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.

Avaliação da sustentabilidade corporativa: estudo das relações híbridas pelo modelo do Hybrid Bottom Line

A presente tese reflete sobre os temas do desenvolvimento sustentável, da sustentabilidade corporativa, da responsabilidade social corporativa e das dimensões do Triple Bottom Line. O principal objetivo do nosso trabalho é contribuir para o conhecimento das relações que se estabelecem nas interseções entre a dimensão económica, social e ambiental da sustentabilidade corporativa, aqui designadas de relações híbridas. Neste sentido, desenvolveu-se um enquadramento teórico que fundamenta o modelo proposto, designado por Hybrid Bottom Line. De acordo com este enquadramento procurou-se conceber uma metodologia que permitisse analisar como é que estas relações de interseção entre economia-ambiente e economia-social se verificam e de que forma os seus resultados podem beneficiar a compreensão, avaliação e melhorias no entendimento da sustentabilidade corporativa, bem como possibilitar uma análise dirigida a fatores recombinantes específicos. Em complemento, foi desenvolvida uma proposta que permite posicionar o esforço desenvolvido pela empresa no âmbito da sustentabilidade e desta forma tipificar as suas ações. Nesta tese a abordagem empírica recaiu na análise dos relatórios de sustentabilidade publicados pelas empresas e baseados nas diretivas de relato propostas pelo Global Reporting Initiative. A amostra para o estudo abrangeu um total de 85 empresas de diferentes dimensões de 36 sectores económicos e representando 36 países de 5 continentes. A análise dos resultados foi feita utilizando diversos métodos de análise de dados (de frequência e de conteúdo) e análises estatísticas (análise de contingência, variância e de correspondências múltiplas) que permitiram observar as relações entre as dimensões do Triple Bottom Line, dando lugar à construção de uma matriz de relações híbridas. Seguidamente foi realizada uma análise longitudinal de uma das empresas da amostra tendo como referência a matriz híbrida obtida, assim como a tipificação da empresa no âmbito da sustentabilidade. Os resultados alcançados nas diferentes fases indicam que o enquadramento teórico que foi utilizado é útil para a análise das interseções entre as dimensões e permite uma avaliação dirigida a fatos ocorridos entre pares dimensionais, bem como projetar análises e posicionamentos futuros. Os resultados obtidos sugerem que a proposta apresentada é útil e deverá ser utilizada e desenvolvida noutros contextos. Esta tese contribui para a ideia de que a responsabilidade corporativa não deve ser só vista e operacionalizada como uma realidade de dimensões segmentadas mas também deve ser observada como um conjunto possível de interações que se manifestam nas interseções das suas diferentes dimensões.

Rating corporate groups a modelling experience

This paper aims to provide a model that allows BPI to measure the credit risk, through its rating scale, of the subsidiaries included in the corporate groups who are their clients. This model should be simple enough to be applied in practice, accurate, and must give consistent results in comparison to what have been the ratings given by the bank. The model proposed includes operational, strategic, and financial factors and ends up giving one of three results: no support, partial support, or full support from the holding to the subsidiary, and each of them translates in adjustments in each subsidiary’s credit rating. As it would be expectable, most of the subsidiaries should have the same credit rating of its parent company.

Hybrid investment strategy active portfolio management – US stock market

This thesis aims to develop an alternative active managed portfolio strategy based on companies‟ Fundamental and Technical Analysis and analyze its finals results. There is a big distinction between the two approaches and the main objective is to understand if it is possible to take advantage of both. With this in mind a Hybrid investment strategy for the US stock market, due to its dimension and liquidity, which was able to outperform the S&P 500 index, the benchmark, during both Bear and Bull Markets between 2000 and 2015.

Does companionate love express itself unequally in different organizational forms (private companies, hybrid and non-governmental organizations)?

Although, the word “Love” in organizations is seen as a rare concept, but it has gained importance in management theoretical foundation. This study seeks to explore the companionate love in distinct of organizational forms (Private companies; Social organizations; NGO and IPSS) through interviews. The results propose that it is a tensional concept with a complex dynamic: tension of personal behavior, tension of professional behavior; tension of individual impact and tension of community impact. The love dynamic has common points to all organizations, but its expression depends on the specific form of the organization.

Experimental and numerical approaches for structural assessment in new footbridge designs (SFRSCC–GFPR hybrid structure)

Within the civil engineering field, the use of the Finite Element Method has acquired a significant importance, since numerical simulations have been employed in a broad field, which encloses the design, analysis and prediction of the structural behaviour of constructions and infrastructures. Nevertheless, these mathematical simulations can only be useful if all the mechanical properties of the materials, boundary conditions and damages are properly modelled. Therefore, it is required not only experimental data (static and/or dynamic tests) to provide references parameters, but also robust calibration methods able to model damage or other special structural conditions. The present paper addresses the model calibration of a footbridge bridge tested with static loads and ambient vibrations. Damage assessment was also carried out based on a hybrid numerical procedure, which combines discrete damage functions with sets of piecewise linear damage functions. Results from the model calibration shows that the model reproduces with good accuracy the experimental behaviour of the bridge.

Development of innovative hybrid sandwich panel slabs: Experimental results

The authors appreciate the collaboration of the following labs: Civitest for developing DHCC materials, PIEP for conducting VARTM process (Eng. Luis Oliveira) and Department of Civil Engineering of Minho University to perform the tests (Mr. Antonio Matos and Eng. Marco Jorge).

Assessment of the efficiency of prefabricated hybrid composite plates (HCPs) for retrofitting of damaged interior RC beam–column joints

The effectiveness of prefabricated hybrid composite plates (HCPs) as a seismic retrofitting solution for damaged interior RC beam-column joints is experimentally studied. HCP is composed of a thin plate made of strain hardening cementitious composite (SHCC) reinforced with CFRP sheets/laminates. Two full-scale severely damaged interior beam-column joints are retrofitted using two different configurations of HCPs. The effectiveness of these retrofitting solutions mainly in terms of hysteretic response, dissipated energy, degradation of secant stiffness, displacement ductility and failure modes are compared to their virgin states. According to these criteria, both solutions resulted in superior responses regarding the ones registered in their virgin states.

Two cytotypes and a new hybrid in Salvinia Séguier

Two cytotypes (2n=4x=36 and 2n=6x=54) found in Salvinia minima Bak. are discussed, the first from Brazil and the second from Argentina. The hexaploid cytotype, presumably a hybrid between Salvinia minima and S. sprucei Kuhn, was collected from the Solimões River near Manaus, Brazil and from Trinidad. Discussing its intermediate morphology, the authors attemp to explain the hybridization as a result of the seasonal and sporadic occurrence of Salvinia sprucei in the Amazonian basin, assuming that the still unknown chromosome number of the latter species would correspond to the diploid level (2n=2x=18).

Flexural strengthening of RC beams using hybrid composite plate (HCP): experimental and analytical study

Hybrid Composite Plate (HCP) is a reliable recently proposed retrofitting solution for concrete structures, which is composed of a strain hardening cementitious composite (SHCC) plate reinforced with Carbon Fibre Reinforced Polymer (CFRP). This system benefits from the synergetic advantages of these two composites, namely the high ductility of SHCC and the high tensile strength of CFRPs. In the materialstructural of HCP, the ultra-ductile SHCC plate acts as a suitable medium for stress transfer between CFRP laminates (bonded into the pre-sawn grooves executed on the SHCC plate) and the concrete substrate by means of a connection system made by either chemical anchors, adhesive, or a combination thereof. In comparison with traditional applications of FRP systems, HCP is a retrofitting solution that (i) is less susceptible to the detrimental effect of the lack of strength and soundness of the concrete cover in the strengthening effectiveness; (ii) assures higher durability for the strengthened elements and higher protection to the FRP component in terms of high temperatures and vandalism; and (iii) delays, or even, prevents detachment of concrete substrate. This paper describes the experimental program carried out, and presents and discusses the relevant results obtained on the assessment of the performance of HCP strengthened reinforced concrete (RC) beams subjected to flexural loading. Moreover, an analytical approach to estimate the ultimate flexural capacity of these beams is presented, which was complemented with a numerical strategy for predicting their load-deflection behaviour. By attaching HCP to the beams’ soffit, a significant increase in the flexural capacity at service, at yield initiation of the tension steel bars and at failure of the beams can be achieved, while satisfactory deflection ductility is assured and a high tensile capacity of the CFRP laminates is mobilized. Both analytical and numerical approaches have predicted with satisfactory agreement, the load-deflection response of the reference beam and the strengthened ones tested experimentally.

Assessment of the effectiveness of steel fibre reinforcement for the punching resistance of flat slabs by experimental research and design approach

The present paper deals with the experimental assessment of the effectiveness of steel fibre reinforcement in terms of punching resistance of centrically loaded flat slabs, and to the development of an analytical model capable of predicting the punching behaviour of this type of structures. For this purpose, eight slabs of 2550 x 2550 x 150 mm3 dimensions were tested up to failure, by investigating the influence of the content of steel fibres (0, 60, 75 and 90 kg/m3) and concrete strength class (50 and 70 MPa). Two reference slabs without fibre reinforcement, one for each concrete strength class, and one slab for each fibre content and each strength class compose the experimental program. All slabs were flexurally reinforced with a grid of ribbed steel bars in a percentage to assure punching failure mode for the reference slabs. Hooked ends steel fibres provided the unique shear reinforcement. The results have revealed that steel fibres are very effective in converting brittle punching failure into ductile flexural failure, by increasing both the ultimate load and deflection, as long as adequate fibre reinforcement is assured. An analytical model was developed based on the most recent concepts proposed by the fib Mode Code 2010 for predicting the punching resistance of flat slabs and for the characterization of the behaviour of fibre reinforced concrete. The most refined version of this model was capable of predicting the punching resistance of the tested slabs with excellent accuracy and coefficient of variation of about 5%.

Shear strengthening of damaged reinforced concrete beams with hybrid composite plates

This paper aims to evaluate experimentally the potentialities of Hybrid Composite Plates (HCPs) technique for the shear strengthening of reinforced concrete (RC) beams that were previously subjected to intense damage in shear. HCP is a thin plate of Strain Hardening Cementitious Composite (SHCC) reinforced with Carbon Fiber Reinforced Polymer (CFRP) laminates. For this purpose, an experimental program composed of two series of beams (rectangular and T cross section) was executed to assess the strengthening efficiency of this technique. In the first step of this experimental program, the control beams, without steel stirrups, were loaded up to their shear failure, and fully unloaded. Then, these pre-damaged beams were shear strengthened by applying HCPs to their lateral faces by using a combination of epoxy adhesive and mechanical anchors. The bolts were applied with a certain torque in order to increase the concrete confinement. The obtained results showed that the increase of load carrying capacity of the damaged strengthened beams when HCPs were applied with epoxy adhesive and mechanical anchors was 2 and 2.5 times of the load carrying capacity of the corresponding reference beams (without HCPs) for the rectangular and T cross section beam series, respectively. To further explore the potentialities of the HCPs technique for the shear strengthening, the experimental tests were simulated using an advanced numerical model by a FEM-based computer program. After demonstration the good predictive performance of the numerical model, a parametric study was executed to highlight the influence of SHCC as an alternative for mortar, as well as the influence of torque level applied to the mechanical anchors, on the load carrying capacity of beams strengthened with the proposed technique.

Thermal conditions affecting heat transfer in FDM/FFE: a contribution towards the numerical modelling of the process

The performance of parts produced by Free Form Extrusion (FFE), an increasingly popular additive manufacturing technique, depends mainly on their dimensional accuracy, surface quality and mechanical performance. These attributes are strongly influenced by the evolution of the filament temperature and deformation during deposition and solidification. Consequently, the availability of adequate process modelling software would offer a powerful tool to support efficient process set-up and optimisation. This work examines the contribution to the overall heat transfer of various thermal phenomena developing during the manufacturing sequence, including convection and radiation with the environment, conduction with support and between adjacent filaments, radiation between adjacent filaments and convection with entrapped air. The magnitude of the mechanical deformation is also studied. Once this exercise is completed, it is possible to select the material properties, process variables and thermal phenomena that should be taken in for effective numerical modelling of FFE.

Analysis of polydicyclopentadiene-metal hybrid adhesive joints for automotive exterior body applications

An exterior body panel solution containing a polydicyclopentadiene skin attached to an interior metallic reinforcement through adhesive bonding is being studied to be applied in the MobiCar bonnet. With this solution is expected to achieve lightness, adequate structural integrity and cost-efficiency. However, there is uncertainty regarding to the bonnet adhesiveness since different metallic materials and adhesive types are being considered for its development. Thus, in this paper, several samples are tested through shear loading with the aim of understanding the loading magnitude expected by using polydicyclopentadiene, steel DC04+ZE and aluminum alloy AW5754-H111 as substrates adhesively bonded by an epoxy or a methacrylate. Methacrylate adhesive have shown greater shear strength in all types of adhesive joints. PDCPD joints presented the highest displacements. Surface degradation was considered adequate over abrading once none strength difference was seen between the different surface treatments. Steel treated by cataphoresis has shown the highest joint interface strength.