Modelling and optimization of the ion exchange membrane bioreactor for removal of anionic pollutants from drinking water streams

Dissertação para obtenção do Grau de Doutor em Engenharia Química, especialidade de Engenharia Bioquímica

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.

Polyimide and polyetherimide organic solvent nanofiltration membranes

Integrally asymmetric skinned Lenzing P84 and Matrimid 5218 polymide membranes and Ultem 1000 polyetherimide membranes were prepared. Crosslinking of membranes using aliphatic diamines resulted in marked improvement in chemical stability. This however resulted in a decline in flux with only Lenzing P84 demonstrating good flux in DMF. Further variation of membrane dope parameters and operating conditions allowed for good control of the MWCO of membranes made from Lenzing P84. SEM pictures of Lenzing P84 membranes revealed a significant difference in membranes morphology. The presence of macrovoids increased when using more DMF in the dope solution. These studies demonstrate the possibility of developing OSN membranes using different polyimides and opens up future possibilities for controlling the MWCO of these membranes. Preliminary modelling demonstrates that good control of the MWCO could extend the application of OSN membranes to allow the fraction of molecules in the NF range.

Part I : Comparing derivatization methods for amino acids – one and two-step procedures using gas chromatography – flame ion detector (GC-FID) Part II: Story of an icon from its execution until its conservation

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Conservação e Restauro

SENSITIVITY ANALYSIS OF TRACK VIBRATIONS DUE TO VERTICAL STIFFNESS VARIATION IN HIGH-SPEED RAILWAYS

High speed trains, when crossing regions with abrupt changes in vertical stiffness of the track and/or subsoil, may generate excessive ground and track vibrations. There is an urgent need for specific analyses of this problem so as to allow reliable esimates of vibration amplitude. Full understanding of these phenomena will lead to new construction solutions and mitigation of undesirable features. In this paper analytical transient solutions of dynamic response of one-dimensional systems with sudden change of foundation stiffness are derived. Results are expressed in terms of vertical displacement. Sensitivity analysis of the response amplitude is also performed. The analytical expressions presented herein, to the authors’ knowledge, have not been published yet. Although related to one-dimensional cases, they can give useful insight into the problem. Nevertheless, in order to obtain realistic response, vehicle- rail interaction cannot be omitted. Results and conclusions are confirmed using general purpose commercial software ANSYS. In conclusion, this work contributes to a better understanding of the additional vibration phenomenon due to vertical stiffness variation, permitting better control of the train velocity and optimization of the track design.

Development of polymeric membranes for forward osmosis

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

Caracterização de fibras de ion jelly® obtidas por electrofiação

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

Development of thermoresponsive (polysulfone/polyacrylonitrile) - based membranes for bioseparation processes

Mestrado integrado em Engenharia Química e Bioquímica

Influence of commercially available polyimide and formation conditions on the performance and structure of asymmetric polyimide organic solvent nanofiltration membranes

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

Development of electrospun Ion jelly fibers® for drug delivery

Dissertação para obtenção do Grau de Mestre em Biotecnologia

Critical Velocity obtained using Simplified Models of the Railway Track: Viability and Applicability

Increased demands on the capacity of the railway network gave rise to new issues related to the dynamic response of railway tracks subjected to moving vehicles. Thus, it becomes important to evaluate the applicability of traditionally used simplified models which have a closed form solution. Regarding simplified models, transversal vibrations of a beam on a visco-elastic foundation subjected to a moving load are considered. Governing equations are obtained by Hamilton’s principle. Shear distortion, rotary inertia and effect of axial force are accounted for. The load is introduced as a time varying force moving at a constant velocity. Transversal vibrations induced by the load are solved by the normal-mode analysis. Reflected waves at the extremities of the full beam are avoided by introduction of semi-infinite elements. Firstly, the critical velocity obtained from this model is compared with results of an undamped Euler- Bernoulli formulation with zero axial force. Secondly, a finite element model in ABAQUS is examined. The new contribution lies in the introduction of semi- infinite elements and in the first step to a systematic comparison, which have not been published so fa

The role of halouracils in radiotherapy studied by electron transfer in atom-molecule collisions experiments

Dissertação para obtenção do Grau de Doutor em Engenharia Física

Preparation of affinity membranes using alternative solvents

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

On the track of β-lactam resistance: Studies on the regulation of methicillinresistance in Staphylococcus aureus

Dissertação para obtenção do Grau de Doutor em Biologia

Development of integrated separation processes with green solvents

Dissertação para obtenção do Grau de Doutor em Química Sustentável