Modelado dinámico y control de maniobras de dispositivos submarinos

Es bien conocido por todos que la Primera Revolución Industrial, que tuvo su inicio en la segunda mitad del Siglo XVIII, conllevó un aumento del uso de los recursos energéticos que no se ha detenido para llegar a los niveles de desarrollo tecnológico, industrial y de calidad de vida, de los que se dispone en la actualidad. A simple vista podría intuirse que para disponer de un mayor nivel tecnológico, industrial, de confort, etc. sea necesario un mayor consumo de energía primaria. La actual generación de energía está principalmente basada en el procesamiento de los diversos compuestos del carbono (hidrocarburos, gases y productos derivados del petróleo), que son contaminantes y además, se agotan. Desde hace unas pocas décadas, la humanidad ha sido consciente que es necesario generar energía a partir de fuentes de origen renovable, y que además resulten menos contaminantes. Así, en la actualidad, se ha llegado a un estado de desarrollo avanzado para la explotación de diversas fuentes de energías como la eólica, a la vez que se comienza a mirar con realismo la posibilidad de explotación de diversas energías de origen marino. Se considera que las energías renovables procedentes de los océanos que se encuentran más desarrolladas tecnológicamente hablando, sin tener en cuenta la energía eólica fuera costa (offshore), son la denominada energía undimotriz o de las olas y la energía de las corrientes marinas, no necesariamente en este orden. El trabajo propuesto en esta Tesis se centra en este último recurso energético y, aunque no se dispone todavía de ningún dispositivo en fase de explotación comercial, la concepción, diseño y desarrollo de dispositivos para la extracción de energía de las corrientes, y su evolución, han sido relativamente rápidos e importantes en estos últimos años. Existen ya diferentes dispositivos en fase de pruebas con resultados muy prometedores. Aunque los dispositivos actuales se encuentran limitados a la explotación energética en zonas de poca profundidad, los diferentes estudios del recurso indican la necesidad de explotar corrientes marinas a mayores profundidades, para lo que se están desarrollando actualmente dispositivos, cuya evolución en lo que a sistemas de fondeo se refiere, está siendo muy parecida a la que se ha producido en los parques eólicos fuera costa, similar a su vez, a la evolución llevada a cabo en las plataformas oceánicas para la explotación de recursos petrolíferos (denominados oil & gas) que se extraen de profundidades cada vez mayores. Las soluciones tecnológicas que resulten válidas han de ser también económicamente viables, y en la actualidad se requiere todavía reducir costos en todas las fases de instalación, explotación y mantenimiento de estos dispositivos, sea cual sea su profundidad de operación. Uno de los focos de estudio para abaratar los costes de explotación en general, pasa por abaratar y reducir los costes en las maniobras necesarias de inmersión (de la superficie del mar a la profundidad de operación) y emersión (de la profundidad de operación a la superficie del mar) de estos dispositivos, para llevar a cabo tareas de mantenimiento in situ, en el mar, y sin necesidad de buques especializados ni de su transporte a tierra. En esta Tesis se propone, en primer lugar, un método para evaluar el ciclo de vida de diversos dispositivos de aprovechamiento de las corrientes marinas. Se evidencia que el coste de la energía así generada sigue siendo no plenamente competitivo, por lo que se requiere avanzar en el abaratamiento de costes, principalmente en la instalación y en su mantenimiento. Para ello se propone como novedad principal, introducir sistemas de control en lazo cerrado para realizar maniobras de instalación y mantenimiento de forma automática. También se aporta un modelo dinámico original y muy sencillo para dispositivos bajo estos movimientos de emersión/inmersión, a partir del cual se han desarrollado los algoritmos de control para el propósito mencionado, que no es otro sino automatizar en todo lo posible las maniobras completas. Los algoritmos de control propuestos han sido validados mediante simulación. Se proponen trayectorias de referencia de movimiento suaves (smooth) similares a las utilizadas en robótica. Estos movimientos de cambios de profundidad en lazo cerrado, combinados con secuencias de movimientos en bucle abierto para cuando el dispositivo interacciona en la superficie libre, han dado lugar a nuevas maniobras completas de instalación y mantenimiento que se presentan en esta Tesis, diferentes a las actuales. Finalmente, y como justificación de la viabilidad económica del método novedoso aportado, se ha realizado un estudio comparativo de los costes de la tecnología propuesta, frente a la tecnología actual. Este nuevo sistema de maniobras automáticas implica un ciclo de vida diferente para los dispositivos de aprovechamiento de la energía de las corrientes, ciclo que se cuantifica a partir de un dispositivo base que ha sido modificado y adaptado para la nueva tecnología propuesta, demostrando su viabilidad tanto técnica como económica. ABSTRACT It’s well known that the First Industrial Revolution started in the second half of the eighteenth century, carried the increasing of the use of energy resource which have not been stopped until reach the present technology, industrial evolution and daily life quality. On the surface, it can be known intuitively that a higher consumption of primary energy resource is demanded for benefiting from a higher technological industrial and daily life level. Today, the generation of energy is mainly based in the processing of carbon products (hydrocarbons, gases and petroleum products) which are pollutants, and additionally, are depleted. From a few decades ago, the humanity is aware the energy should be obtained from renewable resources, which besides, should be cleaner. So, at the present, a technical develop has been gained to exploit several energy source, as wind energy, and, at the same time, the extraction of the marine energy starts to seem as a reality. The renewable marine energies considered more advanced and technically developed, without keeping in mind, the offshore wind energy, are the wave energy and the tidal current energy, not necessarily in that order. This Thesis is focused in this last energy resource, and, although, any device is under commercial operation, the concept, design and develop of this type of devices to extract the tidal current energy and their evolution has been comparatively fast and important the last years. There are several devices under test with promising results. Even through the current devices are limited to lower depth areas, the several studies of the tidal energy resource suggest the need to exploit the marine current at greater depths to what is being developed devices, where their evolution in the anchoring system is being very similar to the evolution performed in the offshore wind farms, which is at the same time, similar to the evolution in the oil and gas exploitation which are extracted to greatest depths. Viable technical solutions should be also viable economically and nowadays the cost in all phases of the project (installation, maintenance and operation) should be decreased whatever the operation depth is. One focus of study to lower the operation cost is the cost decreasing of immersion manoeuvring operations (from sea surface to the operation depth) and immersion manoeuvring operations (from operation depth to the sea surface), therefore the maintenance operations can be performed on – site, in the sea, and no specialized vessels are required to transport the devices from the sea to shore. In this dissertation, firstly is proposed a method to evaluate the life cycle of the tidal energy current devices. It is proved the energy generated by these devices is not fully competitive; therefore, the cost falling is mainly an objective in the installation and the maintenance operations. For that, it is proposed as main novelty, the using of closed loop control systems to perform the automatic installation and manoeuvring operations. It is also contributed with an original and simple dynamic model and for controlling the immersion/emersion movements of these devices, from which the control algorithms are developed in order to automate as much as possible the complete manoeuvring. The control algorithms proposed has been validated by simulations. Reference paths with smooth movements, similar which are used in robotics, are suggested. These movements to change the depth using closed loop control, combined with the sequences in open loop movements when the device is in free surface, have been development for a new complete manoeuvring to installation and maintenance operations which are advanced in this Thesis and they are different to the present manoeuvrings. Finally and as justification of the economic viability of this original method, a comparative cost study between the technology proposed and the current technology is performed. This new automatic manoeuvring system involves a different life cycle for the tidal energy current devices, cycle that is quantified from a base device which has been modified and adapted for the new proposed technology, showing the technical and economic viability.

Estudio de la movilidad que presenta el diésel en un suelo contaminado empleando surfactantes

La contaminación de suelos con hidrocarburos de petróleo en México es un problema que se ha vuelto muy común en nuestros días, debido principalmente a derrames, así como a las actividades propias de la industria petrolera. Algunos suelos contaminados, principalmente en el sureste de México, contienen concentraciones de hidrocarburos hasta de 450,000 mg/kg. Por dichas razones, una de las preocupaciones de las autoridades ambientales es el desarrollo de tecnologías eficientes y económicamente factibles que permitan la eliminación de este tipo de contaminantes. El saneamiento del sitio se puede lograr a través de diversos procedimientos, como son la aplicación de métodos físicos, químicos y biológicos (o combinaciones de ellas). La elección de un método depende de la naturaleza del contaminante, su estado físico, concentración, tipo de suelo, espacio físico disponible, tiempo destinado para su tratamiento, así como de los recursos económicos disponibles. Previa a la aplicación de la tecnología es necesario la realización de un diagnóstico de la contaminación del suelo, con el fin de conocer el tipo, concentración y distribución de los contaminantes presentes, así como el volumen de suelo a tratar, las condiciones climáticas de la zona, y características físicas del lugar (vías de acceso y servicios, entre otros). En la presente tesis, el empleo de surfactantes, se ha propuesto como una técnica para incrementar la movilidad de contaminantes orgánicos hidrofóbicos (HOCs) como hidrocarburos totales del petróleo (HTPs), bifenilos policlorados (PCBs), Benceno, Tolueno, Xilenos, explosivos, clorofenoles, pesticidas, entre otros, y así facilitar su degradación. Los surfactantes debido a que reducen la tensión superficial del agua, son moléculas formadas por grupos polares hidrofílicos y largas cadenas carbonadas hidrofóbicas. Sus grupos polares forman puentes hidrógeno con las moléculas de agua, mientras que las cadenas carbonadas se asocian a los hidrocarburos debido a interacciones hidrofóbicas que estos presentan. En soluciones acuosas, los surfactantes forman estructuras esféricas organizadas llamadas micelas. La solubilización de los contaminantes se lleva a cabo solamente cuando se forma la fase micelar, la cual se obtiene cuando la concentración del surfactante es superior a la concentración micelar crítica (CMC), es decir, arriba de la concentración de la cual el monómero se comienza a auto-agregar. La eficiencia de desorción de diésel por un surfactante depende de su naturaleza, de la dosis empleada, de la hidrofobicidad del contaminante, de la interacción surfactante-suelo y del tiempo de contacto surfactante-suelo. Sin embargo, la mejor eficiencia de desorción no está siempre relacionada con la mejor eficiencia de movilidad o solubilidad, debido principalmente a que el empleo de una alta concentración de surfactante puede inhibir la movilización. De acuerdo con información proporcionada por la Procuraduría Federal de Protección al Ambiente (PROFEPA), a la fecha no se ha llevado a cabo en México ninguna restauración de sitios específicamente contaminados con diésel, la técnica de lavado de suelos. Por lo anterior existe la necesidad de emplear la técnica de lavado de suelos ex situ. Específicamente en el suelo extraído de la ex refinería 18 de marzo ubicada en el Distrito Federal México y empleando una solución de surfactantes con agua desionizada, la cual consiste ponerlos en contacto con el suelo contaminado con diésel por medio de columnas de lavado cilíndricas, para lograr la remoción del contaminante. Se emplearon como surfactantes el lauril sulfato de sodio, lauril éter sulfato de sodio y Glucopon AV-100 a diferentes concentraciones de 0.5 a 4.0 [g/L], lográndose obtener una eficiencia del 80 % con este último surfactante. El lavado de suelos contaminados con diésel empleado surfactantes, es una tecnología que requiere que se profundice en el estudio de algunas variables como son el tipo de surfactante, concentración, tiempo de lavado, fenómenos de difusión, desorción, propiedades termodinámicas, entre otros. Los cuales determinarán el éxito o fracaso de la técnica empleada. Nowadays, soil pollution with oil in Mexico is a very common issue due mainly to both oil spill and oil activities. For example, mainly in the southeast area of Mexico, polluted soil contains high concentrations of hydrocarbons, up to 450,000 mg/kg. For these reasons, enviromental authorities have the concern in developing economically feasible and efficient technology that allow the elimination of these type of contaminants. The sanitation in sites can be achieved through several procedures such as physical, chemical and biological methods (or a combination among them). The choice of a method depends on the nature and physical state of the contaminant, the concentration, type of soil, physical space available, time consumption and financial resources. Before any technological application, a diagnostic of the polluted soil is necessary in order to know the type, concentration and distribution of contaminants as well as the soil volume, climatic conditions and physical features of the place (access routes and services, among others). In this thesis, surfactants has been proposed as a technique to increase the mobility of hydrophobic-organic contaminants (HOCs), e.g. total hydrocarbons of petroleum, polychlorinated biphenyls, benzene, toluene, xylenes, explosives, chlorophenols, pesticides, among others, and, hence, to facilitate degradation. Since surfactants reduce the water surface tension, they are molecules comprised of hydrophilic polar groups and long-hydrophobic carbon chains. Surfactant’s polar groups form hydrogen bonding with water molecules while carbon chains, i.e. hydrocarbon chains, have hydrophobic interactios. In aqueous solutions, surfactants form self-organised spherical structures called micelles. The solubilisation of contaminants is carried out only when the micellar phase is formed. This is obtained when the surfactant concentration is higher than the crítical micelle concentration (CMC), i.e. above the concentration where the surfactant monomer begins to self-aggregate. The diesel efficiency desorption by surfactants depends on their nature, the dose use, the contaminant hydrophobicity, the surfactant-soil interaction and the contact time with surfactant soil. However, the best desorption is not always related with the best either mobility or solubility efficiency since high concentration of surfactant can inhibit mobilisation. According to information of the Federal Bureau of Environmental Protection (PROFEPA), up today, there is not any restauration of diesel-polluted sites using the washing-soil technique. Due to the above, there exist the necessity of employing the waching-soil technique ex situ. More specifically, a sample soil from the oil-refinery of “18 de marzo” in Mexico city was extracted and a surfactant solution with deionised water was put in contact with the diesel contaminated soil by means of cylindrical waching columns in order to remove the contaminant. The surfactants employed in this work were sodium lauryl sulfate, sodium lauryl ether sulfate and Glucopon AV-100 at different concentrations of 0.5 to 4 [g/L], obtaining a efficiency of 80 % with this last surfactant. The washing of diesel-polluted soil using surfactants is a technology which requires a deeper study of some variables such as the type of surfactant, concentration, washing time, difusión phenomena, desorption, thermodynamic properties, among others. These parameters determine the succes or failure of the employed technique.

Susceptibility to the biological effects of polyaromatic hydrocarbons is influenced by genes of the major histocompatibility complex

Polyaromatic hydrocarbons are ubiquitous environmental chemicals that are important mutagens and carcinogens. The purpose of this study was to determine whether genes within the major histocompatibility complex (MHC) influence their biological activities. Cell-mediated immunity to dimethylbenz(a)anthracene (DMBA) was investigated in congenic strains of mice. On three different backgrounds, H-2k and H-2a haplotype mice developed significantly greater contact-hypersensitivity responses to DMBA than H-2b, H-2d, and H-2s mice. In B10.A(R1) mice, which are Kk and Id, a vigorous contact-hypersensitivity response was present, indicating that the response was governed by class I, rather than class II, MHC genes. C3H/HeN (H-2k) and C3H.SW (H-2s) strains were also compared for the development of skin tumors and the persistence of DMBA–DNA adducts. When subjected to a DMBA initiation, phorbol 12-tetradecanoate 13-acetate (TPA)-promotion skin-tumorigenesis protocol, C3H/HeN mice, (which develop cell-mediated immunity to DMBA) were found to have significantly fewer tumors than C3H.SW mice (a strain that failed to develop a cell-mediated immune response to DMBA). DMBA–DNA adducts were removed more rapidly in C3H/HeN than in C3H.SW mice. The results indicate that genes within the MHC play an important role in several of the biological activities of carcinogenic polyaromatic hydrocarbons. The observations are consistent with the hypothesis that cell-mediated immunity to chemical carcinogens serves to protect individuals by removing mutant cells before they can evolve into clinically apparent neoplasms.

Paintings of the petroleum industry in Lea County, New Mexico

"The pr1.mary purpose of this thea1a waa to learn about and t .o produce a aeries of pa1nt1n~.a that aymbolized. tbe oil induatry 1n Lea. Count,-, New ltexic.o. The secondary purpose waa to learn more about tho oil industry, which is the big business in Le.a Countj, :New Mexico"

Review and Recommendations for Fast-Track Wetland Permitting for Petroleum Pipeline Maintenance

The petroleum pipeline industry in the United States is challenged with maintaining the integrity of their pipelines, while also protecting the environment during any pipeline repairs. This project provides information on the activities relating to the industry Integrity Management Program, assesses the process that federal agencies are developing to create streamlined permitting processes, and if the necessary federal, state, and local wetland permits can be obtained in the time frame required by the law. Recommendations are also made for implementation of a fast-track wetland permitting process and what pipeline companies can do to speed up the permitting process. This project focuses on the refined petroleum pipelines that originate near the Gulf of Mexico and terminate in the Northeastern United States.

In Situ Bioremediation Methods for Petroleum Pollutants in Soil: A Training Manual for Construction Companies

Construction companies are interested in adopting environmental methods, such as in situ bioremediation, when conducting remediation at petroleum contaminated sites. This interest is due to both the cost benefits associated with in situ bioremediation methods and the environmental movement. This project creates a comprehensive manual comprised of information about site investigations, treatability studies, design, and implementation of in situ bioremediation at petroleum contaminated sites. The training manual also provides information about regulatory requirements and permitting for petroleum contaminated sites.

Stabilisation of low softening point petroleum pitch fibres by HNO3

This paper deals with the stabilisation of low softening point pitch fibres obtained from petroleum pitches using HNO3 as oxidising agent. This method presents some advantages compared with conventional methods: pitches with low softening point (SP) can be used to prepare carbon fibres (CF), the stabilisation time has been reduced, the CF yields are similar to those obtained after general methods of stabilisation, and the initial treatments to increase SP when low SP pitches are used to prepare CF, are avoided. The parent pitches were characterised by different techniques such as diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), elemental analysis and solvent extraction with toluene and quinoline. The interaction between HNO3 and the pitch fibres, as well as the changes occurring during the heat treatment, have been followed by DRIFTS.

Isotropic petroleum pitch as a carbon precursor for the preparation of activated carbons by KOH activation

Results show that it is possible to activate a low softening point isotropic petroleum pitch, without intermediate pre-treatments, by chemical activation with KOH. The chemical activation is carried out by direct heat treatment of a mixture of the isotropic pitch and KOH. It produces activated carbons (ACs) with micropore volumes as high as 1.12 cm3/g, and BET surface areas around 3000 m2/g. The activating agent/precursor ratios studied (from 1/1 to 4/1; wt./wt.) show, as expected, that increasing the ratio enhances the adsorption characteristics of the resulting AC.

Stabilisation of low softening point petroleum pitch fibres by iodine treatment

A method using iodine has been developed for the stabilisation of low softening point (SP) pitch fibres that avoids air stabilisation in the production of carbon fibres (CF). The interaction between iodine and petroleum pitches has been studied by following the changes in the hydrogen content, aromatic or aliphatic, during the heat treatment of iodine-treated pitch fibres. Two low SP petroleum pitches were used and the iodine-treated pitch fibres were analysed by TGA, DSC, DRIFT, XPS and SEM. The results confirm that using this novel method pitches with low SP can be used to prepare CF with two advantages, compared with conventional methods. The stabilisation time is considerably reduced and treatments to increase the SP, usually required when low SP pitches are used to prepare CF, can be avoided.

New insights on the direct activation of isotropic petroleum pitch by alkaline hydroxides

The paper provides interesting evidences that a low softening point isotropic petroleum pitch can be used as a good carbon precursor for the preparation of activated carbons. The activation is carried out by KOH and/or NaOH and the resulting activated carbons present well developed porosity. Such hydroxide activations can be done directly on the pristine petroleum pitch (P) or on the pitch that has been submitted to an air stabilisation followed by a N2 heat treatment (TAN). In general, KOH activation produces better results than NaOH, both in terms of porosity and yield, the results obtained for the activation of TAN being impressive because of the good porosity developments and high yields reached. The different treatments carried out over the petroleum pitch precursor clearly show that they significantly influence the extent of microporosity development. This is due to different changes occurring in the porous structure of the precursor as a function of the treatment carried out. The efficiency of the activation process increases as the mesophase content of the precursor decreases, as well as the mesophase formation during the activation process is avoided.

X-Ray Imaging of SAPO-34 Molecular Sieves at the Nanoscale: Influence of Steaming on the Methanol-to-Hydrocarbons Reaction

The effect of a severe steaming treatment on the physicochemical properties and catalytic performance of H-SAPO-34 molecular sieves during the methanol-to-hydrocarbons (MTH) reaction has been investigated with a combination of scanning transmission X-ray microscopy (STXM), catalytic testing, and bulk characterization techniques, including ammonia temperature programmed desorption and 27Al and 29Si magic angle spinning nuclear magnetic resonance. For this purpose, two samples, namely a calcined and a steamed H-SAPO-34 catalyst powder, have been compared. It has been found that calcined H-SAPO-34 displays a high selectivity towards light olefins, yet shows a poor stability as compared to a zeolite H-ZSM-5 catalyst. Moreover, in situ STXM at the carbon K-edge during the MTH reaction allows construction of nanoscale chemical maps of the hydrocarbon species formed within the H-SAPO-34 aggregates as a function of reaction time and steam post-treatment. It was found that there is an initial preferential formation of coke precursor species within the core of the H-SAPO-34 aggregates. For longer times on stream the formation of the coke precursor species is extended to the outer regions, progressively filling the entire H-SAPO-34 catalyst particle. In contrast, the hydrothermally treated H-SAPO-34 showed similar reaction selectivity, but decreased activity and catalyst stability with respect to its calcined counterpart. These variations in MTH performance are related to a faster and more homogeneous formation of coke precursor species filling up the entire steamed H-SAPO-34 catalyst particle. Finally, the chemical imaging capabilities of the STXM method at the Al and Si K-edge are illustrated by visualizing the silicon islands at the nanoscale before and after steaming H-SAPO-34.

Abatement of hydrocarbons by acid ZSM-5 and BETA zeolites under cold-start conditions

Simulated cold-start tests have been carried out to evaluate the performance of H-ZSM-5 and H-BETA zeolites as hydrocarbon traps under simulated gasoline car exhaust gases, paying special attention to the effect of water on their behaviour. It is concluded that the hydrothermal treatment of the zeolites in the acidic form contributes to the better performance of these materials as hydrocarbon traps since the stabilization of the zeolites takes place. Moreover, the decrease of the surface acidity of the zeolites results in an increase of the Si/Al ratio, which contributes to the decrease of the water affinity for adsorption sites. Thus, the competition with hydrocarbon molecules in the exhaust for the adsorption sites is reduced which increases their trap efficiency. The stabilized H-ZSM-5 is the zeolite that showed the best performance with a propene offset temperature of 240 °C, which should be high enough for the three-way catalyst to carry out its role as catalytic converter.

Polarized–unpolarized ground state of small polycyclic aromatic hydrocarbons

Do polyacenes, circumacenes, periacenes, nanographenes, and graphene nanoribbons show a spin polarized ground state? In this work, we present monodeterminantal (Hartree–Fock (HF) and density functional theory (DFT) types), and multideterminantal calculations (Møller–Plesset and Coupled Cluster), for several families of unsaturated organic molecules (n-Acenes, n-Periacenes and n-Circumacenes). All HF calculations and many DFT show a spin-polarized (antiferromagnetic) ground state, in agreement with previous calculations. Nevertheless, the multideterminantal calculations, carried out with perturbative and variational wavefunctions, show that the more stable state is obtained starting from the unpolarized HF wavefunction. The trend of the stabilization of wavefunctions (polarized or unpolarized) with respect to exchange and correlation potentials, and to the number of benzene rings, has been analyzed. A study of the spin (〈Ŝ2〉) and the spin density on the carbon atoms has also been carried out.

Emissions of Gases, Polycyclic Aromatic Hydrocarbons and Brominated Pollutants during Thermal Degradation of Waste Printed Circuit Boards

Resumen del póster presentado en Symposium on Renewable Energy and Products from Biomass and Waste, CIUDEN (Cubillos de Sil, León, Spain), 12-13 May 2015