Desarrollo de catalizadores en sistemas de reacción avanzados para la producción de hidrógeno a partir de biogás

[ES]En el presente documento se expone el estudio experimental que consiste en la comparación de diferentes catalizadores en sistemas de reacción avanzados, microrreactores, para la producción de hidrógeno a partir de biogás. El hidrógeno es un vector energético que puede emplearse como combustible, y por tanto, un candidato perfecto para sustituir aquellos combustibles provenientes de fuentes fósiles. Este Proyecto de Fin de Grado se ha basado en desarrollar el proceso conocido como tri-reformado de biogás. Esta técnica, al contrario que las técnicas convencionales de producción, presenta numerosas ventajas ya que la materia prima empleada, el biogás, es una fuente de origen renovable. Para llevar a cabo este estudio se han preparado distintos catalizadores, basados todos ellos en platino. La elección de este metal noble es debido a su alto grado de reactividad, especialmente en sistemas de reacción micro-estructurados. Con el objetivo de reducir los costes asociados al propio catalizador, se añadieron, junto con el platino, otros metales más baratos a fin de analizar su idoneidad en el proceso del tri-reformado. Por tanto, partiendo de un catalizador de referencia que contiene un 5% de platino, se prepararon otros catalizadores mantenido constante, en un 5%, la composición de metal total. Estos catalizadores se han denominado de la siguiente manera: 2.5(Pt-Me), siendo Me cada especie metálica diferente. Tras preparar los catalizadores, se llevaron a cabo diferentes experimentos con un reactor convencional de lecho fijo. El objetivo fue establecer unas condiciones de operación tal que asegurasen una adecuada comparación entre catalizadores. De este modo, se realizaron ensayos de actividad catalítica a diferentes temperaturas y velocidades espaciales para someter a los catalizadores a condiciones de operación extremas, bajo las cuales, las diferencias entre catalizadores fueran más notorias. Una vez detalladas las condiciones de operación adecuadas para la comparación de catalizadores, se llevaron a cabo los correspondientes ensayos con los catalizadores impregnados en los sistemas de reacción avanzados, denominados micorreactores. Estos ensayos se basaron en operar a una velocidad espacial constante para estudiar la influencia de la temperatura. Además, se llevaron a cabo ensayos de estabilidad de hasta 110 horas en las condiciones de operación más desfavorables. Por último se compararon las conversiones de CH4 y CO2 y el rendimiento de H2 de todas las formulaciones catalíticas preparadas, y se concluyó que el mejor candidato para el proceso del tri-reformado es el catalizador 2.5(Pt-Pd).

Dynamics of convectively driven banded jets in the laboratory

The banded organization of clouds and zonal winds in the atmospheres of the outer planets has long fascinated observers. Several recent studies in the theory and idealized modeling of geostrophic turbulence have suggested possible explanations for the emergence of such organized patterns, typically involving highly anisotropic exchanges of kinetic energy and vorticity within the dissipationless inertial ranges of turbulent flows dominated (at least at large scales) by ensembles of propagating Rossby waves. The results from an attempt to reproduce such conditions in the laboratory are presented here. Achievement of a distinct inertial range turns out to require an experiment on the largest feasible scale. Deep, rotating convection on small horizontal scales was induced by gently and continuously spraying dense, salty water onto the free surface of the 13-m-diameter cylindrical tank on the Coriolis platform in Grenoble, France. A “planetary vorticity gradient” or “β effect” was obtained by use of a conically sloping bottom and the whole tank rotated at angular speeds up to 0.15 rad s−1. Over a period of several hours, a highly barotropic, zonally banded large-scale flow pattern was seen to emerge with up to 5–6 narrow, alternating, zonally aligned jets across the tank, indicating the development of an anisotropic field of geostrophic turbulence. Using particle image velocimetry (PIV) techniques, zonal jets are shown to have arisen from nonlinear interactions between barotropic eddies on a scale comparable to either a Rhines or “frictional” wavelength, which scales roughly as (β/Urms)−1/2. This resulted in an anisotropic kinetic energy spectrum with a significantly steeper slope with wavenumber k for the zonal flow than for the nonzonal eddies, which largely follows the classical Kolmogorov k−5/3 inertial range. Potential vorticity fields show evidence of Rossby wave breaking and the presence of a “hyperstaircase” with radius, indicating instantaneous flows that are supercritical with respect to the Rayleigh–Kuo instability criterion and in a state of “barotropic adjustment.” The implications of these results are discussed in light of zonal jets observed in planetary atmospheres and, most recently, in the terrestrial oceans.

The role of protecting groups in the formation of organogels through a nano-fibrillar network formed by self-assembling terminally protected tripeptides

A series of eight synthetic self-assembling terminally blocked tripeptides have been studied for gelation. Some of them form gels in various aromatic solvents including benzene, toluene, xylene, and chlorobenzene. It has been found that the protecting groups play an important role in the formation of organogels. It has been observed that, if the C-terminal has been changed from methyl ester to ethyl ester the gelation property does not change significantly (keeping the N-terminal protecting group same), while the change of the protecting group from ethyl ester to isopropyl ester completely abolishes the gelation property. Similarly, keeping the identical C-terminal protecting group (methyl ester) the results of the gelation study indicate that the substitution of N-terminal protection Boc-(tert-butyloxycarbonyl) to Cbz-(benzyloxycarbonyl) does change the gelation property insignificantly, while the change from Boc- to pivaloyl (Piv-) or acetyl (Ac-) group completely eliminates the gelation property. Morphological studies of the dried gels of two of the peptides indicate the presence of an entangled nano-fibrillar network that might be responsible for gelation. FTIR studies of the gels demonstrate that an intermolecular hydrogen bonding network is formed during gelation. Results of X-ray powder diffraction studies for these gelator peptides in different states (dried gels, gel, and bulk solids) reflected that the structure in the wet gel is distinctly different from the dried gel and solid state structures. Single crystal X-ray diffraction studies of a non-gelator peptide, which is structurally similar to the gelator molecules reveal that the peptide forms an antiparallel beta-sheet structure in crystals. (c) 2007 Elsevier Ltd. All rights reserved.

Particle image velocimetry measurements of turbulent flow within outdoor and indoor urban scale models and flushing motions in urban canopy layers

We investigate the spatial characteristics of urban-like canopy flow by applying particle image velocimetry (PIV) to atmospheric turbulence. The study site was a Comprehensive Outdoor Scale MOdel (COSMO) experiment for urban climate in Japan. The PIV system captured the two-dimensional flow field within the canopy layer continuously for an hour with a sampling frequency of 30 Hz, thereby providing reliable outdoor turbulence statistics. PIV measurements in a wind-tunnel facility using similar roughness geometry, but with a lower sampling frequency of 4 Hz, were also done for comparison. The turbulent momentum flux from COSMO, and the wind tunnel showed similar values and distributions when scaled using friction velocity. Some different characteristics between outdoor and indoor flow fields were mainly caused by the larger fluctuations in wind direction for the atmospheric turbulence. The focus of the analysis is on a variety of instantaneous turbulent flow structures. One remarkable flow structure is termed 'flushing', that is, a large-scale upward motion prevailing across the whole vertical cross-section of a building gap. This is observed intermittently, whereby tracer particles are flushed vertically out from the canopy layer. Flushing phenomena are also observed in the wind tunnel where there is neither thermal stratification nor outer-layer turbulence. It is suggested that flushing phenomena are correlated with the passing of large-scale low-momentum regions above the canopy.

Modelling the economics of farm-based anaerobic digestion in a UK whole-farm context

Anaerobic digestion (AD) technologies convert organic wastes and crops into methane-rich biogas for heating, electricity generation and vehicle fuel. Farm-based AD has proliferated in some EU countries, driven by favourable policies promoting sustainable energy generation and GHG mitigation. Despite increased state support there are still few AD plants on UK farms leading to a lack of normative data on viability of AD in the whole-farm context. Farmers and lenders are therefore reluctant to fund AD projects and policy makers are hampered in their attempts to design policies that adequately support the industry. Existing AD studies and modelling tools do not adequately capture the farm context within which AD interacts. This paper demonstrates a whole-farm, optimisation modelling approach to assess the viability of AD in a more holistic way, accounting for such issues as: AD scale, synergies and conflicts with other farm enterprises, choice of feedstocks, digestate use and impact on farm Net Margin. This modelling approach demonstrates, for example, that: AD is complementary to dairy enterprises, but competes with arable enterprises for farm resources. Reduced nutrient purchases significantly improve Net Margin on arable farms, but AD scale is constrained by the capacity of farmland to absorb nutrients in AD digestate.

Family language policy in the Chinese community in Singapore: a question of balance?

This paper focuses on the language shift phenomenon in Singapore as a consequence of the top-town policies. By looking at bilingual family language policies it examines the characteristics of Singapore’s multilingual nature and cultural diversity. Specifically, it looks at what languages are practiced and how family language policies are enacted in Singaporean English-Chinese bilingual families, and to what extend macro language policies – i.e. national and educational language policies influence and interact with family language policies. Involving 545 families and including parents and grandparents as participants, the study traces the trajectory of the policy history. Data sources include 2 parts: 1) a prescribed linguistic practices survey; and 2) participant observation of actual negotiation of FLP in face-to-face social interaction in bilingual English-Chinese families. The data provides valuable information on how family language policy is enacted and language practices are negotiated, and what linguistic practices have been changed and abandoned against the background of the Speaking Mandarin Campaign and the current bilingual policy implemented in the 1970s. Importantly, the detailed face-to-face interactions and linguistics practices are able to enhance our understanding of the subtleties and processes of language (dis)continuity in relation to policy interventions. The study also discusses the reality of language management measures in contrast to the government’s ‘separate bilingualism’ (Creese & Blackledge, 2011) expectations with regard to ‘striking a balance’ between Asian and Western culture (Curdt-Christiansen & Silver 2013; Shepherd, 2005) and between English and mother tongue languages (Curdt-Christiansen, 2014). Demonstrating how parents and children negotiate their family language policy through translanguaging or heteroglossia practices (Canagarajah, 2013; Garcia & Li Wei, 2014), this paper argues that ‘striking a balance’ as a political ideology places emphasis on discrete and separate notions of cultural and linguistic categorization and thus downplays the significant influences from historical, political and sociolinguistic contexts in which people find themselves. This simplistic view of culture and linguistic code will inevitably constrain individuals’ language expression as it regards code switching and translanguaging as delimited and incompetent language behaviour.

The role of subsidy in ensuring the sustainability of small-scale anaerobic digesters in Odisha, India

Small-scale anaerobic digester installation has been a development objective of the Indian government to provide rural households clean fuel. Anaerobic digester installation is heavily subsidised. Depending on caste, the rate of subsidy offered for the smallest system available (1m3) varies between 32.35% and 41.18% of the total installation price. Yet, there are gaps in knowledge regarding the usefulness of such subsidies from a sustainability perspective. A cost-benefit analysis was conducted to evaluate the circumstances required for digester sustainability. The analysis used household data collected from 115 cattle owning households in Odisha, India to evaluate profitability at three levels of subsidy (none, General caste subsidy, and Schedule Caste/Schedule Tribe subsidy). Additional analyses considered the effect of; taking a loan, replacing electric lighting with biogas lighting, and the wealth level of the household. The results indicated that access to subsidy improved profitability. Yet, profitability could be achieved without the use of subsidy. The level of benefit accrued by households was similar independent of wealth. However, the provision of subsidy was essential for ensuring profitability for those households required to take a loan to meet the expense of installation. Such findings highlight the importance of subsidy as a means of including the poor.

Methane conversion reactions on Ni catalysts promoted with Rh: Influence of support

Ni catalysts supported on gamma-Al(2)O(3) and Mg(Al)O were prepared with and without Rh as a promoter and tested in the reforming of methane in the presence of excess methane, simulating a model biogas. The effects of adding synthetic air on the methane conversion and the formation of carbon were assessed. The catalysts were characterized by X-ray spectroscopy (EDS), surface area (BET), X-ray diffraction (XRD), Temperature-programmed reduction (TPR), X-ray absorption near-edge structure (XANES) and XPD. The results showed that in catalysts without Rh, the Ni interacts strongly with the supports, showing high reduction temperatures in TPR tests. The addition of Rh increased the amount of reducible Ni and facilitated the reduction of the species interacting strongly with the support. In the catalytic tests, the samples promoted with Rh suffered higher carbon deposition. The in situ XPD suggested that on the support gamma-Al(2)O(3), the presence of Rh probably led to a segregation of Ni species with time on stream, leading to carbon deposition. On the support MgAlO, the presence of Rh improved the dispersion of Ni, by reducing the Ni(0) crystallite size, suggesting that in this case the carbon deposition was due to a favoring of CH(4) decomposition by Rh. (C) 2011 Elsevier B.V. All rights reserved.

Ferramenta computacional para a medição de campos de velocidade utilizando processamento digital de imagens

A proposta deste trabalho, consiste na elaboração de uma ferramenta computacional para a medição de campos de velocidades em escoamentos com baixas velocidades (< 0,5 m/s) utilizando o processamento digital de imagens. Ao longo dos anos, inúmeras técnicas foram desenvolvidas com este objetivo. Para cada tipo de aplicação, uma técnica se aplica com maior ou menor eficiência do que outras. Para o caso de estudos em fluídos transparentes, onde o escoamento pode ser visualizado, técnicas que utilizam processamento digital de imagens vêm ganhando um grande impulso tecnológico nos últimos anos. Este impulso, é devido a fatores como: câmaras vídeo filmadoras de última geração, dispositivos de aquisição de imagens e componentes de processamento e armazenamento de dados cada vez mais poderosos. Neste contexto, está a velocimetria por processamento de imagens de partículas cuja sigla é PIV (particle image velocimetry). Existem várias formas de se implementar um sistema do tipo PIV. As variantes dependem, basicamente, do equipamento utilizado. Para sua implementação é necessário, inicialmente, um sistema de iluminação que incide em partículas traçadoras adicionadas ao fluido em estudo. Após, as partículas em movimento são filmadas ou fotografadas e suas imagens adquiridas por um computador através de dispositivos de captura de imagens. As imagens das partículas são então processadas, para a obtenção dos vetores velocidade. Existem diferentes formas de processamento para a obtenção das velocidades. Para o trabalho em questão, devido às características dos equipamentos disponíveis, optou-se por uma metodologia de determinação da trajetória de partículas individuais, que, apesar de limitada em termos de módulo de velocidade, pode ser aplicada a muitos escoamentos reais sob condições controladas Para validar a ferramenta computacional desenvolvida, imagens ideais de partículas foram simuladas como se estivessem em escoamento, através do deslocamento conhecido de vários pixels. Seguindo o objetivo de validação, foi utilizada ainda uma imagem real de partículas, obtida com o auxílio de um plano de iluminação de luz coerente (LASER) e câmaras de vídeo tipo CCD. O programa desenvolvido foi aplicado em situações de escoamento real e os resultados obtidos foram satisfatórios dentro da escala de velocidades inicialmente presumida.

Projeto e implementação de um sistema de instrumentação eletro-eletrônica para caracterização de escoamentos através de processamento digital de imagens

Historicamente, devido à incompreensibilidade dos fenômenos físicos envolvidos, diversas técnicas de análise experimental de escoamentos foram desenvolvidas. Inicialmente, estas técnicas consistiam em uma simples visualização do escoamento em questão. Visava-se com isto produzir a intuição física a respeito do sistema físico para que futuras teorias pudessem ser formuladas. No entanto, nos anos posteriores, tornou-se necessária a criação de técnicas quantitativas. Neste segmento, a evolução tecnológica da eletrônica propiciou que técnicas intrusivas e não intrusivas fossem criadas. Tal processo culminou com o surgimento da microeletrônica, quando sensores eletrônicos de imagem puderam ser fabricados. Assim, técnicas não intrusivas de velocimetria através de processamento digital de imagens tornaram-se referência, possibilitando a medição de campos de velocidade do escoamento em análise. Tais técnicas são atualmente utilizadas não apenas no meio acadêmico, na investigação da turbulência, como na indústria, em projetos de engenharia que envolvam alta tecnologia. Neste trabalho, apresenta-se uma metodologia para a concepção de um sistema de velocimetria de 2 dimensões por processamento digital de imagens. Para tanto, o sistema de velocimetria foi dividido em duas partes, sendo os equipamentos bem como os conceitos físicos envolvidos em cada uma analisados e descritos Por fim, projetou-se e implementou-se um sistema de velocimetria de 2 dimensões através de processamento digital de imagens, modo PIV. A sua validação foi efetuada sobre um escoamento altamente turbulento interno a um duto circular, cuja solução é conhecida e exaustivamente estudada no decorrer dos anos. O resultado obtido se apresentou totalmente satisfatório e demonstrou a grande importância atual de tal técnica de medição.

Biogás no estado de São Paulo: novo potencial em um mercado restringido

O trabalho tem como objetivo apresentar o aproveitamento de biogás de aterros como uma alternativa potencial à utilização de gás natural no Estado de São Paulo. O trabalho descreve a produção de biogás e os principais desafios para levar o produto final ao mercado. São descritos os benefícios, tanto econômicos e energéticos quanto ambientais, do aproveitamento de um recurso que é geralmente esquecido. O trabalho analisará o perfil da produção de biogás de aterros no Brasil e como a regulação interage com uma indústria que em grande parte é nova. O trabalho propõe umas ideias a respeito de fontes de verbas para novos projetos, além de analisar algumas experiências internacionais. Utilizando teoria econômica, o trabalho tentará mostrar como esta fonte de energia poderia ser introduzida no mercado, mesmo sob condições econômicas desafiadoras.

Solução Geral de Sistema Linear

Quando a matriz de um sistema linear se encontra na forma escalonada reduzida por linhas é fácil escrever sua solução nesse sistema. Assim, esta videoaula explica como obter a solução geral apresentando as metodologias que serão usadas dependendo de cada caso e as maneiras distintas de achar uma solução geral de um sistema.