Optimization of wastewater quality in the Sines refinery

In order to address and resolve the wastewater contamination problem of the Sines refinery with the main objective of optimizing the quality of this stream and reducing the costs charged to the refinery, a dynamic mass balance was developed nd implemented for ammonia and polar oil and grease (O&G) contamination in the wastewater circuit. The inadequate routing of sour gas from the sour water stripping unit and the kerosene caustic washing unit, were identified respectively as the major source of ammonia and polar substances present in the industrial wastewater effluent. For the O&G content, a predictive model was developed for the kerosene caustic washing unit, following the Projection to Latent Structures (PLS) approach. Comparison between analytical data for ammonia and polar O&G concentrations in refinery wastewater originating from the Dissolved Air Flotation (DAF) effluent and the model predictions of the dynamic mass balance calculations are in a very good agreement and highlights the dominant impact of the identified streams for the wastewater contamination levels. The ammonia contamination problem was solved by rerouting the sour gas through an existing clogged line with ammonia salts due to a non-insulated line section, while for the O&G a dynamic mass balance was implemented as an online tool, which allows for prevision of possible contamination situations and taking the required preventive actions, and can also serve as a basis for establishing relationships between the O&G contamination in the refinery wastewater with the properties of the refined crude oils and the process operating conditions. The PLS model developed could be of great asset in both optimizing the existing and designing new refinery wastewater treatment units or reuse schemes. In order to find a possible treatment solution for the spent caustic problem, an on-site pilot plant experiments for NaOH recovery from the refinery kerosene caustic washing unit effluent using an alkaline-resistant nanofiltration (NF) polymeric membrane were performed in order to evaluate its applicability for treating these highly alkaline and contaminated streams. For a constant operating pressure and temperature and adequate operating conditions, 99.9% of oil and grease rejection and 97.7% of chemical oxygen demand (COD) rejection were observed. No noticeable membrane fouling or flux decrease were registered until a volume concentration factor of 3. These results allow for NF permeate reuse instead of fresh caustic and for significant reduction of the wastewater contamination, which can result in savings of 1.5 M€ per year at the current prices for the largest Portuguese oil refinery. The capital investments needed for implementation of the required NF membrane system are less than 10% of those associated with the traditional wet air oxidation solution of the spent caustic problem. The operating costs are very similar, but can be less than half if reusing the NF concentrate in refinery pH control applications. The payback period was estimated to be 1.1 years. Overall, the pilot plant experimental results obtained and the process economic evaluation data indicate a very competitive solution through the proposed NF treatment process, which represents a highly promising alternative to conventional and existing spent caustic treatment units.

Water treatments in semi-closed cooling circuits and their impact on the quality of effluents discharged by CERN

Dissertação apresentada à Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia do Ambiente, Gestão de Sistemas Ambientais

Water treatments in semi-closed cooling circuits and their impact on the quality of effluents discharged by CERN

Mestrado integrado em Engenharia do Ambiente, perfil: Gestão de Sistemas Ambientais

Acidogenic digestion of effluents of the cheese industry in packed bed biofilm reactors

Dissertation for the Master degree in Biotechnology

Industrial symbiosis potential of the Sines oil refinery – environmental and economic evaluation

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente – Perfil Gestão e Sistemas Ambientais

Transport mechanism in ionic liquid membranes and the study of thiomersal biodegradation

The initial goal of this work was the development of a supported liquid membrane (SLM) bioreactor for the remediation of vaccine production effluents contaminated with a highly toxic organomercurial – thiomersal. Therefore, two main aspects were focused on: 1) the development of a stable supported liquid membrane – using room temperature ionic liquids (RTILs) – for the selective transport of thiomersal from the wastewater to a biological compartment, 2) study of the biodegradation kinetics of thiomersal to metallic mercury by a Pseudomonas putida strain. The first part of the work focused on the evaluation of the physicochemical properties of ionic liquids and on the SLMs’ operational stability. The results obtained showed that, although it is possible to obtain a SLM with a high stability, water possesses nonnegligible solubility in the RTILs studied. The formation of water clusters inside the hydrophobic ionic liquid was identified and found to regulate the transport of water and small ions. In practical terms, this meant that, although it was possible to transport thiomersal from the vaccine effluent to the biological compartment, complete isolation of the microbial culture could not be guaranteed and the membrane might ultimately be permeable to other species present in the aqueous vaccine wastewater. It was therefore decided not to operate the initially targeted integrated system but, instead, the biological system by itself. Additionally, attention was given to the development of a thorough understanding of the transport mechanisms involved in the solubilisation and transport of water through supported liquid membranes with RTILs as well as to the evaluation of the effect of water uptake by the SLM in the transport mechanisms of water-soluble solutes and its effect on SLM performance. The results obtained highlighted the determinant role played by water – solubilised inside the ionic liquids – on the transport mechanism. It became clear that the transport mechanism of water and water-soluble solutes through SLMs with [CnMIM][PF6] RTILs was regulated by the dynamics of water clusters inside the RTIL, rather than by molecular diffusion through the bulk of the ionic liquid. Although the stability tests vi performed showed that there were no significant losses of organic phase from the membrane pores, the formation of water clusters inside the ionic liquid, which constitute new, non-selective environments for solute transport, leads to a clear deterioration of SLM performance and selectivity. Nevertheless, electrical impedance spectroscopy characterisation of the SLMs showed that the formation of water clusters did not seem to have a detrimental effect on the SLMs’ electrical characteristics and highlighted the potential of using this type of membranes in electrochemical applications with low resistance requirements. The second part of the work studied the kinetics of thiomersal degradation by a pure culture of P. putida spi3 strain, in batch culture and using a synthe tic wastewater. A continuous ly stirred tank reactor fed with the synthetic wastewater was also operated and the bioreactor’s performance and robustness, when exposed to thiomersal shock loads, were evaluated. Finally, a bioreactor for the biological treatment of a real va ccine production effluent was set up and operated at different dilution rates. Thus it was possible to treat a real thiomersal-contaminated effluent, lowering the outlet mercury concentration to values below the European limit for mercury effluent discharges.

Waste recovery into activated carbon for water purification from heavy metals

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química Pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecn

Estratigrafia sismica do cenozóico na plataforma continental algarvia: interpretação do controle tectónico da sedimentação

The interpretation of 64 seismic reflection profiles in the Algarve continental platform (36º 20'-37º 00' paralels and 7º 20'-8º 40' meridians) calibrated with five petroleum exploration wells, with the identification of the geometric relations between six Cenozoic seismic units (B to G) and tectonic structures, allowed the construction of sucessive time-isopach maps (twt/s) and detailed interpretation of the geologic evolution. Two major tectonic structures were identified: a) the Portimão-Monchique fracture zone (striking N-S); b) an off-shore NW-SE fault zone, probably the S. Marcos-Quarteira fault. This accident separates two tectonic domains: the western domain (with N-S and E-W predominant structures and, secondarily, NW-SE and NE-SW) and the eastern domain (dominated by WSW-ENE, NW-SE, NE-SW, NNE-SSW and NNW-SSE structures). A persistent halokinetic activity had two major moments: a) sin-C unit; b) sin- and post-E unit. An increasing flexuration of the margin was identified, with spacial and temporal variation of the subsidence. The tectonic regime is considered as generally compressive, but the interpretation of the successíve stress-fields is rendered dificult by the existence of tectonic sub-domains and evaporitic structures.

Integração de informação secundária na modelação geoestatística da qualidade de solos em locais potencialmente contaminados. Aplicação à área subjacente de uma antiga refinaria

Dissertação para obtenção do Grau de Mestre em Engenharia Geológica (Georrecursos)

Toxicological effects of a pharmaceutical, simvastatin, in Gammarus locusta: histopathological evaluation

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente

Production of bacterial biopolymers from industrial fat-containing wastes

Dissertation presented in partial fulfilment of the Requirements for the Degree of Master in Biotechnology

Development of suberin films driven by an ionic liquid-based depolymerisation process

Dissertation presented to obtain the Ph.D degree in Chemistry

Constraint-based modelling of mixed microbial populations: Application to polyhydroxyalkanoates production

Dissertação para obtenção do Grau de Doutor em Engenharia Química e Bioquímica

Modelling of a wastewater treatment plant using GPS-X

Dissertation to obtain the degree of Master in Chemical and Biochemical Engineering

Petróleo: um contributo para o desenvolvimento em São Tomé e Príncipe

São Tomé Príncipe é um dos países mais pobres do mundo totalmente dependente da ajuda externa. Desde a independência, a 12 de Julho de 1975, o país mergulhou num clima de instabilidade sociopolítica e de pobreza que vem afetando e condicionando o desenvolvimento socioeconómico da sociedade santomense. A fraca capacidade governativa dos dirigentes e a falta de consenso na classe política, as sucessivas quedas de governo, o elitismo e o favoritismo reinante tornam quase impossível que se encontre um caminho consensual para que o país possa efetivamente sair da situação de pobreza em que se encontra e começar a dar passos significativos rumo ao desenvolvimento e ao progresso. Sendo um país com imensos problemas estruturais, que se vão agravando com o passar dos anos, São Tomé e Príncipe é um país extremamente frágil, onde a pobreza atinge a maior parte da população. A instabilidade política e social que se vive no país impede que a classe política nacional seja capaz de chegar a um entendimento para o progresso socioeconómico da nação. São Tomé e Príncipe é um país que dispõe de inúmeras potencialidades naturais, muitas delas continuam a ser mal aproveitadas devido à ausência de uma estratégia concertada que conduza o país ao desenvolvimento. Mas para que aconteça é imprescindível que os órgãos decisores do país sejam capazes de primar por políticas credíveis, transparentes e viáveis, para que o progresso e desenvolvimento tão desejado pela sociedade santomense não seja apenas um sonho. Com a descoberta do petróleo no território santomense, a nação tem depositado todas as suas esperanças na exploração petrolífera e que com a arrecadação das receitas daí provenientes o país começará a trilhar o caminho do desenvolvimento e do progresso.