New heterogeneous catalysts for trans-esterification of triglycerides

This paper describes preliminary work done towards the development of new metallic heterogeneous catalysts to be used in the transesterification reaction of triglycerides, which is of considerable interest in the production of biodiesel. Biodiesel, is a mixture of mono-alkyl esters of fatty acids, and is currently manufactured by transesterification of triglycerides with methanol using NaOH or KOH as liquid base catalyst. Catalysts as such are corrosive to the equipment, and as these catalysts are in liquid phase must be neutralized after the completion of the reaction, typically using HCl, thus producing salt streams. Moreover, due to the presence of free fatty acids it reacts to form soaps as unwanted by-products, hence requiring more expensive separation processes. Therefore, there is a great need on the development of industrial processes for biodiesel production using solid acid catalysts. The key benefit of using solid acid catalysts is that no polluting by-products are formed and the catalysts do not have to be removed since they do not mix with the biodiesel product.

Advances on the development of novel heterogeneous catalysts for transesterification of triglycerides in biodiesel

This paper describes experimental work done towards the search for more profitable and sustainable alternatives regarding biodiesel production, using heterogeneous catalysts instead of the conventional homogenous alkaline catalysts, such as NaOH, KOH or sodium methoxide, for the methanolysis reaction. This experimental work is a first stage on the development and optimization of new solid catalysts, able to produce biodiesel from vegetable oils. The heterogeneous catalytic process has many differences from the currently used in industry homogeneous process. The main advantage is that, it requires lower investment costs, since no need for separation steps of methanol/catalyst, biodiesel/catalyst and glycerine/catalyst. This work resulted in the selection of CaO and CaO modified with Li catalysts, which showed very good catalytic performances with high activity and stability. In fact FAME yields higher than 92% were observed in two consecutive reaction batches without expensive intermediate reactivation procedures. Therefore, those catalysts appear to be suitable for biodiesel production.

Copper Bis(oxazoline) Encapsulated in Zeolites and Its Application as Heterogeneous Catalysts for the Cyclopropanation of Styrene

A copper C(2)-symmetric bis(oxazoline), CuBox, was introduced in two forms of commercial Y zeolite: a sodium form (NaY) and an ultrastable form (NaUSY). CuBox was introduced by first partially exchanging the sodium cations of both zeolites for copper and then by refluxing the obtained materials with a solution of bis(oxazoline) (Box). Two different loadings were prepared for each form of zeolite. The materials were characterized by copper ICP-AES, elemental analysis, XPS, FTIR, TG, and nitrogen adsorption isotherms at -196 degrees C. Evidence for Box ligand location in the supercages of NaY and NaUSY zeolites and its coordination to the exchanged copper(II) was obtained by the several techniques used. The materials were all active in the cyclopropanation of styrene with ethyldiazoacetate at room temperature and diastereoselective toward trans cydopropanes. Although the materials containing Box showed low enantioselectivities, their catalytic activities were higher than the parent copper exchanged zeolites, and did not decrease with reuse, at least during three consecutive cycles.

Study on the use of MgAl hydrotalcites as solid heterogeneous catalysts for biodiesel production

This paper, reports experimental work on the use of new heterogeneous solid basic catalysts for biodiesel production: double oxides of Mg and Al, produced by calcination, at high temperature, of MgAl lamellar structures, the hydrotalcites (HT). The most suitable catalyst system studied are hydrotalcite Mg:Al 2:1 calcinated at 507 degrees C and 700 degrees C, leading to higher values of FAME also in the second reaction stage. One of the prepared catalysts resulted in 97.1% Fatty acids methyl esters (FAME) in the 1st reaction step, 92.2% FAME in the 2nd reaction step and 34% FAME in the 3rd reaction step. The biodiesel obtained in the transesterification reaction showed composition and quality parameters within the limits specified by the European Standard EN 14214. 2.5% wt catalyst/oil and a molar ratio methanol:oil of 9:1 or 12:1 at 60 -65 degrees C and 4 h of reaction time are the best operating conditions achieved in this study. This study showed the potential of Mg/Al hydrotalcites as heterogeneous catalysts for biodiesel production. (C) 2011 Elsevier Ltd. All rights reserved.

Copper(II) aza-bis(oxazoline) complex immobilized onto ITQ-2 and MCM-22 based materials as heterogeneous catalysts for the cyclopropanation of styrene

A copper(II) chiral aza-bis(oxazoline) homogeneous catalyst (CuazaBox) was anchored onto the external surface of MCM-22 and ITQ-2 structures, as well as encapsulated into hierarchical MCM-22. The transition metal complex loading onto the porous solids was determined by ICP-AES and the materials were also characterized by elemental analysis (C, N, H, S), FTIR, XPS, TG and low temperature N-2 adsorption isotherms. The materials were tested as heterogeneous catalysts in the benchmark reaction of cyclopropanation of styrene to check the effect of the immobilization procedure on the catalytic parameters, as well as on their reutilization in several catalytic cycles. Catalyst CuazaBox anchored onto the external surface of MCM-22 and ITQ-2 materials were more active and enantioselective in the cyclopropanation of styrene than the corresponding homogeneous phase reaction run under similar experimental conditions. This is due to the propylation of the acidic aza-Box nitrogen. HMCM-22 was nevertheless the best heterogeneous catalyst. Encapsulation of CuazaBox on post-synthesis modified MCM-22 materials led to low activities and enantioselectivities. But reversal on the stereochemical course of the reaction was observed, probably due to confinement effect. (C) 2013 Elsevier Inc. All rights reserved.

A model for heterogeneous networks management and Performance evaluation

In general, modern networks are analysed by taking several Key Performance Indicators (KPIs) into account, their proper balance being required in order to guarantee a desired Quality of Service (QoS), particularly, cellular wireless heterogeneous networks. A model to integrate a set of KPIs into a single one is presented, by using a Cost Function that includes these KPIs, providing for each network node a single evaluation parameter as output, and reflecting network conditions and common radio resource management strategies performance. The proposed model enables the implementation of different network management policies, by manipulating KPIs according to users' or operators' perspectives, allowing for a better QoS. Results show that different policies can in fact be established, with a different impact on the network, e.g., with median values ranging by a factor higher than two.

Dosimetric effect of tissue heterogeneity for 125I prostate implants

Aim - To use Monte Carlo (MC) together with voxel phantoms to analyze the tissue heterogeneity effect in the dose distributions and equivalent uniform dose (EUD) for (125)I prostate implants. Background - Dose distribution calculations in low dose-rate brachytherapy are based on the dose deposition around a single source in a water phantom. This formalism does not take into account tissue heterogeneities, interseed attenuation, or finite patient dimensions effects. Tissue composition is especially important due to the photoelectric effect. Materials and Methods - The computed tomographies (CT) of two patients with prostate cancer were used to create voxel phantoms for the MC simulations. An elemental composition and density were assigned to each structure. Densities of the prostate, vesicles, rectum and bladder were determined through the CT electronic densities of 100 patients. The same simulations were performed considering the same phantom as pure water. Results were compared via dose-volume histograms and EUD for the prostate and rectum. Results - The mean absorbed doses presented deviations of 3.3-4.0% for the prostate and of 2.3-4.9% for the rectum, when comparing calculations in water with calculations in the heterogeneous phantom. In the calculations in water, the prostate D 90 was overestimated by 2.8-3.9% and the rectum D 0.1cc resulted in dose differences of 6-8%. The EUD resulted in an overestimation of 3.5-3.7% for the prostate and of 7.7-8.3% for the rectum. Conclusions - The deposited dose was consistently overestimated for the simulation in water. In order to increase the accuracy in the determination of dose distributions, especially around the rectum, the introduction of the model-based algorithms is recommended.

Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.

Wetting response of KrF laser ablated polyimide surfaces

The wettability of polyimide surfaces microstructured using KrF laser radiation at fluences above the material ablation threshold was studied by static contact angle measurements. The laser-treated surfaces present a morphology consisting of conical features whose dimensions and areal density depend on the fluence. The effect of these parameters on the surface apparent contact angle depends on the wetting regime. When wetting occurs in the homogeneous regime, the apparent contact angle of the treated surfaces increases with the radiation fluence because the cone dimensions increase. In contrast, when wetting occurs in the heterogeneous regime, the apparent contact angle increases with the radiation fluence because the average distance between cones increases. The apparent water contact angle of the laser-treated surfaces can reach values as high as 162 degrees, as compared to 75 degrees for virgin polyimide.

Mobi-system: assistente pessoal de viagem

Este trabalho sugere uma solução de integração de dados em tempo real no contexto dos transportes públicos. Com o aumento das alternativas oferecidas aos utilizadores dos transportes públicos é importante que estes conheçam todas as alternativas com base em informação em tempo real para que realizem a escolha que melhor se enquadre às suas necessidades. Por outro lado, os operadores de transportes públicos deverão ser capazes de disponibilizar toda a informação pretendida com o mínimo de esforço ou de alterações ao sistema que têm implementado. Neste trabalho serão utilizadas ferramentas que permitem fornecer uma visão homogénea das várias fontes de dados heterogéneas, sendo essa homogeneidade o ponto de integração de todas as fontes de dados com as aplicações cliente.

A method to analyse the alignment of core values in collaborative networked organisations

Since collaborative networked organisations are usually formed by independent and heterogeneous entities, it is natural that each member holds his own set of values, and that conflicts among partners might emerge because of some misalignment of values. In contrast, it is often stated in literature that the alignment between the value systems of members involved in collaborative processes is a prerequisite for successful co-working. As a result, the issue of core value alignment in collaborative networks started to attract attention. However, methods to analyse such alignment are lacking mainly because the concept of 'alignment' in this context is still ill defined and shows a multifaceted nature. As a contribution to the area, this article introduces an approach based on causal models and graph theory for the analysis of core value alignment in collaborative networks. The potential application of the approach is then discussed in the virtual organisations' breeding environment context.

Elements of a methodology to assess the alignment of core-values in collaborative networks

Collaborative networks are typically formed by heterogeneous and autonomous entities, and thus it is natural that each member has its own set of core-values. Since these values somehow drive the behaviour of the involved entities, the ability to quickly identify partners with compatible or common core-values represents an important element for the success of collaborative networks. However, tools to assess or measure the level of alignment of core-values are lacking. Since the concept of 'alignment' in this context is still ill-defined and shows a multifaceted nature, three perspectives are discussed. The first one uses a causal maps approach in order to capture, structure, and represent the influence relationships among core-values. This representation provides the basis to measure the alignment in terms of the structural similarity and influence among value systems. The second perspective considers the compatibility and incompatibility among core-values in order to define the alignment level. Under this perspective we propose a fuzzy inference system to estimate the alignment level, since this approach allows dealing with variables that are vaguely defined, and whose inter-relationships are difficult to define. Another advantage provided by this method is the possibility to incorporate expert human judgment in the definition of the alignment level. The last perspective uses a belief Bayesian network method, and was selected in order to assess the alignment level based on members' past behaviour. An example of application is presented where the details of each method are discussed.

A new sedimentary benchmark for the Deccan Traps volcanism?

The origin of the Cretaceous-Paleogene boundary (KPB) mass extinction is still the center of acrimonious debates by opposing partisans of the bolide impact theory to those who favored a terrestrial origin linked to the Deccan Traps volcanism. Here we apply an original and high-resolution environmental magnetic study of the reference Bidart section, France. Our results show that the KPB is identified by an abrupt positive shift of the magnetic susceptibility (MS), also observed by others at the KPB elsewhere. In addition, an anomalous interval of very low MS, carried by an unknown Cl-bearing iron oxide similar to specular hematite, is depicted just below the KPB. Grain-size and morphology of the Cl-iron oxide are typically in the range of hematitic dust currently transported by winds from Sahara to Europe. This discovery is confirmed in the referenced Gubbio section (Italy) suggesting a global scale phenomenon. As a conjecture we suggest an origin by heterogeneous reaction between HCl-rich volcanic gas and liquid-solid aerosols within buoyant atmospheric plumes formed above the newly emitted Deccan flood basalts. Based on this hypothesis, our discovery provides a new benchmark for the Deccan volcanism and witnesses the nature and importance of the related atmospheric change.

Medições de dose no cristalino e na tiróide em tomografia computorizada: projecto

Mestrado em Radiações Aplicadas às Tecnologias da Saúde. Área de especialização: Protecção Contra Radiações

Avaliação da dose absorvida na tiróide, em cintigrafias com 123I e Na99mTcO4 utilizando modelos biocinéticos e métodos de Monte Carlo

Mestrado em Radiações Aplicadas às Tecnologias da Saúde. Área de especialização: Protecção contra Radiações