Real time optimization in chemical process: evaluation of strategies, improvements and industrial application.

The increasing economic competition drives the industry to implement tools that improve their processes efficiencies. The process automation is one of these tools, and the Real Time Optimization (RTO) is an automation methodology that considers economic aspects to update the process control in accordance with market prices and disturbances. Basically, RTO uses a steady-state phenomenological model to predict the process behavior, and then, optimizes an economic objective function subject to this model. Although largely implemented in industry, there is not a general agreement about the benefits of implementing RTO due to some limitations discussed in the present work: structural plant/model mismatch, identifiability issues and low frequency of set points update. Some alternative RTO approaches have been proposed in literature to handle the problem of structural plant/model mismatch. However, there is not a sensible comparison evaluating the scope and limitations of these RTO approaches under different aspects. For this reason, the classical two-step method is compared to more recently derivative-based methods (Modifier Adaptation, Integrated System Optimization and Parameter estimation, and Sufficient Conditions of Feasibility and Optimality) using a Monte Carlo methodology. The results of this comparison show that the classical RTO method is consistent, providing a model flexible enough to represent the process topology, a parameter estimation method appropriate to handle measurement noise characteristics and a method to improve the sample information quality. At each iteration, the RTO methodology updates some key parameter of the model, where it is possible to observe identifiability issues caused by lack of measurements and measurement noise, resulting in bad prediction ability. Therefore, four different parameter estimation approaches (Rotational Discrimination, Automatic Selection and Parameter estimation, Reparametrization via Differential Geometry and classical nonlinear Least Square) are evaluated with respect to their prediction accuracy, robustness and speed. The results show that the Rotational Discrimination method is the most suitable to be implemented in a RTO framework, since it requires less a priori information, it is simple to be implemented and avoid the overfitting caused by the Least Square method. The third RTO drawback discussed in the present thesis is the low frequency of set points update, this problem increases the period in which the process operates at suboptimum conditions. An alternative to handle this problem is proposed in this thesis, by integrating the classic RTO and Self-Optimizing control (SOC) using a new Model Predictive Control strategy. The new approach demonstrates that it is possible to reduce the problem of low frequency of set points updates, improving the economic performance. Finally, the practical aspects of the RTO implementation are carried out in an industrial case study, a Vapor Recompression Distillation (VRD) process located in Paulínea refinery from Petrobras. The conclusions of this study suggest that the model parameters are successfully estimated by the Rotational Discrimination method; the RTO is able to improve the process profit in about 3%, equivalent to 2 million dollars per year; and the integration of SOC and RTO may be an interesting control alternative for the VRD process.

Mathematical approach for predicting non-negative tristimulus values using the CAT02 chromatic adaptation transform

It has been reported that for certain colour samples, the chromatic adaptation transform CAT02 imbedded in the CIECAM02 colour appearance model predicts corresponding colours with negative tristimulus values (TSVs), which can cause problems in certain applications. To overcome this problem, a mathematical approach is proposed for modifying CAT02. This approach combines a non-negativity constraint for the TSVs of corresponding colours with the minimization of the colour differences between those values for the corresponding colours obtained by visual observations and the TSVs of the corresponding colours predicted by the model, which is a constrained non-linear optimization problem. By solving the non-linear optimization problem, a new matrix is found. The performance of the CAT02 transform with various matrices including the original CAT02 matrix, and the new matrix are tested using visual datasets and the optimum colours. Test results show that the CAT02 with the new matrix predicted corresponding colours without negative TSVs for all optimum colours and the colour matching functions of the two CIE standard observers under the test illuminants considered. However, the accuracy with the new matrix for predicting the visual data is approximately 1 CIELAB colour difference unit worse compared with the original CAT02. This indicates that accuracy has to be sacrificed to achieve the non-negativity constraint for the TSVs of the corresponding colours.

Capital humano y turismo: rendimiento educativo, desajuste y satisfacción laboral

El capital humano es un elemento clave para el logro de objetivos en términos de competitividad y crecimiento del sector de turismo en España. En este trabajo se utilizan datos muy recientes (procedentes de la Encuesta de Calidad de Vida en el Trabajo, ECVT) para abordar tres aspectos fundamentales en su análisis: el rendimiento educativo que los trabajadores obtienen a cambio de la inversión que realizan en su formación reglada; la medición de los niveles de desajuste entre dicha formación y los puestos de trabajo que ocupan, y su relación con el salario; y, por último, el análisis de diversas dimensiones de la satisfacción laboral y de la relación que se establece entre ellas y la sobre-educación de los trabajadores.

Sentiment classification for early detection of health alerts in the chemical textile domain

In the chemical textile domain experts have to analyse chemical components and substances that might be harmful for their usage in clothing and textiles. Part of this analysis is performed searching opinions and reports people have expressed concerning these products in the Social Web. However, this type of information on the Internet is not as frequent for this domain as for others, so its detection and classification is difficult and time-consuming. Consequently, problems associated to the use of chemical substances in textiles may not be detected early enough, and could lead to health problems, such as allergies or burns. In this paper, we propose a framework able to detect, retrieve, and classify subjective sentences related to the chemical textile domain, that could be integrated into a wider health surveillance system. We also describe the creation of several datasets with opinions from this domain, the experiments performed using machine learning techniques and different lexical resources such as WordNet, and the evaluation focusing on the sentiment classification, and complaint detection (i.e., negativity). Despite the challenges involved in this domain, our approach obtains promising results with an F-score of 65% for polarity classification and 82% for complaint detection.

Applying reactive models to column experiments to assess the hydrogeochemistry of seawater intrusion: optimising ACUAINTRUSION and selecting cation exchange coefficients with PHREEQC

Three sets of laboratory column experimental results concerning the hydrogeochemistry of seawater intrusion have been modelled using two codes: ACUAINTRUSION (Chemical Engineering Department, University of Alicante) and PHREEQC (U.S.G.S.). These reactive models utilise the hydrodynamic parameters determined using the ACUAINTRUSION TRANSPORT software and fit the chloride breakthrough curves perfectly. The ACUAINTRUSION code was improved, and the instabilities were studied relative to the discretisation. The relative square errors were obtained using different combinations of the spatial and temporal steps: the global error for the total experimental data and the partial error for each element. Good simulations for the three experiments were obtained using the ACUAINTRUSION software with slight variations in the selectivity coefficients for both sediments determined in batch experiments with fresh water. The cation exchange parameters included in ACUAINTRUSION are those reported by the Gapon convention with modified exponents for the Ca/Mg exchange. PHREEQC simulations performed using the Gains-Thomas convention were unsatisfactory, with the exchange coefficients from the database of PHREEQC (or range), but those determined with fresh water – natural sediment allowed only an approximation to be obtained. For the treated sediment, the adjusted exchange coefficients were determined to improve the simulation and are vastly different from those from the database of PHREEQC or batch experiment values; however, these values fall in an order similar to the others determined under dynamic conditions. Different cation concentrations were simulated using two different software packages; this disparity could be attributed to the defined selectivity coefficients that affect the gypsum equilibrium. Consequently, different calculated sulphate concentrations are obtained using each type of software; a smaller mismatch was predicted using ACUAINTRUSION. In general, the presented simulations by ACUAINTRUSION and PHREEQC produced similar results, making predictions consistent with the experimental data. However, the simulated results are not identical to the experimental data; sulphate (total S) is overpredicted by both models, most likely due to such factors as the kinetics of gypsum, the possible variations in the exchange coefficients due to salinity and the neglect of other processes.

Tiempo de desplazamiento al trabajo y desajuste educativo en el mercado de trabajo español

En este trabajo se analiza cómo el tiempo de trayecto y las características de los mercados laborales locales influyen en el desajuste puesto de trabajo- nivel educativo del individuo, basado en la hipótesis de que los individuos que tienen un mayor tiempo de trayecto al trabajo y mejores condiciones en mercado laboral se asocian a una menor incidencia de la sobreeducación. La sobreeducación afecta a 17 % de los trabajadores en España, y se eleva al 22,4 % para los trabajadores menores de 35 años. El análisis se basa en los datos individuales de los trabajadores españoles que se refiere al período inicial de la crisis económica mundial (2007-2010). La variable dependiente, desajuste educativo-puesto se mide mediante el método subjetivo, basado en las respuestas del individuo a la pregunta de cómo ajusta su nivel de educación a las necesidades del trabajo que actualmente ocupan. La variable de interés son: (a) el tiempo de trayecto, es decir, el tiempo que tarda el individuo en llegar a su trabajo, y (b) dos variables que tienen en cuenta de las condiciones del mercado local: la tasa regional de desempleo (esta variable se refieren a la división territorial de España a nivel NUTS 2 y desglose por sexo y nivel de educación de cada Comunidad Autónoma sobre la base de las cifras medias anuales de la Encuesta de Población Activa española (EPA) para el período 2007-2010) y el tamaño del municipio. Se incluyen las variables de control habituales relativas al puesto de trabajo y variables dummy de los años de la muestra. Los resultados sugieren que las difíciles condiciones de trabajo regionales en términos de altas tasas de desempleo pueden actuar contra el efecto hipotético de la movilidad en la reducción del desajuste educativo, por lo tanto, se obtiene a una conclusión opuesta a la planteada en algunos trabajos anteriores.

Effects of Fe addition on the mechanical and thermo-mechanical properties of SiC/FeSi2/Si composites produced via reactive infiltration

Remaining silicon in SiC-based materials produced via reactive infiltration limits their use in high-temperature applications due to the poor mechanical properties of silicon: low fracture toughness, extreme fragility and creep phenomena above 1000 °C. In this paper SiC–FeSi2 composites are fabricated by reactive infiltration of Si–Fe alloys into porous Cf/C preforms. The resulting materials are SiC/FeSi2 composites, in which remaining silicon is reduced by formation of FeSi2. For the richest Fe alloys (35 wt% Fe) a nominal residual silicon content below 1% has been observed. However this, the relatively poor mechanical properties (bending strength) measured for those resulting materials can be explained by the thermal mismatch of FeSi2 and SiC, which weakens the interface and does even generate new porosity, associated with a debonding phenomenon between the two phases.

Una aproximación al problema del sujeto femenino a través del debate Butler-Žižek

El artículo pretende acercarse al debate mantenido por Judith Butler y Slavoj Žižek sobre la identidad femenina a partir de sus respectivos planteamientos sobre la subjetividad. Ambos autores coinciden en señalar la negatividad e incompletud del sujeto, aunque difieren a la hora de explicar cómo se constituye y cómo puede ejercer la autonomía. Sus respectivos planteamientos reflejan dos maneras de entender la diferencia sexual.

Terahertz Response of Excitons in Nanorod Heterostructures

Quantum-confined systems are one of the most promising ways to enable us to control a material's interactions with light. Nanorods in particular offer the right dimensions for exploring and manipulating the terahertz region of the spectrum. In this thesis, we model excitons confined inside a nanorod using the envelope function approximation. A region-matching transfer matrix method allows us to simulate excitonic states inside arbitrary heterostructures grown along the length of the rod. We apply the method to colloidal CdSe rods 70 nm in length and under 10 nm in diameter, capped with ligands of DDPA and pyridine. We extend past studies on these types of rods by taking into account their dielectric permittivity mismatch. Compared to previous calculations and experimentally measured terahertz absorption, we predict a higher energy main 1S$z$ to 2P$z$ transition peak. This indicates that the rods are likely larger in diameter than previously thought. We also investigate a nanorod with GaAs/Al$_{0.3}$Ga$_{0.7}$As coupled double dots. The excitonic transitions were found to be manipulable by varying the strength of an applied electric field. We employ quasi-static state population distributions to simulate the effects of exciton relaxation from optically active states to dim ground states. A critical value of the applied field, corresponding to the exciton binding energy of ~18 meV, was found to dramatically alter the terahertz absorption due to state mixing. Above this critical field, more nuanced shifts in transition energies were observed, and gain from radiative relaxation to the ground state is predicted.

Y-box binding protein 1 (YB-1) relevance in estrogen receptor-positive (ER+) breast cancer

Tese de mestrado, Biologia Molecular e Genética, Universidade de Lisboa, Faculdade de Ciências, 2016

Síndrome de bronquiolite obliterante após o transplante pulmonar : factores de risco

Trabalho Final do Curso de Mestrado Integrado em Medicina, Faculdade de Medicina, Universidade de Lisboa, 2014

Rural Labour Market Developments in the Former Yugoslav Republic of Macedonia. Factor Markets Working Paper No. 5, September 2011

The significant changes in the quantitative and qualitative characteristics of human resources in rural Macedonia can be explained by the continued trend of emigration from villages to urban areas and abroad. The intensity of emigration has altered the demographic structure and reproductive base of the rural population, along with the income of rural households. The rural and agricultural labour market faces a mismatch with respect to the unfavourable age, education and spatial distribution of the total labour force. A reduction in the participation of women in the agricultural labour force is a new feature. The overall transformation is apparent in the income structure of rural households. An increase in the share of households with mixed income sources notably stems from households that receive remittances and foreign currency funds from family members abroad. The demographic revitalisation of rural areas depends on economic revitalisation, with a more rational use of the labour force and human resources, as well as a restructuring of agricultural production and agricultural holdings. In addition, improvements are necessary in the functioning of market institutions to better meet the needs of smaller farmers and the rural economy.

The Strategic Planning of EU Military Operations - The Case of EUFOR TCHAD / RCA. IES WORKING PAPER 5/2008

On 28 January 2008 the European Union launched the military operation EUFOR in Chad and the Central African Republic. Its mandate was to contribute to the security of the civilian population, the numerous refugees from neighboring Darfur and the local presence of the United Nations. This paper describes and analyses the planning process of this operation at the political-strategic and military-strategic levels with the aim of understanding how the military instrument was intended to generate the desired political effects. The paper argues that, from a military perspective, the EUFOR operation is based on the concept of humanitarian deterrence: the threat of military force is used to discourage potential spoilers from targeting the civilian population. As with any military operation, the planning of EUFOR was plagued by various elements of friction. At least some of this friction seems to flow from the mismatch in expectations between the political-strategic and military-strategic levels. The various political and military-technical constraints within which the operation was planned resulted in an operational posture that is less decisive than what the political ambitions would have suggested.

EU Naval Force EUNAVFOR MED sets sail in troubled waters. CEPS Commentary, 26 June 2015

Apprehending pirates in the Indian Ocean is one thing. Defeating the networks through which smugglers traffic migrants through North Africa is quite another. The European Union’s new naval force deployment in the Mediterranean - EUNAVFOR MED - drew criticism from international partners and the general public alike when plans for a “boat-sinking” operation were unveiled, raising fears about unacceptable levels of violence and collateral damage; a European version of Mexico’s drug war. Yet the problems of EUNAVFOR MED lie less in clumsy public diplomacy than in the perilous mismatch between its stated objectives and the absence of a clear strategy and mandate, and this creates both operational and political risks for member states. Phase 1 of the operation: surveillance and assessment, has begun with no legal mandate to carry out the crucial phases 2 and 3: seek and destroy, whose military planning and outcomes are undetermined. Despite these limitations, the naval force could nevertheless mark a turning point in the EU’s security narrative, because it means that the Union is finally addressing the threats to security and the humanitarian tragedies in its southern neighbourhood.

Practical domain-specific debuggers using the Moldable Debugger framework

Understanding the run-time behavior of software systems can be a challenging activity. Debuggers are an essential category of tools used for this purpose as they give developers direct access to the running systems. Nevertheless, traditional debuggers rely on generic mechanisms to introspect and interact with the running systems, while developers reason about and formulate domain-specific questions using concepts and abstractions from their application domains. This mismatch creates an abstraction gap between the debugging needs and the debugging support leading to an inefficient and error-prone debugging effort, as developers need to recover concrete domain concepts using generic mechanisms. To reduce this gap, and increase the efficiency of the debugging process, we propose a framework for developing domain-specific debuggers, called the Moldable Debugger, that enables debugging at the level of the application domain. The Moldable Debugger is adapted to a domain by creating and combining domain-specific debugging operations with domain-specific debugging views, and adapts itself to a domain by selecting, at run time, appropriate debugging operations and views. To ensure the proposed model has practical applicability (i.e., can be used in practice to build real debuggers), we discuss, from both a performance and usability point of view, three implementation strategies. We further motivate the need for domain-specific debugging, identify a set of key requirements and show how our approach improves debugging by adapting the debugger to several domains.