The thermal effects on the methanol-to-olefins reaction: A modelling and experimental approach

With the projection of an increasing world population, hand-in-hand with a journey towards a bigger number of developed countries, further demand on basic chemical building blocks, as ethylene and propylene, has to be properly addressed in the next decades. The methanol-to-olefins (MTO) is an interesting reaction to produce those alkenes using coal, gas or alternative sources, like biomass, through syngas as a source for the production of methanol. This technology has been widely applied since 1985 and most of the processes are making use of zeolites as catalysts, particularly ZSM-5. Although its selectivity is not especially biased over light olefins, it resists to a quick deactivation by coke deposition, making it quite attractive when it comes to industrial environments; nevertheless, this is a highly exothermic reaction, which is hard to control and to anticipate problems, such as temperature runaways or hot-spots, inside the catalytic bed. The main focus of this project is to study those temperature effects, by addressing both experimental, where the catalytic performance and the temperature profiles are studied, and modelling fronts, which consists in a five step strategy to predict the weight fractions and activity. The mind-set of catalytic testing is present in all the developed assays. It was verified that the selectivity towards light olefins increases with temperature, although this also leads to a much faster catalyst deactivation. To oppose this effect, experiments were carried using a diluted bed, having been able to increase the catalyst lifetime between 32% and 47%. Additionally, experiments with three thermocouples placed inside the catalytic bed were performed, analysing the deactivation wave and the peaks of temperature throughout the bed. Regeneration was done between consecutive runs and it was concluded that this action can be a powerful means to increase the catalyst lifetime, maintaining a constant selectivity towards light olefins, by losing acid strength in a steam stabilised zeolitic structure. On the other hand, developments on the other approach lead to the construction of a raw basic model, able to predict weight fractions, that should be tuned to be a tool for deactivation and temperature profiles prediction.

Continuous catalyst free production of biodiesel from agro industrial waste with green solvents

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

Alternative solvents in carvone hydrogenation

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquimica

Green synthesis of 2-Oxazoline-based polymers with antimicrobial activity using scCO2

Using a green methodology, 17 different poly(2-oxazolines) were synthesized starting from four different oxazoline monomers. The polymerization reactions were conducted in supercritical carbon dioxide under a cationic ring-opening polymerization (CROP) mechanism using boron trifluoride diethyl etherate as the catalyst. The obtained living polymers were then end-capped with different types of amines, in order to confer them antimicrobial activity. For comparison, four polyoxazolines were end-capped with water, and by their hydrolysis the linear poly(ethyleneimine) (LPEI) was also produced. After functionalization the obtained polymers were isolated, purified and characterized by standard techniques (FT-IR, NMR, MALDI-TOF and GPC). The synthesized poly(2-oxazolines) revealed an unusual intrinsic blue photoluminescence. High concentration of carbonyl groups in the polymer backbone is appointed as a key structural factor for the presence of fluorescence and enlarges polyoxazolines’ potential applications. Microbiological assays were also performed in order to evaluate their antimicrobial profile against gram-positive Staphylococcus aureus NCTC8325-4 and gram-negative Escherichia coli AB1157 strains, two well known and difficult to control pathogens. The minimum inhibitory concentrations (MIC)s and killing rates of three synthesized polymers against both strains were determined. The end-capping with N,N-dimethyldodecylamine of living poly(2- methyl-2-oxazoline) and poly(bisoxazoline) led to materials with higher MIC values but fast killing rates (less than 5 minutes to achieve 100% killing for both bacterial species) than LPEI, a polymer which had a lower MIC value, but took a longer time to kill both E.coli and S.aureus cells. LPEI achieved 100% killing after 45 minutes in contact with E. coli and after 4 hours in contact with S.aureus. Such huge differences in the biocidal behavior of the different polymers can possibly underlie different mechanisms of action. In the future, studies to elucidate the obtained data will be performed to better understand the killing mechanisms of the polymers through the use of microbial cell biology techniques.

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.

Development of novel ionic liquids based on biological molecules

Ionic Liquids (ILs) belong to a class of compounds with unusual properties: very low vapour pressure; high chemical and thermal stability and the ability to dissolve a wide range of substances. A new field in research is evaluating the possibility to use natural chiral biomolecules for the preparation of chiral ionic liquids (CILs). This important challenge in synthetic chemistry can open new avenues of research in order to avoid some problems related with the intrinsic biodegradability and toxicity associated to conventional ILs. The research work developed aimed for the synthesis of CILs, their characterization and possible applications, based on biological moieties used either as chiral cations or anions, depending on the synthetic manipulation of the derivatives. Overall, a total of 28 organic salts, including CILs were synthesized: 9 based on L-cysteine derivatives, 12 based on L-proline, 3 based on nucleosides and 4 based on nucleotides. All these new CILs were completely characterized and their chemical and physical properties were evaluated. Some CILs based on L-cysteine have been applied for discrimination processes, including resolution of racemates and as a chiral catalyst for asymmetric Aldol condensation. L-proline derived CILs were also studied as chiral catalysts for Michael reaction. In parallel, the interactions of macrocyclic oligosugars called cyclodextrins (CDs) with several ILs were studied. It was possible to improve the solubility of CDs in water and serum. Additionally, fatty acids and steroids showed an increase in water solubility when ILs-CDs systems were used. The development of efficient and selective ILs-CDs systems is indispensable to expand the range of their applications in host-guest interactions, drug delivery systems or catalytic reactions. Novel salts derived from nucleobases were used in order to enhance the fluorescence in aqueous solution. Additionally, preliminary studies regarding ethyl lactate as an alternative solvent for asymmetric organocatalysis were performed.

Light harvesting in solar cells using natural pigments from red fruits adsorbed to mesoporous TiO2

Nature has developed strategies to present us with a wide variety of colours, from the green of leaves to the bright colours seen in flowers. Anthocyanins are between these natural pigments that are responsible for the great diversity of colours seen in flowers and fruits. Anthocyanins have been used to sensitize titanium dioxide (TiO2) in Dye-Sensitized Solar Cells (DSSCs). DSSCs have become one of the most popular research topic in photovoltaic cells due to their low production costs when compared to other alternatives. DSSCs are inspired in what happens in nature during photosynthesis. A primary charge separation is achieved by means of a photoexcited dye capable of performing the electron injection into the conduction band of a wide band-gap semiconductor, usually TiO2. With this work we aimed to synthesize a novel mesoporous TiO2 structure as the semiconductor in order to increase the dye loading. We used natural occurring dyes such as anthocyanins and their synthetic flavylium relatives, as an alternative to the widely used metal complexes of Ru(II) which are expensive and are environmentally unsafe. This offers not only the chance to use safer dyes for DSSCs, but also to take profit of waste biological products, such as wine and olive oil production residues that are heavily loaded with anthocyanin dyes. We also performed a photodegradation study using TiO2 as the catalyst to degrade dye contaminants, such as those from the wine production waste, by photo-irradiation of the system in the visible region of the light spectrum. We were able to succeed in the synthesis of mesoporous TiO2 both powder and thin film, with a high capacity to load a large amount of dye. We proved the concept of photodegradation using TiO2 as catalyst. And finally, we show that wine production waste is a possible dye source to DSSCs application.

Fostering e-participation sustainability through a BPM-driven semantic model

According to a recent Eurobarometer survey (2014), 68% of Europeans tend not to trust national governments. As the increasing alienation of citizens from politics endangers democracy and welfare, governments, practitioners and researchers look for innovative means to engage citizens in policy matters. One of the measures intended to overcome the so-called democratic deficit is the promotion of civic participation. Digital media proliferation offers a set of novel characteristics related to interactivity, ubiquitous connectivity, social networking and inclusiveness that enable new forms of societal-wide collaboration with a potential impact on leveraging participative democracy. Following this trend, e-Participation is an emerging research area that consists in the use of Information and Communication Technologies to mediate and transform the relations among citizens and governments towards increasing citizens’ participation in public decision-making. However, despite the widespread efforts to implement e-Participation through research programs, new technologies and projects, exhaustive studies on the achieved outcomes reveal that it has not yet been successfully incorporated in institutional politics. Given the problems underlying e-Participation implementation, the present research suggested that, rather than project-oriented efforts, the cornerstone for successfully implementing e-Participation in public institutions as a sustainable added-value activity is a systematic organisational planning, embodying the principles of open-governance and open-engagement. It further suggested that BPM, as a management discipline, can act as a catalyst to enable the desired transformations towards value creation throughout the policy-making cycle, including political, organisational and, ultimately, citizen value. Following these findings, the primary objective of this research was to provide an instrumental model to foster e-Participation sustainability across Government and Public Administration towards a participatory, inclusive, collaborative and deliberative democracy. The developed artefact, consisting in an e-Participation Organisational Semantic Model (ePOSM) underpinned by a BPM-steered approach, introduces this vision. This approach to e-Participation was modelled through a semi-formal lightweight ontology stack structured in four sub-ontologies, namely e-Participation Strategy, Organisational Units, Functions and Roles. The ePOSM facilitates e-Participation sustainability by: (1) Promoting a common and cross-functional understanding of the concepts underlying e-Participation implementation and of their articulation that bridges the gap between technical and non-technical users; (2) Providing an organisational model which allows a centralised and consistent roll-out of strategy-driven e-Participation initiatives, supported by operational units dedicated to the execution of transformation projects and participatory processes; (3) Providing a standardised organisational structure, goals, functions and roles related to e-Participation processes that enhances process-level interoperability among government agencies; (4) Providing a representation usable in software development for business processes’ automation, which allows advanced querying using a reasoner or inference engine to retrieve concrete and specific information about the e-Participation processes in place. An evaluation of the achieved outcomes, as well a comparative analysis with existent models, suggested that this innovative approach tackling the organisational planning dimension can constitute a stepping stone to harness e-Participation value.

Valorization of olive pomace through combination of biocatalysis with supercritical fluid technology

A supercritical carbon dioxide (scCO2) based oil extraction method was implemented on olive pomace (alperujo), and an oil yield of 25,5 +/- 0,8% (goil/gdry residue) was obtained. By Soxhlet extraction with hexane, an oil extraction yield of 28,9 +/- 0,8 % was obtained, which corresponds to an efficiency of 88,4 +/- 4,8 % for the supercritical method. The scCO2 extraction process was optimized for operating conditions of 50 MPa and 348,15 K, for which an oil loading of 32,60 g oil/kg CO2 was calculated. As a proof of concept, olive pomace was used as feedstock for biodiesel production, in a process combining the use of lipase as a catalyst with the use of scCO2 as a solvent, and integrating the steps of oil extraction, oil to biodiesel transesterification and subsequent separation of the latter. In the conducted experiments, FAME (fatty acid methyl ester) purities of 90% were obtained, with the following operating parameters: an oil:methanol molar ratio of 1:24; a residence time of 7,33 and 11,6 mins; a pressure of 40 MPa; a temperature of 313,15 K; and Lipozyme (Mucor miehei; Sigma-Aldritch) as an enzyme. However, oscillations of FAME purity were registered throughout the experiments, which could possibly be due to methanol accumulation in the enzymatic reactor. Finally, the phenolic content of olive pomace, and the effect of the drying process – oven or freeze-drying – and the extraction methods – hydro-alcoholic method and supercritical method – on the phenolic content were analysed. It was verified that the oven-drying process on the olive pomace preserved 90,1 +/- 3,6 % of the total phenolic content. About 62,3 +/- 5,53% of the oven-dried pomace phenolic content was extracted using scCO2 at 60 MPa and 323,15 K. Seven individual phenols – hydroxytyrosol, tyrosol, oleuropein, quercetin, caffeic acid, ferulic acid and p-coumaric acid – were identified and quantified by HPLC.

Segurança e criminalidade organizada

Globalization brought some deep changes to the world (dis)order. Nowadays, more than in other moment in history, we are closer to the ones physically far, living in “global village” called by Marshall McLuhan (1962). The concepts and premises built in this new order, have totally broken with the ones that “came out from Westphalia”, which had last to the end of the cold war, like, for example, the concept of security. Since then, security has been facing one of its biggest transformations ever, completely disrupting the state border based idea and starting to be extended to other domains, as human, economic, environmental and IT security, among others. In this global and interdependent environment, “new” threats and risks have raised, which are demanding a comprehensive approach from the States, international organizations and other actors, to allow the analysis and understanding its impacts on the various society sectors and orders. Inside the enormous challenges to the global security, it is important to regard the organized crime, which covers, by itself, a set of threats and risks, enhanced by its connection to other types of criminality, such as terrorism. The goals pursued and the tactics used by criminal organizations during the perpetration of illegal activities, specially the drug smuggling, have impact in an wide spectrum of the social, economic financial and politic dimensions, which should not be underestimated, otherwise our own security may be compromised. Therefore, the current investigation intends to be an important catalyst to the idea debate inside security scope, through the analysis of the organized crime and the drug smuggling, adding to a discussion of this issue, which should be deeper and holistic, aiming a better understanding of the challenges provided by our society.

Understanding impact readiness in Portugal’s social sector and designing a framework for capacity-building for social impact

This project is based on the theme of capacity-building in social organisations to improve their impact readiness, which is the predictability of delivering intended outcomes. All organisations which have a social mission, non-profit or for-profit, will be considered to fall within the social sector for the purpose of this work. The thesis will look at (i) what is impact readiness and what are the considerations for building impact readiness in social organisations, (ii) what is the international benchmark in measuring and building impact readiness, (iii) understand the impact readiness of Portuguese social organisations and the supply of capacity building for social impact in Portugal currently, and (iv) provide recommendations on the design of a framework for capacity building for impact readiness adapted to the Portuguese context. This work is of particular relevance to the Social Investment Laboratory, which is a sponsor of this project, in its policy work as part of the Portuguese Social Investment Taskforce (the “Taskforce”). This in turn will inform its contribution to the set-up of Portugal Inovação Social, a wholesaler catalyst entity of social innovation and social investment in the country, launched in early 2015. Whilst the output of this work will be set a recommendations for wider application for capacity-building programmes in Portugal, Portugal Inovação Social will also clearly have a role in coordinating the efforts of market players – foundations, corporations, public sector and social organisations – in implementing these recommendations. In addition, the findings of this report could have relevance to other countries seeking to design capacity building frameworks in their local markets and to any impact-driven organisations with an interest in enhancing the delivery of impact within their work.