Desenvolvimento de biodiesel microemulsionado com reaproveitamento de resíduos de óleos vegetais

Pós-graduação em Engenharia Mecânica - FEG

Thermodynamic analysis and comparison of downdraft gasifiers integrated with gas turbine, spark and compression ignition engines for distributed power generation

The objective of the present article is to assess and compare the performance of electricity generation systems integrated with downdraft biomass gasifiers for distributed power generation. A model for estimating the electric power generation of internal combustion engines and gas turbines powered by syngas was developed. First, the model determines the syngas composition and the lower heating value; and second, these data are used to evaluate power generation in Otto, Diesel, and Brayton cycles. Four synthesis gas compositions were tested for gasification with: air; pure oxygen; 60% oxygen with 40% steam; and 60% air with 40% steam. The results show a maximum power ratio of 0.567 kWh/Nm(3) for the gas turbine system, 0.647 kWh/Nm(3) for the compression ignition engine, and 0.775 kWh/Nm(3) for the spark-ignition engine while running on synthesis gas which was produced using pure oxygen as gasification agent. When these three systems run on synthesis gas produced using atmospheric air as gasification agent, the maximum power ratios were 0.274 kWh/Nm(3) for the gas turbine system, 0.302 kWh/Nm(3) for CIE, and 0.282 kWh/Nm(3) for SIE. The relationship between power output and synthesis gas flow variations is presented as is the dependence of efficiency on compression ratios. Since the maximum attainable power ratio of CIE is higher than that of SIE for gasification with air, more research should be performed on utilization of synthesis gas in CIE. (C) 2014 Elsevier Ltd. All rights reserved.

Removal of dyes by lignocellulose adsorbents originating from biodiesel production

In this study, use was made of tucumã cake, in natura (TCN) and thermally treated (TCT), as potential alternative adsorbents for the adsorption of cationic and anionic dyes. The effects of the parameters: contact time, adsorbent: adsorbate mass ratio, and initial concentration of dye were analyzed. The adsorption isotherms were established from optimized adsorption parameters. The best conditions for adsorption were: equilibrium time of 7 h, concentration of 25 mg L 1 and ratio of 1:200 for the methylene blue dye; and pH 6.5, concentration of 25 mg L 1 and ratio of 1:200 for the congo red dye. The adsorption process was best represented by the Dubinin–Radushkevich and Sips isotherms. The kinetics of adsorption of the dyes were best described by the pseudo-second-order kinetic and Elovich models. TCT showed the best maximum adsorption capacity (Qm) for the methylene blue dye (63.92 mg g 1 ).

Frequency tunable continuous THz wave generation in a periodically poled fiber

An all-fiber approach to terahertz generation using a periodically poled optical fiber is proposed and experimentally demonstrated. In the proposed approach, a continuous-wave THz wave is generated at a periodically poled fiber by beating two optical wavelengths from two laser sources with the wavelength spacing corresponding to the frequency of the THz wave. The key component in the system is the periodically poled fiber, which is made by a twin-hole fiber with the fiber core residing between two holes. The twin-hole fiber is then thermally poled at a temperature of similar to 260 degrees C with a voltage of 3.3 kV applied to the silver electrodes inside the two holes to introduce second-order nonlinearity. The quasi phase matching (QPM) condition is achieved by periodically erasing the thermal poling induced second-order nonlinearity with an ultraviolet laser, which enhances the energy conversion efficiency. The proposed approach is validated by an experiment. The emission of a THz wave centered at 3.8 THz with an output power of 0.5 mu W is observed. The frequency tunability between 2.2 and 3.8 THz is also experimentally demonstrated.

Características Físico-Químicas, energéticas e desempenho da fibra de coco na sorção de óleo diesel e biodiesel

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dynamic Lightpath Scheduling in Next-Generation WDM Optical Networks

Lightpath scheduling is an important capability in next-generation wavelength-division multiplexing (WDM) optical networks to reserve resources in advance for a specified time period while provisioning end-to-end lightpaths. In this study, we propose an approach to support dynamic lightpath scheduling in such networks. To minimize blocking probability in a network that accommodates dynamic scheduled lightpath demands (DSLDs), resource allocation should be optimized in a dynamic manner. However, for the network users who desire deterministic services, resources must be reserved in advance and guaranteed for future use. These two objectives may be mutually incompatible. Therefore, we propose a two-phase dynamic lightpath scheduling approach to tackle this issue. The first phase is the deterministic lightpath scheduling phase. When a lightpath request arrives, the network control plane schedules a path with guaranteed resources so that the user can get a quick response with the deterministic lightpath schedule. The second phase is the lightpath re-optimization phase, in which the network control plane re-provisions some already scheduled lightpaths. Experimental results show that our proposed two-phase dynamic lightpath scheduling approach can greatly reduce WDM network blocking.

REALISTIC IVUS IMAGE GENERATION IN DIFFERENT INTRALUMINAL PRESSURES

Intravascular ultrasound (IVUS) phantoms are important to calibrate and evaluate many IVUS imaging processing tasks. However, phantom generation is never the primary focus of related works; hence, it cannot be well covered, and is usually based on more than one platform, which may not be accessible to investigators. Therefore, we present a framework for creating representative IVUS phantoms, for different intraluminal pressures, based on the finite element method and Field II. First, a coronary cross-section model is selected. Second, the coronary regions are identified to apply the properties. Third, the corresponding mesh is generated. Fourth, the intraluminal force is applied and the deformation computed. Finally, the speckle noise is incorporated. The framework was tested taking into account IVUS contrast, noise and strains. The outcomes are in line with related studies and expected values. Moreover, the framework toolbox is freely accessible and fully implemented in a single platform. (E-mail: fernando.okara@gmail.com) (c) 2012 World Federation for Ultrasound in Medicine & Biology.

Plantar flexion force induced by amplitude-modulated tendon vibration and associated soleus V/F-waves as an evidence of a centrally-mediated mechanism contributing to extra torque generation in humans

Background: High-frequency trains of electrical stimulation applied over the human muscles can generate forces higher than would be expected by direct activation of motor axons, as evidenced by an unexpected relation between the stimuli and the evoked contractions, originating what has been called “extra forces”. This phenomenon has been thought to reflect nonlinear input/output neural properties such as plateau potential activation in motoneurons. However, more recent evidence has indicated that extra forces generated during electrical stimulation are mediated primarily, if not exclusively, by an intrinsic muscle property, and not from a central mechanism as previously thought. Given the inherent differences between electrical and vibratory stimuli, this study aimed to investigate: (a) whether the generation of vibration-induced muscle forces results in an unexpected relation between the stimuli and the evoked contractions (i.e. extra forces generation) and (b) whether these extra forces are accompanied by signs of a centrally-mediated mechanism or whether intrinsic muscle properties are the redominant mechanisms. Methods: Six subjects had their Achilles tendon stimulated by 100 Hz vibratory stimuli that linearly increased in amplitude (with a peak-to-peak displacement varying from 0 to 5 mm) for 10 seconds and then linearly decreased to zero for the next 10 seconds. As a measure of motoneuron excitability taken at different times during the vibratory stimulation, short-latency compound muscle action potentials (V/F-waves) were recorded in the soleus muscle in response to supramaximal nerve stimulation. Results: Plantar flexion torque and soleus V/F-wave amplitudes were increased in the second half of the stimulation in comparison with the first half. Conclusion: The present findings provide evidence that vibratory stimuli may trigger a centrally-mediated mechanism that contributes to the generation of extra torques. The vibration-induced increased motoneuron excitability (leading to increased torque generation) presumably activates spinal motoneurons following the size principle, which is a desirable feature for stimulation paradigms involved in rehabilitation programs and exercise training.

Generation of the Cape Ghir upwelling filament: a numerical study

[EN] Filaments are narrow, shallow structures of cool water originating from the coast. They are typical features of the four main eastern boundary upwelling systems (EBUS). In spite of their significant biological and chemical roles, through the offshore exportation of nutrient-rich waters, the physical processes that generate them are still not completely understood. This paper is a process-oriented study of filament generation mechanisms. Our goal is twofold: firstly, to obtain a numerical solution able to well represent the characteristics of the filament off Cape Ghir (30°38'N, northwestern Africa) in the Canary EBUS and secondly, to explain its formation by a simple mechanism based on the balance of potential vorticity. The first goal is achieved by the use of the ROMS model (Regional Ocean Modeling System) in embedded domains around Cape Ghir, with a horizontal resolution going up to 1.5 km for the finest domain. The latter gets its initial and boundary conditions from a parent solution and is forced by climatological, high-resolution atmospheric fields. The modeled filaments display spatial, temporal and physical characteristics in agreement with the available in situ and satellite observations. This model solution is used as a reference to compare the results with a set of process-oriented experiments. These experiments allow us to reach the second objective. Their respective solution serves to highlight the contribution of various processes in the filament generation. Since the study is focused on general processes present under climatological forcing conditions, inter-annual forcing is not necessary. The underlying idea for the filament generation is the balance of potential vorticity in the Canary EBUS: the upwelling jet is characterized by negative relative vorticity and flows southward along a narrow band of uniform potential vorticity. In the vicinity of the cape, an injection of relative vorticity induced by the wind breaks the existing vorticity balance. The upwelling jet is prevented from continuing its way southward and has to turn offshore to follow lines of equal potential vorticity. The model results highlight the essential role of wind, associated with the particular topography (coastline and bottom) around the cape. The mechanism presented here is general and thus can be applied to other EBUS.

Automatic code generation: from process algebraic architectural descriptions to multithreaded java programs

Process algebraic architectural description languages provide a formal means for modeling software systems and assessing their properties. In order to bridge the gap between system modeling and system im- plementation, in this thesis an approach is proposed for automatically generating multithreaded object-oriented code from process algebraic architectural descriptions, in a way that preserves – under certain assumptions – the properties proved at the architectural level. The approach is divided into three phases, which are illustrated by means of a running example based on an audio processing system. First, we develop an architecture-driven technique for thread coordination management, which is completely automated through a suitable package. Second, we address the translation of the algebraically-specified behavior of the individual software units into thread templates, which will have to be filled in by the software developer according to certain guidelines. Third, we discuss performance issues related to the suitability of synthesizing monitors rather than threads from software unit descriptions that satisfy specific constraints. In addition to the running example, we present two case studies about a video animation repainting system and the implementation of a leader election algorithm, in order to summarize the whole approach. The outcome of this thesis is the implementation of the proposed approach in a translator called PADL2Java and its integration in the architecture-centric verification tool TwoTowers.

Probabilistic approaches in civil engineering: generation of random fields and structural identification with genetic algorithms

The inherent stochastic character of most of the physical quantities involved in engineering models has led to an always increasing interest for probabilistic analysis. Many approaches to stochastic analysis have been proposed. However, it is widely acknowledged that the only universal method available to solve accurately any kind of stochastic mechanics problem is Monte Carlo Simulation. One of the key parts in the implementation of this technique is the accurate and efficient generation of samples of the random processes and fields involved in the problem at hand. In the present thesis an original method for the simulation of homogeneous, multi-dimensional, multi-variate, non-Gaussian random fields is proposed. The algorithm has proved to be very accurate in matching both the target spectrum and the marginal probability. The computational efficiency and robustness are very good too, even when dealing with strongly non-Gaussian distributions. What is more, the resulting samples posses all the relevant, welldefined and desired properties of “translation fields”, including crossing rates and distributions of extremes. The topic of the second part of the thesis lies in the field of non-destructive parametric structural identification. Its objective is to evaluate the mechanical characteristics of constituent bars in existing truss structures, using static loads and strain measurements. In the cases of missing data and of damages that interest only a small portion of the bar, Genetic Algorithm have proved to be an effective tool to solve the problem.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

In vitro generation and characterization of acute myeloid leukemia-reactive CD8 + cytotoxic T-lymphocyte clones from healthy donors

Donor-derived CD8+ cytotoxic T lymphocytes (CTLs) eliminating host leukemic cells mediate curative graft-versus-leukemia (GVL) reactions after allogeneic hematopoietic stem cell transplantation (HSCT). The leukemia-reactive CTLs recognize hematopoiesis-restricted or broadly expressed minor histocompatibility and leukemia-associated peptide antigens that are presented by human leukocyte antigen (HLA) class I molecules on recipient cells. The development of allogeneic CTL therapy in acute myeloid leukemia (AML) is hampered by the poor efficiency of current techniques for generating leukemia-reactive CTLs from unprimed healthy donors in vitro. In this work, a novel allogeneic mini-mixed lymphocyte/leukemia culture (mini-MLLC) approach was established by stimulating CD8+ T cells isolated from peripheral blood of healthy donors at comparably low numbers (i.e. 10e4/well) with HLA class I-matched primary AML blasts in 96-well microtiter plates. Before culture, CD8+ T cells were immunomagnetically separated into CD62L(high)+ and CD62L(low)+/neg subsets enriched for naive/central memory and effector memory cells, respectively. The application of 96-well microtiter plates aimed at creating multiple different responder-stimulator cell compositions in order to provide for the growth of leukemia-reactive CTLs optimized culture conditions by chance. The culture medium was supplemented with interleukin (IL)-7, IL-12, and IL-15. On day 14, IL-12 was replaced by IL-2. In eight different related and unrelated donor/AML pairs with complete HLA class I match, numerous CTL populations were isolated that specifically lysed myeloid leukemias in association with various HLA-A, -B, or -C alleles. These CTLs recognized neither lymphoblastoid B cell lines of donor and patient origin nor primary B cell leukemias expressing the corresponding HLA restriction element. CTLs expressed T cell receptors of single V-beta chain families, indicating their clonality. The vast majority of CTL clones were obtained from mini-MLLCs initiated with CD8+ CD62L(high)+ cells. Using antigen-specific stimulation, multiple CTL populations were amplified to 10e8-10e10 cells within six to eight weeks. The capability of mini-MLLC derived AML-reactive CTL clones to inhibit the engraftment of human primary AML blasts was investigated in the immunodeficient nonobese diabetic/severe combined immune deficient IL-2 receptor common γ-chain deficient (NOD/SCID IL2Rγnull) mouse model. The leukemic engraftment in NOD/SCID IL2Rγnull was specifically prevented if inoculated AML blasts had been pre-incubated in vitro with AML-reactive CTLs, but not with anti-melanoma control CTLs. These results demonstrate that myeloid leukemia-specific CTL clones capable of preventing AML engraftment in mice can be rapidly isolated from CD8+ CD62L(high)+ T cells of healthy donors in vitro. The efficient generation and expansion of these CTLs by the newly established mini-MLLC approach opens the door for several potential applications. First, CTLs can be used within T cell-driven antigen identification strategies to extend the panel of molecularly defined AML antigens that are recognizable by T cells of healthy donors. Second, because these CTLs can be isolated from the stem cell donor by mini-MLLC prior to transplantation, they could be infused into AML patients as a part of the stem cell allograft, or early after transplantation when the leukemia burden is low. The capability of these T cells to expand and function in vivo might require the simultaneous administration of AML-reactive CD4+ T cells generated by a similar in vitro strategy or, less complex, the co-transfer of CD8-depleted donor lymphocytes. To prepare clinical testing, the mini-MLLC approach should now be translated into a protocol that is compatible with good manufacturing practice guidelines.

A chemical-loop approach for the generation of hydrogen by means of ethanol reforming

The work investigates the feasibility of a new process aimed at the production of hydrogen with inherent separation of carbon oxides. The process consists in a cycle in which, in the first step, a mixed metal oxide is reduced by ethanol (obtained from biomasses). The reduced metal is then contacted with steam in order to split the water and sequestrating the oxygen into the looping material’s structure. The oxides used to run this thermochemical cycle, also called “steam-iron process” are mixed ferrites in the spinel structure MeFe2O4 (Me = Fe, Co, Ni or Cu). To understand the reactions involved in the anaerobic reforming of ethanol, diffuse reflectance spectroscopy (DRIFTS) was used, coupled with the mass analysis of the effluent, to study the surface composition of the ferrites during the adsorption of ethanol and its transformations during the temperature program. This study was paired with the tests on a laboratory scale plant and the characterization through various techniques such as XRD, Mössbauer spectroscopy, elemental analysis... on the materials as synthesized and at different reduction degrees In the first step it was found that besides the generation of the expected CO, CO2 and H2O, the products of ethanol anaerobic oxidation, also a large amount of H2 and coke were produced. The latter is highly undesired, since it affects the second step, during which water is fed over the pre-reduced spinel at high temperature. The behavior of the different spinels was affected by the nature of the divalent metal cation; magnetite was the oxide showing the slower rate of reduction by ethanol, but on the other hand it was that one which could perform the entire cycle of the process more efficiently. Still the problem of coke formation remains the greater challenge to solve.

Cut-first branch-and-price-second for the capacitated arc-routing problem

This paper presents the first full-fledged branch-and-price (bap) algorithm for the capacitated arc-routing problem (CARP). Prior exact solution techniques either rely on cutting planes or the transformation of the CARP into a node-routing problem. The drawbacks are either models with inherent symmetry, dense underlying networks, or a formulation where edge flows in a potential solution do not allow the reconstruction of unique CARP tours. The proposed algorithm circumvents all these drawbacks by taking the beneficial ingredients from existing CARP methods and combining them in a new way. The first step is the solution of the one-index formulation of the CARP in order to produce strong cuts and an excellent lower bound. It is known that this bound is typically stronger than relaxations of a pure set-partitioning CARP model.rnSuch a set-partitioning master program results from a Dantzig-Wolfe decomposition. In the second phase, the master program is initialized with the strong cuts, CARP tours are iteratively generated by a pricing procedure, and branching is required to produce integer solutions. This is a cut-first bap-second algorithm and its main function is, in fact, the splitting of edge flows into unique CARP tours.