Pyrolysis oil upgrading for Co-processing in standard refinery units

This thesis considers the route that comprises the upgrading of pyrolysis oil (produced from lingo-cellulosic biomass) and its further co-processing in standard refineries to produce transportation fuels. In the present concept, pyrolysis oil is produced where biomass is available and then transported to a central upgrading unit. This unit is located next or inside a standard petroleum refinery, enabling the use of existing facilities. The obtained product can be further distributed using existing distribution networks.\ud \ud The present thesis describes and discusses pyrolysis oil upgrading by high pressure thermal treatment (HPTT) and hydrodeoxygenation (HDO), and its subsequent co-processing in lab-scale refinery units. The oil produced by HPTT had higher energy density than the feed due to its lower oxygen and water content. Conversion and transfer of water soluble organics to the oil phase was observed, increasing the energy recovery in the final product. However, severe and fast polymerisation was also observed. This polymerisation created a product with high coking tendency that could not be co-processed in lab-scale refinery units. HDO of pyrolysis oil (and fractions obtained by adding water to it) also created an oil with lower oxygen and water content. However, during HDO, polymerisation was avoided. HDO oils (with high remaining oxygen content) produced at different conditions and from various pyrolysis oil fractions, could be co-processed with Long Residue in a lab-scale catalytic cracking unit. The resulting yields to gasoline and light cycle oil (diesel precursor) were near the same as obtained using the pure fossil reference feed. The presence of such fossil co-feed enabled hydrogen transfer reactions from the fossil feed to the HDO oils components and appeared to be crucial to obtain a good product distribution. Co-processing HDO oils with straight run gas oil in a lab-scale hydrodesulphurisation unit was performed without operational problems, but competition between oxygen and sulphur removal reactions was detected. Dedicated HDO experiments showed that mass transfer resistances can limit the extent of the hydrotreating reactions (favouring in this way the extent of undesired polymerisation reactions, thus deteriorating product quality) and need careful consideration when designing demo units and industrial HDO reactors

Nitrosamine degradation by UV light in post-combustion CO2 capture: Effect of solvent matrix

AbstractPotential production and emission of nitrosamines during post-combustion CO2 capture has drawn some attention due to their toxicity and potential carcinogenicity. One of the possible ways to reduce the concentration of nitrosamines is irradiation of the liquid streams of the capture plant with UV light. This paper shows experimental results of the degradation of nitrosamines such as N-nitroso-diethanolamine (NDELA) and N-mononitroso-piperazine (MNPZ) in different solvent matrices. These solvent matrices include water and laboratory grade monoethanolamine (MEA) aqueous solutions, as well as aqueous MEA solution and wash water that had been used in a CO2 capture pilot plant connected to a coal-fired power plant. Experiments were conducted in dedicated batch set-ups and in a continuous mini CO2 capture plant. Results show that the UV absorbance of impurities (degradation products and/or dissolved metals) present in MEA solvent that had been used in a pilot plant significantly reduces the UV degradation rate of nitrosamines. Furthermore, UV light seems to accelerate the degradation of the capture solvent itself. For these reasons, if UV light treatment is to be used in full-scale post-combustion CO2 capture plants, suitable locations would be the absorber's washing section or the stripper's condensate. At these locations, less interference of degradation products can occur and there is less solvent to be degraded

Validación de un nuevo método de preconcentración y medición de mercurio en sedimentos utilizando materiales sol-gel dopados con extractantes sulfurados

El mercurio es un metal pesado altamente tóxico presente en el ambiente por causas naturales o antropogénicas. El mercurio contenido en los cuerpos receptores de agua tiende a precipitarse y acumularse en los sedimentos. Por lo tanto, las mediciones de mercurio en sedimentos representan un buen indicativo de la calidad del ecosistema. En este trabajo se presentan las diferentes etapas involucradas en el desarrollo de un nuevo método de separación, preconcentración y medición de mercurio en sedimentos con contenidos naturales de este elemento. La separación y preconcentración se realizó mediante el uso de nuevos materiales sorbentes preparados a través del proceso sol-gel utilizando CYANEX 471X (sulfuro de triisobutilfosfina) y CYANEX 301 (ácido bis (2,4,4-trimetilpentil) ditiofosfínico) como extractantes de mercurio. Se describe la optimización de la etapa de acoplamiento de los materiales empacados en columna, utilizando un sistema automatizado de inyección de flujo, para conectarla en línea con un espectrómetro de absorción atómica donde se realizó la medición de mercurio por generación de vapor frío. Como parte importante en el desarrollo de un nuevo método analítico, se encuentra su validación, la cual es materia de este trabajo. Por lo tanto, una vez optimizado, el método fue validado evaluando los siguientes parámetros: robustez, intervalo lineal y de trabajo, límite de detección y de cuantificación, selectividad, exactitud (repetibilidad y veracidad) e incertidumbre. El método fue aplicado para la medición de mercurio en un sedimento de presa con contenidos naturales de este analito. Los resultados se compararon con los obtenidos mediante espectrometría de masas con plasma inductivamente acoplado (ICP-MS) y espectrometría de fluorescencia atómica con generación de vapor frío (CV-AFS

La restauración del muelle embarcadero del Clevedon. Un ejemplo de implicación de la sociedad en la defensa del patrimonio cultural.

La ciudad de Clevedon, situada en la costa del Canal de Bristol, al suroeste de Inglaterra, es una población que conserva todavía la mayoría de sus edificios tradicionales y, entre ellos, el muelle de Clevedon, que está considerado hoy el ejemplo más bello e importante de los embarcaderos británicos del siglo XIX que aún permanecen en pie. En el año 1970, el ayuntamiento local decidió la reparación del muelle como atractivo local pero en una inadecuada prueba de carga, un pórtico del muelle se derrumbó y el muelle permaneció cerrado durante años hasta que, finalmente, el ayuntamiento, decidió derribarlo. La masiva respuesta popular a favor de su conservación, trascendió a la prensa nacional, y a la propia administración británica en materia de patrimonio, que lo catalogó como edificio protegido, Monumento de interés excepcional (Grade I), y prohibió su demolición. En el año 1980 se presentó un proyecto de reconstrucción del embarcadero y en 1992 terminaron las obras. El remozado muelle se inauguró con una fiesta popular a la que asistió la población de Clevedon ataviada de trajes victorianos en un acto que simbolizaba el triunfo del tesón puesto al servicio de la conservación de un edificio del mayor interés histórico y cultural que hoy luce en su esplendor y constituye un modelo de actuación en defensa del patrimonio arquitectónico industrial

Solar decathlon latino América y Caribe. Cali 2015 (Colombia), Proyecto AURA

Solar Decathlon Latin America and the Caribbean 2015 will take place in the city of Cali, Colombia. Coming from North America and after the European and Asian editions, now the competition for sustainable housing arrives Latin America. ‘Solar Decathlon’ is an international competition inviting students around the world from universities specialized in Engineering, Architecture, Urban Design, Renewable Energies and related careers to participate on creating, building and operating Self-sustaining social solutions, run by solar power. In addition to the founding principles of the original Solar Decathlon, the SD LAC2015 Organization has decided to focus on the following four components, which will be fundamental to the proposals in order to adapt them to tropical climate and cultural conditions. The components are: 1. Social Housing: As social inequality is one of the most pressing issues in Latin America and the Caribbean, the Solar Decathlon should strive to prove that sustainable housing based on alternative energy sources can be accessible to the population at large, prioritizing dense urban areas where most of the population is living. 2. Density: Nowadays, most of the population lives in cities where building areas are increasingly scarce and expensive. Moreover, denser housing solutions can help minimize the environmental impact. Consequently, the SD LAC2015 will favour projects that optimize the architectural and urban footprint. 3. Rational Use of Environmental Resources: The vast majority of the Latin American population lives in the tropics, enjoying high solar radiation all year long and exceptional availability of water sources. 4. Regional Relevance: The SD LAC2015 embraces the goal of developing and promoting ideas, capacities and technologies that can be implemented for the benefit of the inhabitants of the LAC region. The actual construction of prototypes will take place in the ‘Universidad del Valle’ campus. The competition combines both theoretical and practical knowledge considering projects must be built on real scale and be tested on 10 different contests. The hisCali team, from the Sevilla University, will take part in competition together with the ‘University of Santiago de Cali’, and with the support of the IUACC and the official masters of Innovation and Sustainability, both from the Sevilla University.El Decatlón Solar para América Latina y el Caribe - SD LAC2015 – se llevará a cabo en la ciudad de Cali, Colombia, convirtiéndose en la primera sede de esta versión del concurso, tras la primigenia norteamericana y las sucesivas versiones europeas y asiáticas. "Solar Decathlon" es un concurso internacional que invita a los estudiantes de las universidades especializadas en arquitectura, diseño urbano, energías renovables y carreras afines a que participen en el diseño, la construcción y la operación de soluciones de vivienda auto-sostenibles y energéticamente eficientes para contribuir a la mitigación del cambio climático a través de la implantación de tecnologías limpias. Los proyectos que se presentan a este concurso deben seguir un esquema reglamentario específico que se adapta a las condiciones climáticas y culturales de la región presentando propuestas de viviendas sociales como soluciones de impacto positivo para la región. 1. Vivienda Social: Debido a las circunstancias de desigualdad social y económica que enfrenta la región de América Latina y del Caribe, SDLAC2015 se presenta como un espacio dinámico de elaboración de propuestas y construcción de soluciones reales que impacten de manera positiva a la comunidad. 2. Densidad: Como consecuencia del desplazamiento masivo de la población hacia la zona urbana, una de las características de diseño y distribución que debe tenerse en cuenta para las construcciones del futuro es la densidad. 3. Uso Racional de Recursos del Medio Ambiente: La mayoría de la población de América Latina y del Caribe vive en la zona tropical, enfrentando emisiones de radiación solar a lo largo del año y una disponibilidad excepcional de las fuentes de agua. 4. Relevancia Regional: La meta será desarrollar ideas y tecnologías que beneficien a los habitantes de la región. El campus de la Universidad del Valle, en la ciudad de Cali, Colombia, es el escenario escogido para llevar a cabo la construcción real de los prototipos diseñados por cada equipo participante que serán evaluados en 10 pruebas diferentes a lo largo de la competencia. A esta convocatoria de Solar Decathlon Latino América y Caribe 2015, se presenta el equipo hísCali, con profesores de áreas de conocimiento de la Universidad de Sevilla tales como Construcción, Urbanismo, Proyectos, Estructuras, Derecho, Economía, Matemática Aplicada y Bellas Artes, junto con la Universidad de Santiago de Cali y con el apoyo del IUACC y los másteres de Innovación y de Sostenibilidad, ambos asimismo de la Universidad de Sevilla

Rare-EDIFICA-SOS: recuperación arquitectónica de lo inconcluso-obsoleto, desde una rehabilitación más sostenible

...ante el conjunto de edificios existentes que, por razones energéticas, históricas, estéticas o económicas, han dejado de ser considerados como eficientes desde el punto de vista de la habitabilidad contemporánea [obsoletos]... ...ante el conjunto de edificios en los cuales el hecho arquitectónico no ha llegado a ser completado, por razones ciertamente relacionadas con la deriva económico-social de los años precedentes, dando lugar a “elefantes blancos” varados a lo largo y ancho de la geografía andaluza [inconclusos]... ...ante el conjunto de edificios e inmuebles concluidos pero no habitados (o bien, habitados de manera a-legal), dando lugar a consideraciones y problemáticas sociales de imperiosa actualidad [quiméricos]... ...se habrán de conjeturar una serie de factores que, a la postre, repercutirán en la viabilidad de la conservación, reparación, consolidación, transformación, reforma, rehabilitación o, en definitiva, de su recuperación optimizada, con la premisa de que las construcciones a considerar constarán –en su mayoría- de condiciones tecnológicas, estructurales, constructivas y de materialidad distintas a las usuales hoy en día. Bajo tales consideraciones, el principal objetivo del trabajo de investigación sería la detección del conjunto de edificaciones obsoletas, inconclusas y quiméricas en Andalucía y su clasificación por grados de obsolescencia y falta de terminación, así como estado de ocupación para, tras una estratégica diagnosis sobre oportunidades de recuperación (en las que podría englobarse la viabilidad de nuevos usos o la aplicación de nuevas formas de gestión de la habitabilidad contemporánea), diseñar finalmente propuestas que permitan la recuperación de las edificaciones a través soluciones constructivas sostenibles para un ámbito característico (el hábitat mediterráneo), relacionadas con la envolvente del edificio y su rehabilitación energética....given the set of existing buildings that, for energetic, historical, aesthetic or economic reasons, are no longer considered efficient from the point of view of contemporary habitability [obsolete]... ...given the set of buildings in which the architectonic fact has not become completed, for reasons certainly related with the economic-social results from previous years, resulting white elephants stranded, in this case along the andalusian geography [inconclusive]... ...given the sets of constructed building uninhabited or habited but without the normal and legal consideration and social issues [chimeric]......then, a whole set of factors, that ultimately will have an impact on the viability of the maintenance, repair, consolidation, transformation, reform, rehabilitation or, definitively, its optimized recovery, will have to be surmised, with the premise that the constructions considered will feature, mostly, with technological, structural, constructive and materials conditions different from the actual. Under the above considerations, the main aim of the research would be the detection of the set of obsolete, inconclusive and chimeric buildings in Andalusia and its classification by degree of obsolescence, failure to complete and occupation status to, after a strategic diagnosis about opportunities recovery (in which could be encompassed the viability of new uses or the application of new management of contemporary habitability), design proposals that allow the recovery of buildings through sustainable constructional solutions for a characteristic mediterranean habitat, related to the building envelope and its energy rehabilitation

Integrated biorefineries: CO2 utilization for maximum biomass conversion

Biomass-derived fuels can contribute to energy sustainability through diversifying energy supply and mitigating carbon emissions. However, the biomass chemistry poses an important challenge, i.e., the effective hydrogen to carbon ratio is significantly lower for biomass compared to petroleum, and biomass conversion technologies produce a large amount of carbon dioxide by-product. Therefore, CO2 capture and utilization will be an indispensable element of future biorefineries. The present research explores the economic feasibility and environmental performance of utilizing CO2 from biomass pyrolysis for biodiesel production via microalgae. The results suggest that it is possible to increase biomass to fuel conversion from 55% to 73%. In addition, if subsidies and fuel taxes are included in the economic analysis, the extra produced fuel can compensate the cost of CO2 utilization, and is competitive with petroleum-derived fuels. Finally, the proposed integrated refinery shows promise as CO2 in the flue gas is reduced from 45% of total input carbon to 6% with another 19% in biomass residue waste streams

Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover

Phenolic oils were produced from fast pyrolysis of two different biomass feedstocks, red oak and corn stover, and evaluated in hydroprocessing tests for production of liquid hydrocarbon products. The phenolic oils were produced with a bio-oil fractionating process in combination with a simple water wash of the heavy ends from the fractionating process. Phenolic oils derived from the pyrolysis of red oak and corn stover were recovered with yields (wet biomass basis) of 28.7 and 14.9 wt %, respectively, and 54.3% and 60.0% on a carbon basis. Both precious metal catalysts and sulfided base metal catalyst were evaluated for hydrotreating the phenolic oils, as an extrapolation from whole bio-oil hydrotreatment. They were effective in removing heteroatoms with carbon yields as high as 81% (unadjusted for the 90% carbon balance). There was substantial heteroatom removal with residual O of only 0.4% to 5%, while N and S were reduced to less than 0.05%. Use of the precious metal catalysts resulted in more saturated products less completely hydrotreated compared to the sulfided base metal catalyst, which was operated at higher temperature. The liquid product was 42–52% gasoline range molecules and about 43% diesel range molecules. Particulate matter in the phenolic oils complicated operation of the reactors, causing plugging in the fixed-beds especially for the corn stover phenolic oil. This difficulty contrasts with the catalyst bed fouling and plugging, which is typically seen with hydrotreatment of whole bio-oil. This problem was substantially alleviated by filtering the phenolic oils before hydrotreating. More thorough washing of the phenolic oils during their preparation from the heavy ends of bio-oil or online filtration of pyrolysis vapors to remove particulate matter before condensation of the bio-oil fractions is recommended.Reprinted with permission from ACS Sustainable Chem. Eng., 2015, 3 (5), pp 892–902. Copyright 2015 American Chemical Society.</p

Radar on RAIA: High frequency radars in the RAIA Observatory

The RADAR ON RAIA project aims to update and extend beyond the Galician border the High Frequency (HF) radar network that has been operating since 2011 in the framework of the RAIA Observatory. The Project is allowing the establishment of a cross-border collaboration beyond the physical infrastructure itself, developing a sharing strategy of maintenance procedures, validation and data processing on both sides of the border, as well as an easy and public access to all the information. In addition, new products are being developed to exploit the potential of the HF radar technology.Peer Reviewe

FCC testing at bench scale: New units, new processes, new feeds

As the FCC process has evolved over decades, several laboratory scale equipment have appeared to maintain a proper assessment of catalysts activity. Several laboratory equipments are available for simulating the FCC process, from the well known fixed bed, MicroActivity Test to newer, fluid bed or transported bed units. As well, a number of units have been created to simulate other parts of the process such as regenerator or stripper, The increased pressure for treating non-conventional feeds, from reprocessing gasoline to extra-heavy feeds or oils produced from biomass containing large amounts of heteroatoms, increase the needs to have a laboratory test which is as close as possible to the process so that data extraction from the laboratory test are simplified, thus less prone to errors or misunderstanding.Financial support by MICINN (Consolider-Ingenio 2010 MULTICAT) and MINECO (Project MAT2011-29020-0O2-02 and Subprogram for excellence Severo Ochoa, SEV 2012 0267) is gratefully acknowledged.Corma Canós, A.; Sauvanaud, LL. (2013). FCC testing at bench scale: New units, new processes, new feeds. Catalysis Today. 218-219:107-114. doi:10.1016/j.cattod.2013.03.038S107114218-21