Síntese de acetato de decilo por catálise enzimática em meio supercrítico

Este trabalho teve como objectivo o estudo, em reactor fechado, da produção de ésteres de cadeia longa por catálise enzimática em meio supercrítico com vista ao desenvolvimento de um processo sustentável, tecnologicamente eficiente e limpo e que constitua uma alternativa aos processos químicos tradicionais. Como composto modelo a produzir foi seleccionado o acetato de decilo, um éster com aplicação na indústria de fragrâncias. A reacção estudada foi a transesterificação do acetato de vinilo com o decanol, obtendo-se como principal produto o acetato de decilo. O catalisador escolhido foi a lipase B de Candida antarctica (CALB), imobilizada na resina macroporosa Lewatit B (Novozym 435®). A síntese de acetato de decilo foi estudada numa instalação experimental de alta pressão, equipada com um reactor fechado de volume variável, a operar isotermicamente a 35 ºC e a 100 bar, usando-se como solvente CO2 em condições supercríticas. Fez-se a determinação do conteúdo enzimático por tamanho de partícula de catalisador, tendo-se verificado que as partículas mais pequenas têm uma quantidade específica de enzima mais elevada, havendo uma relação inversamente proporcional entre o conteúdo enzimático e o tamanho de partícula. Verificou-se também que a enzima deve estar localizada numa camada exterior da partícula, seguindo um modelo do tipo “casca de ovo”, sendo a espessura dessa camada de 60 μm (assumindo distribuição uniforme) e independente do tamanho de partícula. Analisaram-se as resistências à transferência de massa, tanto externas como internas. Para as primeiras, fez-se apenas variar a agitação dentro do reactor, mantendo todas as outras condições de operação constantes (temperatura, pressão, quantidade de enzima, tamanho de partícula, concentração de substratos na alimentação). Verificou-se que a partir de 950 r.p.m. as resistências externas à transferência de massa são eliminadas. Relativamente às resistências internas, realizaram-se várias reacções com diferentes tamanhos de partícula, mas com a mesma quantidade de enzima, a mesma concentração dos dois substratos na alimentação, a mesma agitação, temperatura e pressão. Os resultados obtidos mostram que não há influência significativa do tamanho das partículas de catalisador sobre a velocidade inicial de reacção, pelo que as resistências internas à transferência de massa se podem considerar desprezáveis. Estudou-se também o efeito da variação da concentração dos substratos na alimentação sobre as velocidades iniciais de reacção. Observou-se que a partir de uma determinada concentração de decanol em excesso relativamente ao acetato de vinilo, a reacção é inibida pelo álcool. Pelo contrário, a reacção é favorecida quando a alimentação tem excesso de acetato de vinilo, havendo um aumento significativo da sua velocidade inicial. Estes resultados são consistentes com um mecanismo do tipo Ping-pong bi-bi com inibição competitiva por parte do álcool, comum na descrição de reacções enzimáticas de esterificação/transesterificação. Por último, fez-se uma comparação dos resultados obtidos em meio supercrítico (CO2) e em meio orgânico (hexano). Observou-se que as reacções em hexano apresentam uma velocidade inicial significativamente superior.

Evolução geológica de Portugal continental durante o Cenozóico - sedimentação aluvial e marinha numa margem continental passiva (Ibéria ocidental)

6º Simposio sobre el Margen Ibérico Atlántico MIA09

Biocombustível a partir de celulose – hidrogenação de isómeros da hidroximetilpiranona

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Química e Bioquímica

The Neogene of the Lower Tagus Basin (Portugal)

Revista Española de Paleontologia 19 (2), 229-242

Recuperação de nanopartículas metálicas por ultrafiltração

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Química e Bioquímica

Membrane design and characterisation by incorporation of ionic liquids

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química, especialidade de Operações Unitárias e Fenómenos de Transferência, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Análise do comportamento alimentar de uma população escolar do concelho de Sintra

Dissertação apresentada para obtenção do Grau de Mestre em Tecnologia Alimentar/Qualidade pela Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa

La cuirasse ferrugineuse conglomératique de Cabatuquila (Malanje - R. P. d'Angola) et sa signification paléogéographique

Cabatuquila conglomerate ferricrete (Malanje Province, located North Central Angola) corresponds to a thick (1O-15m) and hardcornice at the top of "Baixa de Cassanje" escarpment. "Baixa de Cassanje" is a large graben part of South Congo basin. Cabatuquila conglomerate ferricrete seems to correspond to a Plio-Pleistocene morphology which has already disappeared. Laterization dynamics and ferricrete formation processes took place on the Tertiary surface, before being tilted to the Congo Basin. Materials submitted to these processes are mainly alluvial deposits from a pre-Cuanza drainage system. This drainage system flowed to the North before being captured to the Atlantic, as a consequence of the movement which deformed the Tertiary surface during the Pleistocene. The erosion dynamics, which created the Cassanje depression, has occurred after the late Tertiary surface deformation. That dynamics might be related to the Cuango drainage system, which was reorganized after that deformation.

Les formations fluviatiles quaternaires de la plaine de Doukkala (Méséta Occidentale Marocaine). Sédimentologie et nouvelles données chronostratigraphiques

The Quaternary fluvial formations of the Doukkala plain are, until now, slightly studied. Our study has allowed to precise that the fluvial terraces of the oued "the Ourn Rbia oued", are clearly distinguished from the secondary oueds terraces by the dynamic deposit of the alluvial materials. Moreover, the mammal fossils recolted from some of these terraces allow to review the ages attributed by Gigout (1951).

Assinatura tectono-sedimentar do auge da compressão bética em Portugal: a descontinuidade sedimentar Valesiano terminal-Turoliano

An Upper Miocene important sedimentary break can be accurately recognised in the Portuguese basins and is reflected by a drastic palaeogeographic change in relation to a large-scale tectonic event of probable uppermost Vallesian-Turolian (9,5 Ma; middle Tortonian) age. The characterisation of the sedimentary record of this tectonic event, as well as its relations with interpreted active faults is made for different situations: Douro (NW border), Mondego, Lower-Tagus and Sado Tertiary basins. The sedimentary record, considered upper Tortonian-Messinian ? (uppermost Vallesian-Turolian ?) is interpreted mainly as endorheic alluvial fans (internal drainage), developed along active NNE-SSW indent-linked strike-slip faults and NE-SW reverse faults. At NE Portugal, proximal fluvial systems of an endorheic hydrographic network drained eastwards to the Spanish Duero interior Basin. The main evidences of the betic compression clímax in Portugal mainland are presented; the interpreted active tectonic structures are in accordance with an intense NNW-SSE crustal shortening, but some regional differences are also documented.

Estratigrafia e interpretação paleogeográfica do Cenozóico continental do norte de Portugal

Palaeogeographic and tectono-sedimentary interpretation of northern Portugal, in which previous studies (geomorphology, lithostratigraphy, mineralogy, sedimentology, palaeontology, etc.) were considered, is here proposed. Cenozoic shows different features according to its morphotectonic setting in the eestern region (Trás-os-Montes) or near to the Atlantic coast (western region, Minho and Douro Litoral areas). Although in the eastern region the sedimentary record is considered late Neogene, in some places Paleogene (?) was identified. This oldest record, represented by alluvial deposits, was preserved from complete erosion because of its position inside Bragança-Vilariça-Manteigas fault zone grabens. Later sedimentary episodes (upper Tortonian-Zanclean ?), represented by two allostratigraphical units, were interpreted as proximal fluvial braided systems of an endorheic hydrographic network, draining to the Spanish Duero Basin (eastwards); nowadays, they still remained in tectonic depressions and incised-valleys. Later on, eastern sedimentation becomes scarcer because Atlantic fluvial systems (e.g. the pre-Douro), successively, captured previous endorheic drainages. The proximal reaches of the allostratigraphic unit considered Placencian is recorded in Mirandela (western Trás-os-Montes) but the following fluvial episode (Gelasian-early Pleistocene ?) was already documented in east Trás-os-Montes, preserved in high platforms and in tectonic depressions. Placencian and Quaternary sedimentary records in the western coastal zone, mainly represented by terraces, are located in the Minho, Lima, Alverães, Cávado and Ave large fluvial valleys and in the Oporto littoral platform. In conclusion, northern Portugal Tertiary sedimentary episodes were mainly controlled by tectonics, but later on (Placencian-Quaternary) also by eustasy.

Mineralogia da fracção argilosa da Formação de Vale Álvaro (Bragança, NE Portugal)

The studied materials were sampled from several conglomerate and carbonate sandstone units, overlapped for 23 meters. This formation represents a debris flow dominated alluvial fan alternating with quiet sedimentary conditions. These deposits of probably Paleogene age were placed upon mafic and ultramafic rocks that are the exclusive source of sediments. Optical and SEM identification, microanalysis and XRD studies (with decomposition procedures) of clay fractions obtained after high-speed centrifugation were performed in order to characterise the clay minerals content. The results of the analytical program allowed the establishment of the following remarks: a) Fe-rich montmorillonite dominance over paligorskite, chlorite, chlorite-smectite mixed-layers, serpentine and talc; b) smectites in the 12.4 - 15 A range, expanding to about 17 A after EG treatment; c) serpentine and talc as secondary minerals in the interior of altered clasts; d) chlorite and clorite smectite mixed-layer compositions in the borders of the clasts and in the cement. The composition of sediments results from coarse clasts eroded from mafic and ultramafic rocks and clayey material. Clasts show evidences of post-depositional weathering (coatings of chlorite and smectite). Clayey material has the contributions of i) inherired chlorite, smectite and chlorite-smectite mixed-layers; ii ) authigenic crystallisation of Fe-montmorillonite (due to availability of Fe in the crystallising solutions following previous weathering events); iii) authigenic paligorskite associated to a carbonate cement.

Evolução cenozóica da área de Longroiva-Vilariça (NE Portugal)

In the Longroiva-Vilariça area, the identification of Cenozoic lithostratigraphic units, the sedimentology and the characterization of its geometric relations with tectonic structures allowed the interpretation of the palaeogeographic main stages: 1) the greenwhitish Vilariça Arkoses (Middle Eocene to Oligocene ?) represent proximal sediments of a very low gradient drainage towards the eastern Spanish Tertiary Duero Basin; 2)Quintãs Formation (late Miocene ?) are brown-reddish coloured piedmont alluvial deposits, correlative of important vertical displacement (western tectonic block relative uplift) along the NNE-SSW indent-linked strike-slip Bragança-Vilariça-Longroiva fault zone, interpreted as a reactivated deep hercynian fracture, with left-lateral movement; 3) the red Sampaio Formation (Gelasian-early Pleistocene ?)was interpreted as downhill conglomeratic deposits related with important overtrusting along this fault zone (the definition of the present-day narrow graben configuration) and correlative of the atlantic hydrographic incision stage beginning; 4) conglomeratic terraces (middle and late Pleistocene ?); 5) alluvial plains and colluvial deposits (Holocene).

Depósitos continentais e marinhos na plataforma litoral da região do Porto. Importância da tectónica na sua organização espacial

One of the most common characteristics of Portuguese littoral is the existence of a planed surface (the so-called "littoral platform"), situated at different altitudes and bordered from the inland by a straight relief, strongly contrasting with that planed surface. This one is generally covered with several outcrops of the so-called Plio-Pleistocene deposits. Till the eighties this platform has been interpreted as stable staircase of old marine levels, registering in a passive way the eustatic variations. The rigid step bordering it easterly should be a fossil cliff. However, our study has proved that many of these deposits have a continental origin. These continental deposits have fluvial or alluvial fan facies and they are lying above 40 meters. Marine deposits seem to be quite rare and they only occupy a small western area, beneath the altitude of 40 meters and developing into three different marine levels. There is a rigid step between the two kinds of deposits. We think that the clear geometric separation between these deposits together with this rigid step, indicates a tectonic origin. It seems that the sea must have touched only the western part of this surface, when neotectonic movements lowered it down. There are more evidences for neotectonic movements: a) there are faults (mainly inverse faults) affecting the higher deposits of this littoral platform; b) the same marine level seems to appear at different altitudes, developing an irregular pattern with a general trend dipping from the North to the South.

Litostratigrafia do Terciario da região Miranda do Corvo-Viseu (Bacia do Mondego, Portugal)

The lithostratigraphic units (2 groups, 5 formations and 4 members) of the Tertiary of the Miranda do Corvo-Viseu region (Central Portugal) are here described. For each unit the characterization and description (boundaries, diagnostic properties and atributes) were included. The stratigraphic, lithological, sequential and tectonic data allow correlations with other units of the same Tertiary basin located more to west and support the chronostratigraphic attribution. Sedimentologic characteristics of the deposits lead to the interpretation of the influence of tectonism, climate and eustasy during the sedimentary evolution of this Basin.