Eliminação do Cr(VI) na fase de neutralização de um efluente industrial proveniente de processos de galvanoplastia

A presente tese teve por base a identificação e resolução de um problema existente no tratamento de efluentes provenientes dos processos de tratamento de superfícies por galvanoplastia, na OGMA – Indústria Aeronáutica de Portugal S.A.. Observou-se a ocorrência, esporádica, de crómio hexavalente, (Cr (VI)), em valor superior ao valor limite de emissão (VLE). Os resultados foram monitorizados e os dados recolhidos no decorrer da actividade de tratamento de efluentes, durante o período de, aproximadamente, 5 anos (2006 a 2011). A recolha de resultados decorreu no âmbito da actividade profissional da mestranda, que, para além da responsabilidade técnica dos processos de galvanoplastia na empresa, é também responsável pelo suporte técnico ao processo de tratamento de efluentes resultantes da actividade de tratamento de superficies por processos de galvanoplastia. A empresa OGMA – Indústria Aeronáutica de Portugal S.A., é uma empresa de actividade aeronáutica dedicada à Fabricação e Manutenção de aeronaves, nomeadamente a prestação de serviços de Manutenção, Revisão e Modernização de, Aeronaves, Motores e Componentes, bem como Fabricação e Montagem de Aeroestruturas. Integrada na OGMA, S.A. encontra-se a área de tratamentos electroquímicos, onde são realizados processos de tratamento de materiais metálicos por electrodeposição, deposição química e conversão química. Desta actividade resulta uma quantidade considerável de efluentes líquidos que necessitam de tratamento adequado previamente à sua descarga em cursos de água. Devido ao tipo de contaminantes que estes efluentes possuem, o tratamento dos mesmos é realizado em várias etapas, passando pela oxidação de cianetos, a redução de cromatos e a neutralização. Posteriormente segue-se uma sedimentação e a remoção de lamas. De modo a garantir um controlo dos parâmetros de descarga dos efluentes tratados, de acordo com a legislação ambiental em vigor, o efluente obtido é analisado periodicamente em laboratório acreditado. Na perspectiva de solucionar o problema em questão, procedeu-se à realização de ensaios experimentais utilizando os efluentes provenientes dos tanques de reacção da redução de cromatos e da oxidação de cianetos da linha com cádmio, com especial incidência na variação dos intervalos de pH recomendados para cada uma das fases do tratamento de efluentes, e observação do comportamento das misturas em termos de presença de Cr (VI), quando sujeitos a variações de pH. Após análise dos dados disponíveis e realização de todos os ensaios, conclui-se que, o processo de oxidação de cianeto da linha com cádmio e o processo de redução de cromatos na mesma linha estão a funcionar adequadamente. Concluiu-se que o reaparecimento de Cr (VI) ocorre devido à existência de hipoclorito de sódio, em excesso, no tanque de oxidação de cianeto que, quando passa para o tanque de neutralização e entra em contacto com o efluente proveniente do tanque de redução de cromatos, oxida parte do crómio trivalente, (Cr (III)), existente, a Cr (VI). Para impedir a ocorrência deste fenómeno separou-se todo o efluente contendo crómio que passou a ser tratado na linha de tratamento de efluentes isenta de cádmio, não entrando assim em contacto com o efluente que contém hipoclorito não reagido, evitando a oxidação do Cr (III) a Cr (VI).

Aumento de capacidade em sistemas MIMO coordenados para advanced LTE com utilização de repetidores fixos

Com vista a revolucionar o sector das comunicações móveis, muito à custa dos elevados débitos prometidos, a tecnologia LTE recorre a uma técnica que se prevê que seja bastante utilizada nas futuras redes de comunicações móveis: Relaying. Juntamente com esta técnica, o LTE recorre à técnica MIMO, para melhorar a qualidade da transmissão em ambientes hostis e oferecer elevados ritmos de transmissão. No planeamento das próximas redes LTE, o recurso à técnica Relaying é frequente. Esta técnica, tem como objectivo aumentar a cobertura e/ou capacidade da rede, e ainda melhorar o seu desempenho em condições de fronteira de célula. A performance de uma RS depende da sua localização, das condições de propagação do canal rádio a que tanto a RS como o EU estão sujeitos, e ainda da capacidade que a RS tem de receber, processar e reencaminhar a informação. O objectivo da tese é estudar a relação existente entre o posicionamento de uma RS e o seu desempenho. Desta forma, pretende-se concluir qual a posição ideal de uma RS (tanto do tipo AF como SDF). Para além deste estudo, é apresentado um comparativo do desempenho dos modos MIMO TD e OL-SM, onde se conclui em que condições deverão ser utilizados, numa rede LTE equipada com FRSs.

Novel Scorpionate and Pyrazole Dioxovanadium Complexes, Catalysts for Carboxylation and Peroxidative Oxidation of Alkanes

The dioxovanadium(V) complexes [VO2(3,5-Me(2)Hpz)(3)][BF4] (1) (pz = pyrazolyl), [VO2{SO3C(pz)(3)}] (2), [VO2{HB(3,5-Me(2)pz)(3)}] (3) and [VO2{HC(pz)(3)}][BF4] (4), bearing pyrazole or scorpionate ligands, were obtained by reaction of triethyl vanadate [VO(OEt)(3)] with hydrotris(3,5-dimethyl-1-pyrazolyl)methane [HC(3,5-Me(2)pz)(3)] or 3,5-dimethylpyrazole (3,5-Me(2)Hpz; 1), lithium tris(1-pyrazolyl)methanesulfonate {Li[SO3C(pz)(3)], 2}, potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate {K[HB(3,5-Me(2)pz)(3)], 3} and hydrotris(1-pyrazolyl)methane [HC(pz)(3), 4], respectively. Treatment of [VO(OEt)(3)] with potassium hydrotris(1-pyrazolyl)borate {K[HB(pz)(3)]} led to the mixed eta(3)-tris(pyrazolyl)borate and eta(2)-bis(pyrazolyl)borate oxovanadium(IV) complex [VO{HB(pz)(3)}{H2B(pz)(2)}, 5]. The compounds were characterized by elemental analyses, IR, NMR and EPR spectroscopy, FAB and ESI mass spectrometry, cyclic voltammetry and, for 5, also by single crystal X-ray diffraction analysis. All complexes exhibit catalytic activity in the single-pot carboxylation [in trifluoroacetic acid/potassium peroxodisulfate (CF3COOH/K2S2O8)] of gaseous alkanes (methane and ethane) to carboxylic acids (yields up to 40%. TONs up to 157) and in the peroxidative oxidation [in water/acetonitrile (H2O/NCMe)] of liquid alkanes (cyclohexane and cyclopentane) to the corresponding alcohols and ketones (yields up to 24%, TONs up to 117), under mild conditions.

Oxorhenium Complexes Bearing the Water-Soluble Tris(pyrazol-1-yl)methanesulfonate, 1,3,5-Triaza-7-phosphaadamantane, or Related Ligands, as Catalysts for Baeyer-Villiger Oxidation of Ketones

New rhenium(VII or III) complexes [ReO3(PTA)(2)][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4] (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)(2)] [ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(eta(2)-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)(3), pz = pyrazolyl), [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)(3)(-)] and [ReCl2{N2C(O)Ph} (PTA)(3)] (7) have been prepared from the Re(VII) oxide Re2O2 (1-6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2(N2C-(O)Ph}(Hpz)(PPh3)(2)], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re-PTA bond energy and hard-soft acid-base theory. The oxo-rhenium complexes 1-6 act as selective catalysts for the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process.

Novel coordination polymers with (Pyrazolato)-based tectons: catalytic activity in the peroxidative oxidation of alcohols and cyclohexane

Coupling five rigid or flexible bis(pyrazolato)based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340-500 degrees C. As demonstrated by N-2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135-1758 m(2)/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (0 the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cydohexane to cydohexanol and cydohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 x 10(3)) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cydohexane, the latter value being higher than that granted by the current industrial process.

The portuguese insurance industry: basis for strategic process decision

Nowadays, the Portuguese insurance industry operates in a market with a much more aggressive structure than a few decades ago. Markets and the economy have become globalised since the last decade of the 20th century. Market forces have gradually shifted – power is now mainly on the demand side. In order to meet the new requirements, the insurance industry must develop a strong strategic ability to respond to constant changes of the new international economic order.One of the basic aspects of this strategic development will focus on the ability to predict the future. We introduce the subject by briefly describing the sector, its organisational structure in the Portuguese market, and challenges arising from the development of the European Union. We then analyse the economic and financial structure of the sector. From this point of view, we aim at the possibility of designing models that could explain the demand for insurance, claims and technical reserves evolution. Such models, (even if based on the past), would resolve, at least partly, one of the greatest difficulties experienced by insurance companies when estimating the budget. Thus, we examine the existence of variables that explain the previous points, which are capable of forming a basis for designing models that are simple but efficient, and can be used for strategic planning.

Design of improved rail-to-rail low-distortion and low-stress switches in advanced CMOS technologies

This paper describes the efficient design of an improved and dedicated switched-capacitor (SC) circuit capable of linearizing CMOS switches to allow SC circuits to reach low distortion levels. The described circuit (SC linearization control circuit, SLC) has the advantage over conventional clock-bootstrapping circuits of exhibiting low-stress, since large gate voltages are avoided. This paper presents exhaustive corner simulation results of a SC sample-and-hold (S/H) circuit which employs the proposed and optimized circuits, together with the experimental evaluation of a complete 10-bit ADC utilizing the referred S/H circuit. These results show that the SLC circuits can reduce distortion and increase dynamic linearity above 12 bits for wide input signal bandwidths.

RF Receiver Front End for 28.5 GHz Applications on a 70 GHz F-T SiGe BiCMOS Process

This article presents the design and test of a receiver front end aimed at LMDS applications at 28.5 GHz. It presents a system-level design after which the receiver was designed. The receiver comprises an LNA, quadrature mixer and quadrature local oscillator. Experimental results at 24 GHz center frequency show a conversion voltage gain of 15 dB and conversion noise figure of 14 5 dB. The receiver operates from a 2 5 V power supply with a total current consumption of 31 mA.

Advanced side information creation techniques and framework for Wyner-Ziv video coding

Recently, several distributed video coding (DVC) solutions based on the distributed source coding (DSC) paradigm have appeared in the literature. Wyner-Ziv (WZ) video coding, a particular case of DVC where side information is made available at the decoder, enable to achieve a flexible distribution of the computational complexity between the encoder and decoder, promising to fulfill novel requirements from applications such as video surveillance, sensor networks and mobile camera phones. The quality of the side information at the decoder has a critical role in determining the WZ video coding rate-distortion (RD) performance, notably to raise it to a level as close as possible to the RD performance of standard predictive video coding schemes. Towards this target, efficient motion search algorithms for powerful frame interpolation are much needed at the decoder. In this paper, the RD performance of a Wyner-Ziv video codec is improved by using novel, advanced motion compensated frame interpolation techniques to generate the side information. The development of these type of side information estimators is a difficult problem in WZ video coding, especially because the decoder only has available some reference, decoded frames. Based on the regularization of the motion field, novel side information creation techniques are proposed in this paper along with a new frame interpolation framework able to generate higher quality side information at the decoder. To illustrate the RD performance improvements, this novel side information creation framework has been integrated in a transform domain turbo coding based Wyner-Ziv video codec. Experimental results show that the novel side information creation solution leads to better RD performance than available state-of-the-art side information estimators, with improvements up to 2 dB: moreover, it allows outperforming H.264/AVC Intra by up to 3 dB with a lower encoding complexity.

Cork processing wastewater treatment/valorisation by nanofiltration

Nanofiltration process for the treatment/valorisation of cork processing wastewaters was studied. A DS-5 DK 20/40 (GE Water Technologies) nanofiltration membrane/module was used, having 2.09 m(2) of surface area. Hydraulic permeability was determined with pure water and the result was 5.2 L.h(-1).m(-2).bar(-1). The membrane presents a rejection of 51% and 99% for NaCl and MgSO4 salts, respectively. Two different types of regimes were used in the wastewaters filtration process, total recycling mode and concentration mode. The first filtration regime showed that the most favourable working transmembrane pressure was 7 bar working at 25 degrees C. For the concentration mode experiments it was observed a 30% decline of the permeate fluxes when a volumetric concentration factor of 5 was reached. The permeate COD, BOD5, colour and TOC rejection values remained well above the 90% value, which allows, therefore, the concentration of organic matter (namely the tannin fraction) in the concentrate stream that can be further used by other industries. The permeate characterization showed that it cannot be directly discharged to the environment as it does not fulfil the values of the Portuguese discharge legislation. However, the permeate stream can be recycled to the process (boiling tanks) as it presents no colour and low TOC (< 60 ppm) or if wastewater discharge is envisaged we have observed that the permeate biodegradability is higher than 0.5, which renders conventional wastewater treatments feasible.

CVD of CrO(2): Towards a lower temperature deposition process

The deposition of highly oriented a-axis CrO(2) films onto Al(2)O(3)(0001) by atmospheric pressure (AP)CVD at temperatures as low as 330 C is reported. Deposition rates strongly depend on the substrate temperature, whereas for film surface microstructures the dependence is mainly on film thickness. For the experimental conditions used in this work, CrO(2) growth kinetics are dominated by a surface reaction mechanism with an apparent activation energy of (121.0 +/- 4.3) kJ mol(-1). The magnitude and temperature dependence of the saturation magnetization, up to room temperature, is consistent with bulk measurements.

The (well) informed piano : internalization and growth process

The subject matter of this book is about piano methodology, including technical, musical, artistic, ethical and philosophical issues and reflections. The purpose of this work is to share a personal professional experience insight in the field of piano performance. This text assumes a certain continuity to the major contributions of artists like Ludwig Deppe, Tobias Matthay, Grigory Kogan, Heinrich Neuhaus and George Kochevitsky. At the same time, it tries to integrate and complement this selected literature, bringing new ideas and hints to specific professional issues.

Bioconversion of D-glucose into D-glucosone by immobilized glucose 2-oxidase from Coriolus versicolorat moderate pressures

The immobilized glucose 2-oxidase (pyranose oxidase, pyranose:oxygen-2-oxidoreductase, EC 1.1.3.10) from Coriolus versicolor was used to convert D-glucose into D-glucosone at moderate pressures, up to 150 bar, with compressed air in a modified commercial batch reactor. Several parameters affecting biocatalysis at moderate pressures were investigated as follows: pressure, different forms of immobilized biocatalysts, glucose concentration, pH, temperature and the presence of catalase. Glucose 2-oxidase (GOX2) was purified by immobilized metal affinity chromatography on epoxy-activated Sepharose 6B-IDA-Cu(II) column at pH 6.0. Purified enzyme and catalase were immobilized into a polyethersulfone (PES) membrane in the presence of glutaraldehyde and gelatin. Enhancement of the bioconversion of D-glucose was done by the pressure since an increase in the pressure with compressed air increases the conversion rates. The optimum temperature and pH for bioconversion of D-glucose were found to be 62 degrees C and pH 6.0, respectively and the activation energy (E(a)) was 28.01 kJ mol(-1). The apparent kinetic constants (V(max)' K(m)', K(cat)' and K(cat)/K(m)') for this bioconversion were 2.27 U mg(-1) protein, 11.15 mM, 8.33 s(-1) and 747.38 s(-1) M(-1), respectively. The immobilized biomass of C. versicolor as well as crude extract containing GOX2 activity were also useful for bioconversion of D-glucose at 65 bar with a yield of 69.9 +/- 3.8% and 91.3 +/- 1.2%, respectively. The immobilized enzyme was apparently stable for several months without any significant loss of enzyme activity. On the other hand, this immobilized enzyme was also stable at moderate pressures, since such pressures did not affect significantly the enzyme activity. (C) 2010 Elsevier Ltd. All rights reserved.

Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.