Novas tecnologias de produção de biocombustíveis: potencial para o sistema energético Português

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente, perfil Gestão e Sistemas Ambientais

Manutenção baseada no estado de condição. Uma abordagem utilizando cartas de controlo modificadas

Dissertação para obtenção do Grau de Doutor em Engenharia Industrial

Metanólise de óleo de soja em biodiesel através de um reactor de membrana

Com o aumento das necessidades energéticas, bem como dos cada vez mais conhecidos efeitos nocivos dos combustíveis fósseis, tornou-se imperativo pesquisar e desenvolver alternativas sustentáveis e verdes a esses recursos. O biodiesel é considerado como o melhor substituto para o combustível diesel convencional de base petroquímica. A transesterificação de óleos vegetais revela-se como uma importante via de obtenção do biodiesel. Na produção de biodiesel com catalisadores básicos homogéneos, como o hidróxido de sódio, deparamo-nos com um problema na hidrólise de triglicéridos, levando à formação de sabões e emulsões. Mesmo quando são usados reagentes secos, há formação de água devido à reacção do hidróxido com o álcool. Estes problemas podem ser solucionados com a utilização de catalisadores heterogéneos. Este estudo incidiu na preparação de membranas catalíticas de álcool polivinílico (PVA) incorporadas com um catalisador heterogéneo sólido básico (óxido de cálcio) obtido de resíduos industriais (casca de ovo). Caracterizaram-se as membranas catalíticas através da determinação da espessura, ângulos de contacto, grau de inchamento e espectroscopia de infravermelho. As membranas de PVA foram testadas na metanólise de óleo de soja em reactor batch e reactor de membrana catalítica. Estudou-se o efeito da reticulação química e por irradiação gama, nas propriedades das membranas e na actividade catalítica.

Ageing on commercial automotive catalysts, a structure reactivity study

Increasingly stringed regulations for diesel engine emissions have a significant impact on the required efficiency of DOC. Lowered DOC oxidation efficiency due to thermal aging effects influences the efficiency of the exhaust aftertreatment systems downstream of the DOC. In this work carried out in the Jean Le Rond d’Alembert Institute the effect of hydrothermal aging on the reactivity and structure of a commercial DOC was investigated. The characterization of the catalytic performance was carried out on a synthetic gas bench using carrots catalyst under conditions close to the realistic conditions i.e. using a synthetic gas mixture, representative of the exhaust gases from diesel engines. Different structural characterization techniques were performed: textural and morphological proprieties were analyzed by BET and TEM, the characterization of the presented crystallographic phases was performed by DRX and the determination of the number of reducible species was possible by TPR. TEM results shown, an increase of the metal particle size with the aging caused by the agglomeration of metal particles, revealing the presence of metal sintering. DRX results also suggest the presence of support sintering. Furthermore, DRX and BET results unexpectedly reveal that the most drastic aging conditions used actually activated the catalyst surface. As expected, the aging affected negatively the catalyst performance on the oxidation of methane and CO, however an improvement of the NO oxidation performance with the aging was observed. Nevertheless, for the aging conditions used, catalytic activity results show that the influence of aging in DOC performance was not significant, and therefore, more drastic aging conditions must be used.

Metanólise de óleo de soja em reator de membrana compósita PVA/casca de ovo calcinada. Estudo do efeito da reticulação

Com a crise energética atual e os efeitos nocivos associados ao consumo de combustíveis fósseis e seus derivados, tornou-se imperativo pesquisar e desenvolver alternativas sustentáveis e economicamente viáveis face a esse recurso. Surgiu então o biodiesel, um combustível derivado de recursos renováveis e potencial substituto do diesel convencional de base petroquímica. A transesterificação de óleos vegetais apresenta ser a principal via na produção de biodiesel. A utilização de catalisadores básicos homogéneos, tal como o hidróxido de sódio, na produção de biodiesel apresenta algumas adversidades, nomeadamente, o aparecimento de reações secundárias de hidrólise dos triglicéridos, na presença de água, que promovem a formação de sabões e emulsões. Mesmo com o uso de reagentes secos, ocorrem reações entre o hidróxido e o álcool, formando-se água. Uma solução para este tipo de problemas é a utilização de catalisadores heterogéneos. Contudo, a produção de biodiesel apresenta custos associados elevados que podem ser diminuídos com a utilização de catalisadores provenientes de resíduos alimentares. Este trabalho consistiu na preparação de membranas catalítica de álcool polivinílico (PVA) incorporadas com um catalisador heterogéneo sólido básico (óxido de cálcio) obtido a partir de resíduos alimentares industriais (casca de ovo de galinha). Procedeu-se à caraterização das membranas por determinação da espessura, ângulos de contato, grau de inchamento e por espectroscopia de infravermelho. As membranas de PVA foram testadas na transesterificação de óleo de soja com metanol em reator de membrana catalítica. Analisou-se o efeito da reticulação química nas propriedades das membranas e na atividade catalítica.

Fuel switching

The present Master dissertation is a project whose main objective is to identify value creation opportunities through fuel switching in the Portuguese industry, services, agriculture and fishing sectors. Fuel switching opportunities are characterized by type of fuel transition, type of technology transition, economy subsectors prone to have fuel switching and value created through fuel shift. Results suggest tomato concentrate, dairy, beer manufacturing and sugar refining subsectors is where prevalence of fuel oil steam boilers is high, for such cases conversion to natural gas steam boilers should result in operations having a ratio of NPV over CAPEX larger than ten and a payback period just under one year. Results further suggest food, beverages, textile, chemicals and wood subsectors currently operate between ten and twenty cogeneration Diesel engines that can be either modified to operate with natural gas or replaced by new natural gas cogeneration systems. Financial modeling indicates that both options have great value creation potential. The current analysis aims to be used by natural gas suppliers and energy project promoters to identify new potential deals as well as by heavy energy consumers to mitigate their energy related costs.

Ants obtained from trees of a "Jacareuba" (Calophyllum brasiliense) forest plantation in Central Amazonia by canopy fogging: first results

Canopies of the locally occurring Amazonian tree species Calophyllum brasiliense. Camb. (Guttiferae, height 10 m) were fogged after dawn on the same day at five adjacent localities in a 20-year-old plantation at the Adolpho Ducke Forest Reserve near Manaus/Brazil, using natural pyrethrum (0.5%, 1.0%, 1.5%), Baythroid (0.3%) and diesel oil, respectively. The 1152 ants collected represented 52 species, 17 genera and five subfamilies. The highest number of ant species was obtained with the synthetic pyrethrum Baythroid 0.3% and with natural pyrethrum 1.5%. About 46% of the total ant species were only collected in the first hour after fogging, and 17% only during the second hour, after trees had been heavily shaken. About 73% of the total ant specimens dropped in the first hour. Data on alpha-diversity, eveness and frequency of ants indicated a rapidly decreasing knock-down effect of both the synthetic and natural pyrethrum after application. The ant fauna in the canopy of C. brasiliense is somewhat distinct compared with that of Goupia glabra Aubl. (Celastraceae, height 45 m) from the primary forest of the reserve.

Engineering of fatty acid production and secretion in Saccharomyces cerevisiae

Tese de Doutoramento em Ciências - Especialidade em Biologia

Utilização de gás natural comprimido em veículos pesados de passageiros

Dissertação de mestrado em Engenharia Mecânica

Aromatic amines sources, environmental impact and remediation

Aromatic amines are widely used industrial chemicals as their major sources in the environment include several chemical industry sectors such as oil refining, synthetic polymers, dyes, adhesives, rubbers, perfume, pharmaceuticals, pesticides and explosives. They result also from diesel exhaust, combustion of wood chips and rubber and tobacco smoke. Some types of aromatic amines are generated during cooking, special grilled meat and fish, as well. The intensive use and production of these compounds explains its occurrence in the environment such as in air, water and soil, thereby creating a potential for human exposure. Since aromatic amines are potential carcinogenic and toxic agents, they constitute an important class of environmental pollutants of enormous concern, which efficient removal is a crucial task for researchers, so several methods have been investigated and applied. In this chapter the types and general properties of aromatic amine compounds are reviewed. As aromatic amines are continuously entering the environment from various sources and have been designated as high priority pollutants, their presence in the environment must be monitored at concentration levels lower than 30 mg L1, compatible with the limits allowed by the regulations. Consequently, most relevant analytical methods to detect the aromatic amines composition in environmental matrices, and for monitoring their degradation, are essential and will be presented. Those include Spectroscopy, namely UV/visible and Fourier Transform Infrared Spectroscopy (FTIR); Chromatography, in particular Thin Layer (TLC), High Performance Liquid (HPLC) and Gas chromatography (GC); Capillary electrophoresis (CE); Mass spectrometry (MS) and combination of different methods including GC-MS, HPLC-MS and CE-MS. Choosing the best methods depend on their availability, costs, detection limit and sample concentration, which sometimes need to be concentrate or pretreated. However, combined methods may give more complete results based on the complementary information. The environmental impact, toxicity and carcinogenicity of many aromatic amines have been reported and are emphasized in this chapter too. Lately, the conventional aromatic amines degradation and the alternative biodegradation processes are highlighted. Parameters affecting biodegradation, role of different electron acceptors in aerobic and anaerobic biodegradation and kinetics are discussed. Conventional processes including extraction, adsorption onto activated carbon, chemical oxidation, advanced oxidation, electrochemical techniques and irradiation suffer from drawbacks including high costs, formation of hazardous by-products and low efficiency. Biological processes, taking advantage of the naturally processes occurring in environment, have been developed and tested, proved as an economic, energy efficient and environmentally feasible alternative. Aerobic biodegradation is one of the most promising techniques for aromatic amines remediation, but has the drawback of aromatic amines autooxidation once they are exposed to oxygen, instead of their degradation. Higher costs, especially due to power consumption for aeration, can also limit its application. Anaerobic degradation technology is the novel path for treatment of a wide variety of aromatic amines, including industrial wastewater, and will be discussed. However, some are difficult to degrade under anaerobic conditions and, thus, other electron acceptors such as nitrate, iron, sulphate, manganese and carbonate have, alternatively, been tested.

Zylinderdruckbasierte Auflade- und Abgasrückführregelung für PKW-Dieselmotoren

Boost pressure, egr, cylinder pressure, ecu, model based control strategy, diesel engine

Modellierung der Ruß- und NOx-Emissionen des Dieselmotors

Diesel Engine, Soot- and NOx-Emissions, Potency Product Approaches, zero-dimensional Models, optical and thermodynamical Methods, semi-empirical, Combustion Strategy, Injection Rate Shape

Influences of alternative fuels and EGR on thermodynamic parameters and emissions of a heavy duty engine

Heavy duty Diesel engine, alternative fuels, EGR, exhaust emissions, HC, NOx, FSN

Oxidative potential for fine/ultrafine particles in occupational situations

Introduction : The redox properties of fine/ultrafine particles as well as nanoparticles (NP) are suggested to be important to explain their biological activity and could constitute a novel and promising metric for hazard evaluation. The acellular in vitro dithiothreitol (DTT) assay allows measuring this property. Objectives : (1) to evaluate sampling requirements for fine/ultrafine particle allowing measurement of their oxidative potential (2) to apply the methodology to occupational situations where particle from combustion sources are generated. Material and method : Sampling parameters (type of filters and loaded amount) and storage duration affecting the DTT measurements were evaluated. Based on these results, a methodological approach was defined and applied in two occupational situations where diesel and other combustion particles are present (toll station in a tunnel and mechanical yard for bus reparation). Results : Teflon filters loaded with diesel particles were found more suitable for the DTT assay, due to their better chemical inertness compared to quartz filters: after storage durations larger than 150 hours, an increased reactivity toward DTT was observed only with quartz filters. Reactivity was linearly correlated to the loaded mass until about 1000 μg/filter. Different redox reactivities were determined in both working places, with the mechanical yard presenting a higher DTT consumption rate. Discussion and conclusions : These results demonstrate the feasibility of this method to determine the oxidative potential of fine/ultrafine particles in occupational situations. We propose to include this approach for hazard assessment of work places with exposure to manufactured and other NP.

(No)competition in the Spanish retailing gasoline market: a variance filter approach

Various methodologies in economic literature have been used to analyse the international hydrocarbon retail sector. Nevertheless at a Spanish level these studies are much more recent and most conclude that generally there is no effective competition present in this market, regardless of the approach used. In this paper, in order to analyse the price levels in the Spanish petrol market, our starting hypothesis is that in uncompetitive markets the prices are higher and the standard deviation is lower. We use weekly retail petrol price data from the ten biggest Spanish cities, and apply Markov chains to fill the missing values for petrol 95 and diesel, and we also employ a variance filter. We conclude that this market demonstrates reduced price dispersion, regardless of brand or city.