A computational study of ionic liquids used in the production of fuels and biofuels

For the past decades it has been a worldwide concern to reduce the emission of harmful gases released during the combustion of fossil fuels. This goal has been addressed through the reduction of sulfur-containing compounds, and the replacement of fossil fuels by biofuels, such as bioethanol, produced in large scale from biomass. For this purpose, a new class of solvents, the Ionic Liquids (ILs), has been applied, aiming at developing new processes and replacing common organic solvents in the current processes. ILs can be composed by a large number of different combinations of cations and anions, which confer unique but desired properties to ILs. The ability of fine-tuning the properties of ILs to meet the requirements of a specific application range by mixing different cations and anions arises as the most relevant aspect for rendering ILs so attractive to researchers. Nonetheless, due to the huge number of possible combinations between the ions it is required the use of cheap predictive approaches for anticipating how they will act in a given situation. Molecular dynamics (MD) simulation is a statistical mechanics computational approach, based on Newton’s equations of motion, which can be used to study macroscopic systems at the atomic level, through the prediction of their properties, and other structural information. In the case of ILs, MD simulations have been extensively applied. The slow dynamics associated to ILs constitutes a challenge for their correct description that requires improvements and developments of existent force fields, as well as larger computational efforts (longer times of simulation). The present document reports studies based on MD simulations devoted to disclose the mechanisms of interaction established by ILs in systems representative of fuel and biofuels streams, and at biomass pre-treatment process. Hence, MD simulations were used to evaluate different systems composed of ILs and thiophene, benzene, water, ethanol and also glucose molecules. For the latter molecules, it was carried out a study aiming to ascertain the performance of a recently proposed force field (GROMOS 56ACARBO) to reproduce the dynamic behavior of such molecules in aqueous solution. The results here reported reveal that the interactions established by ILs are dependent on the individual characteristics of each IL. Generally, the polar character of ILs is deterministic in their propensity to interact with the other molecules. Although it is unquestionable the advantage of using MD simulations, it is necessary to recognize the need for improvements and developments of force fields, not only for a successful description of ILs, but also for other relevant compounds such as the carbohydrates.

Direct functionalization of heterocyclic and non-heterocyclic arenes

L’application des métaux de transition à la fonctionnalisation directe a ouvert la voie à une nouvelle classe de réactions pour la formation de liens carbone-carbone. De par l'omniprésence des liaisons C–H, l’introduction de nouvelles fonctionnalités chimiques par voie directe et pré-activation minimale s’impose comme une stratégie de synthèse très attrayante. Ainsi, il est envisageable de préparer de manière rapide et efficace des supports complexes menant à des molécules complexes, qui pourraient être utiles dans divers domaines de la chimie. L'objectif principal de la présente thèse vise la fonctionnalisation directe des arènes hétérocycliques et non hétérocycliques et, plus précisément, les techniques d’arylation. Dans un premier temps, nous allons aborder le thème de l’arylation directe tout en mettant l’accent sur les pyridines (Chapitre 1). Ces molécules sont à la base d'une multitude de composés biologiquement actifs et jouent un rôle important dans le domaine des sciences des matériaux, de l’agrochimie et de la synthèse des produits naturels. Dans un deuxième temps, nous discuterons de nos travaux sur l’arylation directe catalysé par un complex de palladium sur des ylures de N-iminopyridinium en soulignant la dérivatisation du sel de pyridinium après une phénylation sp2 (Chapitre 2). L’étude de ce procédé nous a permis de mettre en lumière plusieurs découvertes importantes, que nous expliquerons en détails une à une : l’arylation benzylique directe lorsque des ylures N-iminopyridinium substituées avec un groupement alkyl à la position 2 sont utilisés comme partenaires dans la réaction; les allylations Tsuji-Trost catalysée par un complex de palladium; et l’alkylation directe et sans métal via une catalyse par transfert de phase. Plusieurs défis restent à relever pour le développement de procédés directs utilisant des métaux de transition peu coûteux, d’autant plus que la synthèse par transformation directe des pyridines 2-alcényles, lesquelles sont pertinentes sur le plan pharmacologique, n’a pas encore été rapportée à ce jour. Avec cette problématique en tête, nous avons réussi à mettre au point une alcénylation directe catalysé par un complex de cuivre sur des ylures de N-iminopyridinium. Nous discuterons également d’une nouvelle méthode pour la préparation des iodures de vinyle utilisés dans les couplages. Ces réactions sont non seulement remarquablement chimiosélectives, mais sont aussi applicables à plusieurs substrats (Chapitre 3). En optimisant ce procédé direct, nous avons découvert une façon unique de synthétiser les pyrazolo[1,5-a]pyridines 2-substituées (Chapitre 4). Le mécanisme global met en jeu une séquence tandem de fonctionnalisation-cyclisation directe et un procédé direct en cascade, qui n’avais jamais été rapporté. Cela simplifie ansi la synthèse autrement compliquée de ces substrats en y apportant une solution à un problème de longue date. Dans les deux derniers chapitres, nous examinerons en détail les techniques d’arylation directe qui n'impliquent pas les partenaires de couplage hétérocycliques. Entre autres, au Chapitre 5, nous soulignerons notre découverte d’un umpolung dirigé et catalysé par un complexe de palladium du benzène et de quelques autres dérivés arènes. Il s’agit là du premier cas de fonctionnalisation directe dans laquelle le groupe directeur se trouve sur le partenaire halogène et il s’ajoute à la courte liste d’exemples connus dans la littérature rapportant une arylation directe du benzène. Finalement, au Chapitre 6, nous passerons en revue une nouvelle arylation directe catalysée au fer, qui se veut un procédé peu coûteux, durable et présentant une économie d’atomes. Nous discutons des substrats possibles ainsi des études mécanistiques réalisés.

From projects into operations: lessons for data handover

Data from civil engineering projects can inform the operation of built infrastructure. This paper captures lessons for such data handover, from projects into operations, through interviews with leading clients and their supply chain. Clients are found to value receiving accurate and complete data. They recognise opportunities to use high quality information in decision-making about capital and operational expenditure; as well as in ensuring compliance with regulatory requirements. Providing this value to clients is a motivation for information management in projects. However, data handover is difficult as key people leave before project completion; and different data formats and structures are used in project delivery and operations. Lessons learnt from leading practice include defining data requirements at the outset, getting operations teams involved early, shaping the evolution of interoperable systems and standards, developing handover processes to check data rather than documentation, and fostering skills to use and update project data in operations

Gestão do conhecimento: os desafios da implantação de um modelo integrado : o caso ANS

A Gestão do Conhecimento vem adquirindo uma importância notória dentro das organizações, tanto públicas quanto privadas. Suas características e aplicações permeiam as discussões acadêmicas e atingem, de forma reflexiva e inovadora, as práticas de trabalho. Seu foco está na elaboração de processos sistemáticos de captura, organização e armazenamento, análise e compartilhamento do conhecimento organizacional (individual e coletivo) voltados à criação de novos conhecimentos, novos produtos, ou novos processos de trabalho. Pretende-se com este estudo levantar os desafios à implantação de um modelo de Gestão do Conhecimento na Agência Nacional de Saúde Suplementar (ANS), tendo como base o discurso dos principais responsáveis por criar estratégias neste sentido e por conceder os instrumentos necessários à sua implementação. Com fundamento na literatura científica sobre o tema, faz-se uma revisão conceitual de conhecimento e de Gestão do Conhecimento, buscando explicitar suas dimensões que passam pela transversalidade do conhecimento, pela aprendizagem individual e organizacional, pelo compartilhamento do conhecimento e pelos sistemas de informação. Como metodologia, optou-se por realizar uma pesquisa qualitativa do tipo explicativa, desenvolvida por meio de estudo de caso, de forma a aprofundar o entendimento da realidade investigada. Os resultados das entrevistas e da análise documental possibilitaram verificar que a ANS tem adotado algumas práticas isoladas associadas à Gestão do Conhecimento. Constatou-se, no discurso, que existe uma predisposição dos gestores de conseguir maior efetividade em suas ações relativas ao compartilhamento do conhecimento e à implantação de um modelo de Gestão do Conhecimento na ANS. A pesquisa, contudo, revelou uma desarticulação institucional ocasionada por cultura hierarquizada e fragmentada, que se mostra profundamente desfavorável à um ambiente de criação e compartilhamento do conhecimento.

Tear identitário:a prática docente em arte como conhecimento compartilhado

This investigative tissue is about the formation of identification processes of teachers and pedagogical practice of Art, in Teresina city. This search comprised the sum of the needs presented, agreed upon with the teachers engaged in the process, it was developed through the establishment of interactive environment Loom Team where collaboration and critical reflection were steering actions to promote the understanding of existing connections or relations within the processes of identifications and the pedagogical practice of Art. The tissue is formed by the polyphonic plot of the critical reflection of nine teachers of Art who engaged voluntarily and this investigation of formative nature and a production of knowledge. All these teachers have degree and the course of artistic education and especial qualification in Fine Arts and/or Drawing. The texture, which we denominated Identification Loom: The pedagogical practice of Art as share knowledge is (de) (re) construction of knowledge resulting from the critical reflection, in an environment of collaboration, which may have implications and ethical political attitudes in the pedagogical practice of the group. Within this context, we pose the following question: - How does the pedagogical practice in Art influence and/or be influenced by the identification processes of the teachers, and how do they interfere with the search and manifestation of the knowledge involved and the investment in professionalization? In view of this query, we make use of the cooperative investigation, having social history as theoretical reference and as analytic perspective of interactive and dialogical-reflexive processes. Thus, social historic theory, cooperative approach and pedagogical practice were the major components of the plot. The methodological texture counted on the threads of dialogical reflexion, of mediation and of collaboration. The conceptual formulation, the recording in videos of classes and the narratives of formations were the main threads of the analytic substrate of the investigation. With this articulation, theses threads appear as developers of processes leading to a major approximation of the thought on the identity/alterity dialectical pair of the participants involved. The language within this plot had a decisive importance in all the moments of the search of signification, embracing and connecting the identification/alterative processes, the pedagogical practice of Art and the knowledge shared. In such processes involving (de) (re) construction, one can notice a close correlation of the triad social identity, pedagogical practice and knowledge shared. For this reason, the vigotskian, guetmanovian and kopnian theoretizations were the major framework for the analysis of conceptual formulations; and, as for discourse analysis, Baktin and Orlandi were our masters. For these teachers, the experience shared throughout the process of this typology of tri-axial investigation focused the experience of many theoretical and practical assumptions. Such an experience enabled them to state that this, with collaboration, can make reflection on the practice a starting and promoting element, within the individual level of self-management, in addition to being a space of (de)(re)construction of meanings, of knowledge and of reinvention per se

A formação do professor reflexivo sob o olhar da epistemologia marxiana

Pós-graduação em Educação - FFC

A Aplicação de um modelo matemático na resolução de um problema de carregamento de paletes

Global competitiveness has been increased significantly in the last decade and, as consequence, companies are always looking for developing better processes in supply chain operations in order to maintain their competitive costs and keep themselves in the business. Logistics operations represent a large part of the product's final cost. Transportation can represent more than fifty percent of final cost sometimes. The solutions for cutting and packing problems consist in simple and low investment actions, as enhancing the arrangement of the transported load in order to decrease both material and room wastes. As per the presented reasons, the objective of this paper is to show and analyze a real application of a mathematical model to solve a manufacturer pallet-loading problem, comparing results from the model execution and the solution proposed by the company studied. This study will not only find the best arrangement to load pallets (which will optimize storage and transportation process), but also to check the effectiveness of existing modeling in the literature. For this study a computational package was used, which consists of a modeling language GAMS with the CPLEX optimization solver and two other existing software in the market, all of them indicating that an accurate mathematical model for solving this kind of problem in a two-dimensional approach is difficult to be found, in addition to a long execution time. However, the study and the software utilization indicate that the problem would be easily solved by heuristics in a shorter execution time

A Aplicação de um modelo matemático na resolução de um problema de carregamento de paletes

Global competitiveness has been increased significantly in the last decade and, as consequence, companies are always looking for developing better processes in supply chain operations in order to maintain their competitive costs and keep themselves in the business. Logistics operations represent a large part of the product's final cost. Transportation can represent more than fifty percent of final cost sometimes. The solutions for cutting and packing problems consist in simple and low investment actions, as enhancing the arrangement of the transported load in order to decrease both material and room wastes. As per the presented reasons, the objective of this paper is to show and analyze a real application of a mathematical model to solve a manufacturer pallet-loading problem, comparing results from the model execution and the solution proposed by the company studied. This study will not only find the best arrangement to load pallets (which will optimize storage and transportation process), but also to check the effectiveness of existing modeling in the literature. For this study a computational package was used, which consists of a modeling language GAMS with the CPLEX optimization solver and two other existing software in the market, all of them indicating that an accurate mathematical model for solving this kind of problem in a two-dimensional approach is difficult to be found, in addition to a long execution time. However, the study and the software utilization indicate that the problem would be easily solved by heuristics in a shorter execution time

Modern environmental improvement pathways for the coal power generation industry in Australia

In this work we assess the pathways for environmental improvement by the coal utilization industry for power generation in Australia. In terms of resources, our findings show that coal is a long term resource of concern as coal reserves are likely to last for the next 500 years or more. However, our analysis indicates that evaporation losses of water in power generation will approach 1000 Gl (gigalitres) per year, equivalent to a consumption of half of the Australian residential population. As Australia is the second driest continent on earth, water consumption by power generators is a resource of immediate concern with regards to sustainability. We also show that coal will continue to play a major role in energy generation in Australia and, hence, there is a need to employ new technologies that can minimize environmental impacts. The major technologies to reduce impacts to air, water and soils are addressed. Of major interest, there is a major potential for developing sequestration processes in Australia, in particular by enhanced coal bed methane (ECBM) recovery at the Bowen Basin, South Sydney Basin and Gunnedah Basin. Having said that, CO2 capture technologies require further development to support any sequestration processes in order to comply with the Kyoto Protocol. Current power generation cycles are thermodynamic limited, with 35-40% efficiencies. To move to a high efficiency cycle, it is required to change technologies of which integrated gasification combined cycle plus fuel cell is the most promising, with efficiencies expected to reach 60-65%. However, risks of moving towards an unproven technology means that power generators are likely to continue to use pulverized fuel technologies, aiming at incremental efficiency improvements (business as usual). As a big picture pathway, power generators are likely to play an increasing role in regional development; in particular EcoParks and reclaiming saline water for treatment as pressures to access fresh water supplies will significantly increase.

Reengineering helps improve materials procurement in Indian oil refinery

The materials management function is always a major concern to the management of any organisation as high inventory and inefficient procurement processes have a significant effect on profitability. The problems multiply in the face of a very dynamic business environment, as is the present case in India. Hence, the existing system of materials planning, procurement processes and inventory management require reviewing with respect to the changed business environment. This study shows a radical improvement in materials procurement function of an Indian petroleum refinery through Business Process Reengineering (BPR) by analysing current process, identifying key issues, deriving paradigm shifts and developing reengineered processes through customer value analysis. BPR has been carried out on existing processes of 'material planning and procurement' and 'warehousing and surplus disposal'. The reengineered processes for the materials management function triggered several improvement projects that were identified by the group of executives who took part in the reengineering exercise. Those projects were implemented in an integrated framework, with the application of state of the art information technology tools and building partnership alliance among all stakeholders. Considerable improvements in overall functions of the organisation are observed, along with financial benefits. Copyright © 2006 Inderscience Enterprises Ltd.

Parameter design considerations in precision engineering

Parameter design is an experimental design and analysis methodology for developing robust processes and products. Robustness implies insensitivity to noise disturbances. Subtle experimental realities, such as the joint effect of process knowledge and analysis methodology, may affect the effectiveness of parameter design in precision engineering; where the objective is to detect minute variation in product and process performance. In this thesis, approaches to statistical forced-noise design and analysis methodologies were investigated with respect to detecting performance variations. Given a low degree of process knowledge, Taguchi's methodology of signal-to-noise ratio analysis was found to be more suitable in detecting minute performance variations than the classical approach based on polynomial decomposition. Comparison of inner-array noise (IAN) and outer-array noise (OAN) structuring approaches showed that OAN is a more efficient design for precision engineering. ^

Transição demográfica e a questão educacional: uma abordagem para o ensino médio do Rio Grande do Norte

Due to demographic transition process, the educational public sector politics formers encounter a highly specific demographic situation because, nowadays, despite the demographic transition, population is still growing because of the demographic inertia; however, due to steady decline in fertility, young population tends to decrease in next years. In this way, aiming to make high school widely accessible in the country, the issue of education quality is highlighted as well the importance of the physical structure of schools and their teaching equipments to confirm a favorable or not environment for developing educational processes. In this way, this work aims to relate the enrollment of students as school types with the demand of young people who will be able to attend high school on the Rio Grande do Norte state by the year of 2020, emphasizing teaching unities structural aspects, from a school profiling to the design of three prospective alternatives. So, from INEP's Scholar Census data and IBGE population's projections, this work is composed by four stages: i) literature review about research related subjects; ii) database design and build; iii) school profiling; and, iv) prospective alternatives creation. As results, three alternatives relate potential demand and enrollment using the built profiles and they are: i) “Alternative A” attends PEE's requirements related to demands but do not provide improvements in the school structural aspects; ii) “Alternative B” points into an increase of enrollment offering to the detriment of school's structural conditions which are offered to these students; iii) “Alternative C” propitiates a quantitative enrollment increasing combined with improvements on school's physical structure. These alternatives help to support decision making related to goals and realization of universal access with physical conditions which are necessary to a favorable environment to educational activity development.

Recrutamento e selecção na Tap Portugal

Mestrado em Gestão de Recursos Humanos

A competência educativa do professor: concepções de professores com funções inspectivas

Dissertação de mest., Unidade de Ciências Exactas e Humanas, Escola Superior de Educação, Univ. do Algarve,1998

Creencias y prácticas de autoevaluación del aprendizaje vigentes en los procesos de formación profesional desarrollados en el CIDE durante el 2007

This article identifies beliefs and practices of self-learning existing processes developed in the CIDE during 2007. It is based on a research project with two groups of informants both academics from CIDE, that during the decade of the 90 participated in the experience of self-learning, some of themas teachers and other as students. Current practices being carried out by academics in the field of self-reporting of apprenticeships in the CIDE, show that they attach great importance to this process in the lesson and agree on the necessity to implement this process in concrete terms, that because, experiences become isolated initiatives that do not fall within any policy, guideline or orientation openly raised by the community CIDE. The beliefs of the participants with regard to the possibility of implementing self-evaluation processes of learning in the training that develops the CIDE, highlight the need for scholars to train group of academics and students in this field and also create more spaces for student involvement. Moreover, scholars believe that the self-assessment of learning is a strategy for developing metacognitive processes and reflective, which is considered a core importance in the training provided by the Centre.