An optimized process design for oxymethylene ether production from woody-biomass-derived syngas

The conversion of biomass for the production of liquid fuels can help reduce the greenhouse gas (GHG) emissions that are predominantly generated by the combustion of fossil fuels. Oxymethylene ethers (OMEs) are a series of liquid fuel additives that can be obtained from syngas, which is produced from the gasification of biomass. The blending of OMEs in conventional diesel fuel can reduce soot formation during combustion in a diesel engine. In this research, a process for the production of OMEs from woody biomass has been simulated. The process consists of several unit operations including biomass gasifi- cation, syngas cleanup, methanol production, and conversion of methanol to OMEs. The methodology involved the development of process models, the identification of the key process parameters affecting OME production based on the process model, and the development of an optimal process design for high OME yields. It was found that up to 9.02 tonnes day1 of OME3, OME4, and OME5 (which are suitable as diesel additives) can be produced from 277.3 tonnes day1 of wet woody biomass. Furthermore, an optimal combination of the parameters, which was generated from the developed model, can greatly enhance OME production and thermodynamic efficiency. This model can further be used in a techno- economic assessment of the whole biomass conversion chain to produce OMEs. The results of this study can be helpful for petroleum-based fuel producers and policy makers in determining the most attractive pathways of converting bio-resources into liquid fuels.

An optimized reverse-phase high performance liquid chromatographic method for evaluating percutaneous absorption of glucosamine hydrochloride

A relatively simple, selective, precise and accurate high performance liquid chromatography (HPLC) method based on a reaction of phenylisothiocyanate (PITC) with glucosamine (GL) in alkaline media was developed and validated to determine glucosamine hydrochloride permeating through human skin in vitro. It is usually problematic to develop an accurate assay for chemicals traversing skin because the excellent barrier properties of the tissue ensure that only low amounts of the material pass through the membrane and skin components may leach out of the tissue to interfere with the analysis. In addition, in the case of glucosamine hydrochloride, chemical instability adds further complexity to assay development. The assay, utilising the PITC-GL reaction was refined by optimizing the reaction temperature, reaction time and PITC concentration. The reaction produces a phenylthiocarbamyl-glucosamine (PTC-GL) adduct which was separated on a reverse-phase (RP) column packed with 5 microm ODS (C18) Hypersil particles using a diode array detector (DAD) at 245 nm. The mobile phase was methanol-water-glacial acetic acid (10:89.96:0.04 v/v/v, pH 3.5) delivered to the column at 1 ml min-1 and the column temperature was maintained at 30 degrees C. Galactosamine hydrochloride (Gal-HCl) was used as an internal standard. Using a saturated aqueous solution of glucosamine hydrochloride, in vitro permeation studies were performed at 32+/-1 degrees C over 48 h using human epidermal membranes prepared by a heat separation method and mounted in Franz-type diffusion cells with a diffusional area 2.15+/-0.1 cm2. The optimum derivatisation reaction conditions for reaction temperature, reaction time and PITC concentration were found to be 80 degrees C, 30 min and 1% v/v, respectively. PTC-Gal and GL adducts eluted at 8.9 and 9.7 min, respectively. The detector response was found to be linear in the concentration range 0-1000 microg ml-1. The assay was robust with intra- and inter-day precisions (described as a percentage of relative standard deviation, %R.S.D.) <12. Intra- and inter-day accuracy (as a percentage of the relative error, %RE) was <or=-5.60 and <or=-8.00, respectively. Using this assay, it was found that GL-HCl permeates through human skin with a flux 1.497+/-0.42 microg cm-2 h-1, a permeability coefficient of 5.66+/-1.6x10(-6) cm h-1 and with a lag time of 10.9+/-4.6 h.

Avaliação ecológica do efeito combinado de contaminantes ambientais

The assessment of ecological status of lotic freshwater bodies, based on stringent criteria of classification, has been defined by the Water Framework Directive (WFD), as a result of the implementation and optimization of methodologies that integrate physico-chemical, biological, and hydromorphological parameters. It is recognized that the application of this methodology is not easy, because it requires deep technical and scientific knowledge; it is time consuming in its application involving high financial costs. Thus, the main objective of this study was the development of cheaper and faster complementary methodologies that may contribute to the technical application of the classification criteria defined by the WFD, achieving the same final results of evaluation. In order to achieve this main goal, the river Mau, a small mountain river subjected to different stressors (eg, metals, pesticides), was established as the main sampling area. This thesis reviewed the historical development of various biotic indexes and its application in assessing water quality, especially highlighting the new paradigm defined by the WFD, and the corresponding actions developed for optimization and intercalibration of methodologies, evaluating the final state of water bodies. The ecological spatiotemporal characterization of the river Mau focused on the application of the WFD methodology, using at this stage only macroinvertebrates collected during four seasons. Results were compared with historical data of the last three years and they demonstrated that the river is in good condition. However, the ecological quality decreased at certain locations indicating that organisms were subjected to some type of disturbance. As the ecological quality can be conditioned by pulses of contamination from the sediments, in environmental adverse conditions, assays were performed with elutriates, obtained from sediments collected near the mining complex Braçal-Palhal. Results showed that this method was effective achieving the state of contamination, which may be important in prioritizing/scoring of critical areas within river ecosystems potentially impacted, using the WFD methodology. However, this methodology requires the collection of sediment which can promote the modification and / or loss of contaminants. To solve this potential problem, we developed a new methodology to obtain similar results. For this, we used a benthic microalga, belonging to the Portuguese flora, sensitive to organic pollution and metals. This methodology was optimized for application in situ, by immobilization of diatom in calcium alginate beads. The results showedthat their sensitivity and normal growth rate are similar to data obtained when used free cells of diatom. This new methodology allowed the achievement of a very quick response on the degree of contamination of a site, providing a complementary methodology to WFD.

Biovalorização de soro de queijo por processos anaeróbios/aeróbios

Este trabalho abordou a valorização de um subproduto da indústria de lacticínios (soro de queijo) através da alteração do funcionamento de processos habitualmente utilizados no contexto do tratamento biológico. Foi avaliada a fermentação acidogénica deste subproduto para maximizar a conversão do seu elevado teor de matéria orgânica em ácidos orgânicos voláteis (AOV) que actualmente são produtos com elevada procura, nomeadamente para produção de polihidroxialcanoatos (PHA). Em ensaios descontínuos e semi-contínuos foi caracterizada a produção e composição de AOV a partir de soro de queijo variando a razão food-to-microorganism (F/M) e a concentração de alcalinidade. Recorrendo à modelação dos resultados através de superfícies de resposta, demonstrou-se que condições de F/M = 4 gCQO g-1SSV combinadas com uma adição elevada de alcalinidade (8 g L-1 expresso como CaCO3) resultaram na conversão de 72% da CQO alimentada em AOV. O acetato e o butirato foram os AOV predominantes (60%), mas elevadas razões F/M combinadas com elevadas alcalinidades promoveram o alongamento da cadeia carboxílica, tendo sido produzidos AOV de maior massa molecular (iso-valerato e n-caproato). O processo de fermentação acidogénica foi posteriormente desenvolvido em modo contínuo num reactor MBBR acidogénico operado a longo prazo. Cargas orgânicas entre 30 e 50 gCQO L-1d-1 permitiram obter um grau de acidificação máximo de 68% no efluente fermentado. Foi ainda demonstrado que uma adição dinâmica de alcalinidade (0 – 4,8 g CaCO3 L-1) nestas condições estimulou a produção de AOV de cadeia ímpar (propionato e n-valerato) até 42%. O efluente acidificado no processo anaeróbio foi usado como substrato em reactores SBR operados para selecção de culturas microbianas mistas acumuladoras de PHA, nos quais foi aplicado um regime de alimentação dinâmica em condições aeróbias (“fartura-fome”). Estes sistemas operaram também a longo prazo, e demonstraram ser capazes de remover mais de 96% da CQO alimentada e simultaneamente convertê-la em PHA, até 36% do peso celular seco. A velocidade de remoção de substrato (valor máximo de 1,33 gCQO g-1SSV h-1) foi proporcional ao teor de polímero acumulado, evidenciando o estabelecimento de uma fase de “fome” prolongada que estimulou a selecção de microrganismos com elevada capacidade de acumulação de PHA. Além disso, o teor molar de hidroxivalerato (HV) no copolímero produzido [P(HB-co-HV)] foi directamente proporcional ao teor de AOV de cadeia ímpar (propionato e n-valerato) presente no soro fermentado que serviu de substrato. Uma estratégia de operação do reactor SBR com variação da carga orgânica, aliada ao regime “fartura-fome” estabelecido, permitiu ainda simular a realidade dos processos de tratamento biológico de efluentes, nos quais a composição e concentração inicial de matéria orgânica variam frequentemente. Este modo de operação do sistema estimulou notavelmente o processo de selecção de culturas acumuladoras de PHA tendo resultado num aumento da acumulação de PHA de 7% para 36%. Os resultados demonstraram com sucesso a possibilidade de valorização do soro de queijo através de eco-biotecnologia, contribuindo para uma mudança de paradigma no tratamento convencional de efluentes: ao invés de serem eliminados enquanto poluentes, os componentes orgânicos presentes neste subproduto industrial podem assim ser convertidos em materiais de valor acrescentado.

Emerging horizons for tick-borne pathogens: from the ‘one pathogen–one disease’ vision to the pathobiome paradigm

Ticks as vectors of several notorious zoonotic pathogens, represent an important and increasing threat for human, animal health in Europe. Recent application of new technology revealed the complexity of the tick microbiome that might impact upon its vectorial capacity. Appreciation of these complex systems is expanding our vision of tick-borne pathogens leading us to evolve a more integrated view that embraces the “pathobiome” representing the pathogenic agent integrated within its abiotic and biotic environments. In this review, we will explore how this new vision will revolutionize our understanding of tick-borne diseases. We will discuss the implications in terms of research approach for the future in order to efficiently prevent and control the threat posed by ticks.

Avaliação da iluminação UV-C como sistema de desinfeção eco-inovador em laranja minimamente processada

Dissertação de mest., Engenharia Biológica, Faculdade de Ciências e Tecnologia, Univ. do Algarve, 2011

Eco ventilação: desenvolvimento de uma ventilação mais ecológica

Neste trabalho é desenvolvido um estudo comparativo de vários sistemas de ventilação, baseados em jactos localizados. Foram avaliados, para cada um deles, o nível da qualidade do ar interior, conforto térmico, desconforto térmico local (risco de resfriamento) a que os ocupantes estão sujeitos e o índice ADI (Air Distribution Index). O estudo foi efectuado numericamente, a partir de dois softwares acoplados, e experimentalmente, a partir de uma sala de aula desenvolvida a escala real. Nesta sala de aulas, equipada com 6 ou 12 ocupantes e com 6 secretárias, foram analisados sistemas de ventilação com jactos verticais descendentes, localizados em cima (mais afastado e mais próximo do nível da cabeça dos ocupantes) e à frente dos ocupantes, e com jactos horizontais, localizados em frente dos ocupantes, em cima e em baixo da secretária. O estudo numérico, da interacção do escoamento com os ocupantes, foi efectuado a partir do acoplamento de um software que simula a resposta térmica dos ocupantes (Human Thermal Comfort) e um que simula o escoamento tridimensional em espaços ocupados (Virtual Air Flow - 3D), utilizando o modelo de turbulência RNG. Foi utilizada uma malha não uniforme, com um maior refinamento junto dos obstáculos e nas entradas e saídas de ar. No estudo do projecto do sistema de ventilação baseado em jactos verticais descendentes localizados em cima e mais afastado do nível da cabeça dos ocupantes, foram efectuadas medições experimentais de forma a validar os softwares acoplados e um modelo desenvolvido para calcular o escoamento unidireccional no interior de condutas. Neste estudo foi ainda utilizado um modelo de cálculo das temperaturas das superfícies. Por fim foi realizada uma simulação num contexto mais real, com 6 ocupantes sentados e um ocupante em pé, simulando 6 alunos e um professor, onde foi utilizado o acoplamento dos modelos Human Thermal Comfort e Virtual Air Flow - 3D, o modelo numérico de escoamentos unidireccionais no interior de condutas e o modelo de cálculo das temperaturas das superfícies. São ainda feitas sugestões para a partir deste trabalho, se efectuarem estudos em geometrias mais complexas.

Efficient content pushing in IEEE 802.11p vehicular environments

Vehicular networking is a new field that is expected to be widely adopted in the near future. One of the key applications inherent to this novel communications paradigm is content delivery to on-board users. In this paper we focus specifically on broadcast-based content delivery. We propose a content delivery scheme that is optimized for performance in order to improve the maximum amount of data than can be delivered, while also reducing delivery time to a minimum. With this goal our study combines both analytical and simulation results to determine the optimal packet size for content delivery so as to achieve the maximum throughput possible at different distances, and considering both static and mobile receivers. Experimental results show that our optimizations provide efficient delivery of multimedia contents for distances up to 200 meters when relying on IEEE 802.lip based broadcasting. Copyright © 2010 ACM.

Design e auto-produção : novos paradigmas para o design de artefactos na sociedade pós-industrial : a contribuição das tecnologias digitais

Tese de doutoramento, Belas-Artes (Design de Equipamento), Universidade de Lisboa, Faculdade de Belas-Artes, 2015

The "Eco" and "Low-carbon" promise: a critical review of China's experience

The scale and speed of China’s urbanization translate into major challenges for sustainability. Could the ‘eco-city’ and ‘low-carbon’ agendas, and the promotion of related pilot cities drive Chinese urban practice towards more environmentally sustainable solutions? We explore this question through a critical review of experience in China, identifying problems relating to the development of space, the treatment of scale and the pursuit of efficiency (the ‘space-scale-efficiency nexus’). China seeks sustainable solutions through eco and low-carbon agendas, but our review finds that current efforts fall short of expectations, and problematic patterns are repeated. We propose that a geo-administrative notion of functional regions could provide a strategic framework to address the range of design, physical and administrative planning problems, ensuring that eco-city and low-carbon city pilots result in comprehensive solutions that can be effectively replicated.

Can illusory deviant stimuli be used as attentional distractors to record vMMN in a passive three stimulus oddball paradigm?

A passive three stimulus oddball paradigm was used to investigate Visual Mismatch Negativity (vMMN) a component of the Event Related Potential (ERP) believed to represent a central pre-attentive change mechanism. Responses to a change in orientation were recorded to monochrome stimuli presented to subjects on a computer screen. One of the infrequent stimuli formed an illusory figure (Kanizsa Square) aimed to capture spatial attention in the absence of an active task. Nineteen electrodes (10-20 system) were used to record the electroencephalogram in fourteen subjects (ten females) mean age 34.5 years. ERPs to all stimuli consisted of a positive negative positive complex recorded maximally over lateral occipital areas. The negative component was greater for deviant and illusory deviant compared to standard stimuli in a time window of 170-190 ms. A P3a component over frontal/central electrodes to the illusory deviant but not to the deviant stimulus suggests the illusory figure was able to capture attention and orientate subjects to the recording. Subtraction waveforms revealed visual discrimination responses at occipital electrodes, which may represent vMMN. In a control study with 13 subjects (11 females; mean age 29.23 years), using an embedded active attention task, we confirmed the existence of an earlier (150-170 ms) and attenuated vMMN. Recordings from an intracranial case study confirmed separation of N1 and discrimination components to posterior and anterior occipital areas, respectively. We conclude that although the illusory figure captured spatial attention in its own right it did not draw sufficient attentional resources from the standard-deviant comparison as revealed when using a concurrent active task.

The continuing popularity of the neighbourhood and neighbourhood governance in the transition from the 'big state' to the 'big society' paradigm

The neighbourhood in both the UK and Europe continues to dominate thinking about the quality of life in local communities, representation and empowerment, and how local services can be delivered most effectively. For several decades a series of centrally funded programmes in neighbour- hood governance have targeted localities suffering deprivation and social exclusion in England. From these much can be learnt about the strengths and limitations of a local approach to achieving multiple objectives.We review the findings of a case study of neighbourhood governance in the City of Westminster and draw on evaluations of two national programmes. In the conclusions we discuss the problems arising from multiple objectives and examine the prospects for neighbourhood governance as the national paradigm moves away from `big state' solutions towards the less-well-defined `big society' approach and the reinvention of `localism'. While the rationale for neighbourhood governance may change, the `neighbourhood' as a site for service delivery and planning remains as important now as in the past.

Doing feminist research in a masculine paradigm

This paper aims to do three things; firstly the authors will present a case for their argument that marketing can be viewed as a masculine paradigm, secondly a critical perspective of traditional research methodologies within marketing and consumer research will be developed and, finally, the authors will share their own experiences of adopting alternative approaches and engaging in research reflexivity.