que la maniobrabilidad y controlabilidad sean fundamentales para el cumplimiento de su misión; adicionalmente, no existen modelos matemáticos validados que permitan predecir en las primeras etapas del diseño la maniobrabilidad de este tipo de buques con los efectos asociados por profundidad. La presente tesis doctoral aborda el desarrollo de un modelo matemático para simulación de maniobrabilidad en aguas poco profundas de buques con relación manga-calado alta y con propulsores acimutales tipo “Pump-Jet”, cuyo chorro además de entregar el empuje necesario para el avance del buque, genera la fuerza de gobierno en función del ángulo de orientación del mismo, eliminando la necesidad de timones. El modelo matemático ha sido validado mediante los resultados obtenidos en las pruebas de maniobrabilidad a escala real del PAF-P, a través de la comparación de trayectorias, series temporales de las variables de estado más significativas y parámetros del círculo evolutivo como son diámetro de giro, diámetro táctico, avance y transferencia. El plan de pruebas se basó en técnicas de Diseño de Experimentos “DOE” para racionalizar el número de corridas en diferentes condiciones de profundidad, velocidad y orientación del chorro (ángulo de timón). En el marco de la presente investigación y para minimizar los errores por efectos ambientales y por inexactitud en los instrumentos de medición, se desarrolló un sistema de adquisición y procesamiento de datos de acuerdo con los lineamientos de ITTC. La literatura existente describe los efectos negativos de la profundidad en los parámetros de maniobrabilidad de buques convencionales (Efecto tipo S), principalmente las trayectorias descritas en los círculos evolutivos aumentan en la medida que disminuye la profundidad; no obstante, en buques de alta relación manga-calado, B/T=7,51 (Yoshimura, y otros, 1.988) y B/T=6,38 (Yasukawa, y otros, 1.995) ha sido reportado el efecto contrario (Efecto tipo NS Non Standart). Este último efecto sin embargo, ha sido observado mediante experimentación con modelos a escala pero no ha sido validado en pruebas de buques a escala real. El efecto tipo NS en buques dotados con hélice y timones, se atribuye al mayor incremento de la fuerza del timón comparativamente con las fuerzas del casco en la medida que disminuye la profundidad; en el caso de estudio, el fenómeno está asociado a la mejor eficiencia de la bomba de agua “Pump-Jet”, debido a la resistencia añadida en el casco por efecto de la disminución de la profundidad. Los resultados de las pruebas con buque a escala real validan el excelente desempeño de esta clase de buques, cumpliendo en exceso los criterios de maniobrabilidad existentes y muestran que el diámetro de giro y otras características de maniobrabilidad mejoran con la disminución de la profundidad en buques con alta relación manga-calado. ABSTRACT The increasingly demanding requirements in terms of missions, operational and environmental constraints as well as new technologies, constantly impose challenges to naval architects to generate alternatives and asses their performance in the early stages of design. That is the case of Riverine Support Patrol Vessel (RSPV), designed and built by COTECMAR for the Colombian Navy. RSPV are riverine ships with a Beam-Draft ratio exceeding most of existing ships (B/T=9,5), mainly due to the restrictions in draft as a result of shallow water environment. The ships are equipped with azimuthal propulsion system of the “Pump-Jet” type. The peculiarities of the ship and the operational environment, characterized by tropical rivers of variable depth depending on the rain and dry seasons, as well as the lack channels and the effect of water current, make manoeuvrability and controllability fundamental to fulfill its mission; on the other hand, there are not validated mathematical models available to predict the manoeuvrability of such ships with the associated water depth effects in the early stages of design. This dissertation addresses the development of a mathematical model for shallow waters’ manoeuvrability simulation of ships with high Beam-Draft ratio and azimuthal propulsion systems type “Pump-Jet”, whose stream generates the thrust required by the ship to advance and also the steering force depending on the orientation angle, eliminating the need of rudders. The mathematical model has been validated with the results of RSPV’s full scale manoeuvring tests, through a comparison of paths, time series of state variables and other parameters taken from turning tests, such as turning diameter, tactical diameter, advance and transfer. The test plan was developed applying techniques of Design of Experiments “DOE”, in order to rationalize the number of runs in different conditions of water depth, ship speed and jet stream orientation (rudder angle). A data acquisition and processing system was developed, following the guidelines of ITTC, as part of this research effort, in order to minimize errors by environmental effects and inaccuracy in measurement instruments, The negative effects of depth on manoeuvrability parameters for conventional ships (Effect Type S: the path described by the ship during turning test increase with decrease of water depth), has been documented in the open literature; however for wide-beam ships, B/T=7,51 (Yoshimura, y otros, 1.988) and B/T=6,38 (Yasukawa, y otros, 1.995) has been reported the opposite effect (Type NS). The latter effect has been observed thru model testing but until now had not been validated with full-scale results. In ships with propellers and rudders, type NS effect is due to the fact that increment of rudder force becomes larger than hull force with decrease of water depth; in the study case, the phenomenon is associated with better efficiency of the Pump-Jet once the vessel speed becomes lower, due to hull added resistance by the effect of the decrease of water depth. The results of full scale tests validates the excellent performance of this class of ships, fulfilling the manoeuvrability criteria in excess and showing that turning diameter and other parameters in high beam-draft ratio vessels do improve with the decrease of depth.