Uso Sustentável de Vapor

Em 2006, a IEA (Agência Internacional de Energia), publicou alguns estudos de consumos mundiais de energia. Naquela altura, apontava na fabricação de produtos, um consumo mundial de energia elétrica, de origem fóssil de cerca 86,16 EJ/ano (86,16×018 J) e um consumo de energia nos sistemas de vapor de 32,75 EJ/ano. Evidenciou também nesses estudos que o potencial de poupança de energia nos sistemas de vapor era de 3,27 EJ/ano. Ou seja, quase tanto como a energia consumida nos sistemas de vapor da U.E. Não se encontraram números relativamente a Portugal, mas comparativamente com outros Países publicitados com alguma similaridade, o consumo de energia em vapor rondará 0,2 EJ/ano e por conseguinte um potencial de poupança de cerca 0,02 EJ/ano, ou 5,6 × 106 MWh/ano ou uma potência de 646 MW, mais do que a potência de cinco barragens Crestuma/Lever! Trata-se efetivamente de muita energia; interessa por isso perceber o onde e o porquê deste desperdício. De um modo muito modesto, pretende-se com este trabalho dar algum contributo neste sentido. Procurou-se evidenciar as possibilidades reais de os utilizadores de vapor de água na indústria reduzirem os consumos de energia associados à sua produção. Não estão em causa as diferentes formas de energia para a geração de vapor, sejam de origem fóssil ou renovável; interessou neste trabalho estudar o modo de como é manuseado o vapor na sua função de transporte de energia térmica, e de como este poderá ser melhorado na sua eficiência de cedência de calor, idealmente com menor consumo de energia. Com efeito, de que servirá se se optou por substituir o tipo de queima para uma mais sustentável se a jusante se continuarem a verificarem desperdícios, descarga exagerada nas purgas das caldeiras com perda de calor associada, emissões permanentes de vapor para a atmosfera em tanques de condensado, perdas por válvulas nos vedantes, purgadores avariados abertos, pressão de vapor exageradamente alta atendendo às temperaturas necessárias, “layouts” do sistema de distribuição mal desenhados, inexistência de registos de produção e consumos de vapor, etc. A base de organização deste estudo foi o ciclo de vapor: produção, distribuição, consumo e recuperação de condensado. Pareceu importante incluir também o tratamento de água, atendendo às implicações na transferência de calor das superfícies com incrustações. Na produção de vapor, verifica-se que os maiores problemas de perda de energia têm a ver com a falta de controlo, no excesso de ar e purgas das caldeiras em exagero. Na distribuição de vapor aborda-se o dimensionamento das tubagens, necessidade de purgas a v montante das válvulas de controlo, a redução de pressão com válvulas redutoras tradicionais; será de destacar a experiência americana no uso de micro turbinas para a redução de pressão com produção simultânea de eletricidade. Em Portugal não se conhecem instalações com esta opção. Fabricantes da República Checa e Áustria, têm tido sucesso em algumas dezenas de instalações de redução de pressão em diversos países europeus (UK, Alemanha, R. Checa, França, etc.). Para determinação de consumos de vapor, para projeto ou mesmo para estimativa em máquinas existentes, disponibiliza-se uma série de equações para os casos mais comuns. Dá-se especial relevo ao problema que se verifica numa grande percentagem de permutadores de calor, que é a estagnação de condensado - “stalled conditions”. Tenta-se também evidenciar as vantagens da recuperação de vapor de flash (infelizmente de pouca tradição em Portugal), e a aplicação de termocompressores. Finalmente aborda-se o benchmarking e monitorização, quer dos custos de vapor quer dos consumos específicos dos produtos. Esta abordagem é algo ligeira, por manifesta falta de estudos publicados. Como trabalhos práticos, foram efetuados levantamentos a instalações de vapor em diversos sectores de atividades; 1. ISEP - Laboratório de Química. Porto, 2. Prio Energy - Fábrica de Biocombustíveis. Porto de Aveiro. 3. Inapal Plásticos. Componentes de Automóvel. Leça do Balio, 4. Malhas Sonix. Tinturaria Têxtil. Barcelos, 5. Uma instalação de cartão canelado e uma instalação de alimentos derivados de soja. Também se inclui um estudo comparativo de custos de vapor usado nos hospitais: quando produzido por geradores de vapor com queima de combustível e quando é produzido por pequenos geradores elétricos. Os resultados estão resumidos em tabelas e conclui-se que se o potencial de poupança se aproxima do referido no início deste trabalho.

Block Copolymers of Unsaturated Polyesters and Functional Elastomers

Block copolymers of unsaturated polyester were prepared by condensation polymerization of hydroxyl or carboxyl terminated liquid rubbers with maleic anhydride, phthalic anhydride, and propylene glycol. The condensate obtained was mixed with styrene monomer to get an unsaturated polyester resin formulation. In this study, copolymers of unsaturated polyesters with hydroxy terminated polybutadiene, carboxy terminated nitrile rubber, and hydroxy terminated natural rubber were prepared. Mechanical properties such as tensile strength, tensile modulus, elongation at break, toughness, impact strength, surface hardness, abrasion resistance, and water absorption were evaluated after the resin was cured in appropriate molds for comparison with the control resin. The fracture toughness and impact resistance of CTBN-modified unsaturated polyester show substantial improvement by this copolymerization without seriously affecting any other property

Auf Basis umfangreicher Messdatensätze experimentell und numerisch validierte Regeln zur optimierten Auslegung von Luft-Erdwärmetauschern

Ein Luft-Erdwärmetauscher (L-EWT) kommt wegen seines niedrigen Energiebedarfs und möglicher guter Aufwandszahlen als umweltfreundliche Versorgungskomponente für Gebäude in Betracht. Dabei ist besonders vorteilhaft, dass ein L-EWT die Umgebungsluft je nach Jahreszeit vorwärmen oder auch kühlen kann. Dem zufolge sind L-EWT zur Energieeinsparung nicht nur für den Wohnhausbau interessant, sondern auch dort, wo immer noch große Mengen an fossiler Energie für die Raumkühlung benötigt werden, im Büro- und Produktionsgebäudesektor. Der Einsatzbereich eines L-EWT liegt zwischen Volumenströmen von 100 m3/h und mehreren 100.000 m3/h. Aus dieser Bandbreite und den instationären Randbedingungen entstehen erhebliche Schwierigkeiten, allgemeingültige Aussagen über das zu erwartende thermische Systemverhalten aus der Vielzahl möglicher Konstruktionsvarianten zu treffen. Hauptziel dieser Arbeit ist es, auf Basis umfangreicher, mehrjähriger Messungen an einer eigens konzipierten Testanlage und eines speziell angepassten numerischen Rechenmodells, Kennzahlen zu entwickeln, die es ermöglichen, die Betriebseigenschaften eines L-EWT im Planungsalltag zu bestimmen und ein technisch, ökologisch wie ökonomisch effizientes System zu identifizieren. Es werden die Kennzahlen elewt (Aufwandszahl), QV (Netto-Volumenleistung), ME (Meterertrag), sowie die Kombination aus v (Strömungsgeschwindigkeit) und VL (Metervolumenstrom) definiert, die zu wichtigen Informationen führen, mit denen die Qualität von Systemvarianten in der Planungsphase bewertet werden können. Weiterführende Erkenntnisse über die genauere Abschätzung von Bodenkennwerten werden dargestellt. Die hygienische Situation der durch den L-EWT transportierten Luft wird für die warme Jahreszeit, aufgrund auftretender Tauwasserbildung, beschrieben. Aus diesem Grund werden alle relevanten lufthygienischen Parameter in mehreren aufwendigen Messkampagnen erfasst und auf pathogene Wirkungen überprüft. Es wird über Sensitivitätsanalysen gezeigt, welche Fehler bei Annahme falscher Randbedingungen eintreten. Weiterhin werden in dieser Arbeit wesentliche, grundsätzliche Erkenntnisse aufbereitet, die sich aus der Betriebsbeobachtung und der Auswertung der umfangreich vorliegenden Messdaten mehrerer Anlagen ergeben haben und für die praktische Umsetzung und die Betriebsführung bedeutend sind. Hinweise zu Materialeigenschaften und zur Systemwirtschaftlichkeit sind detailliert aufgeführt.

Temperature and moist-stability effects on midlatitude orographic precipitation

Idealized, convection-resolving simulations of moist orographic flows are conducted to investigate the influence of temperature and moist stability on the drying ratio (DR), defined as the fraction of the impinging water mass removed as orographic precipitation. In flow past a long ridge, where most of the air rises over the barrier rather than detouring around it, DR decreases as the surface temperature (Ts) increases, even as the orographic cap cloud becomes statically unstable at higher Ts and develops embedded convection. This behaviour is explained by a few physical principles: (1) the Clausius–Clapeyron equation dictates that the normalized condensation rate decreases as the flow gets warmer, (2) the replacement of ice-phase precipitation growth with warm-rain processes decreases the efficiency by which condensate is converted to precipitation, thereby lowering precipitation efficiency, and (3) embedded convection acts more to vertically redistribute moisture than to enhance precipitation. Over an isolated mountain, the effects of (1) and (2) are counteracted by moisture deflection around the barrier, which is stronger in the colder, more stable flows.

A review of the theoretical basis for bulk mass flux convective parameterization

Most parameterizations for precipitating convection in use today are bulk schemes, in which an ensemble of cumulus elements with different properties is modelled as a single, representative entraining-detraining plume. We review the underpinning mathematical model for such parameterizations, in particular by comparing it with spectral models in which elements are not combined into the representative plume. The chief merit of a bulk model is that the representative plume can be described by an equation set with the same structure as that which describes each element in a spectral model. The equivalence relies on an ansatz for detrained condensate introduced by Yanai et al. (1973) and on a simplified microphysics. There are also conceptual differences in the closure of bulk and spectral parameterizations. In particular, we show that the convective quasi-equilibrium closure of Arakawa and Schubert (1974) for spectral parameterizations cannot be carried over to a bulk parameterization in a straightforward way. Quasi-equilibrium of the cloud work function assumes a timescale separation between a slow forcing process and a rapid convective response. But, for the natural bulk analogue to the cloud-work function (the dilute CAPE), the relevant forcing is characterised by a different timescale, and so its quasi-equilibrium entails a different physical constraint. Closures of bulk parameterization that use the non-entraining parcel value of CAPE do not suffer from this timescale issue. However, the Yanai et al. (1973) ansatz must be invoked as a necessary ingredient of those closures.

Aromatic-aromatic interaction between metallacycle and phenyl ring

The X-ray crystal structure of [CuL2]ClO4 where L is the 1:1 condensate of benzil-monohydrazone and 2-pyridinecarboxalde-hyde, reveals unprecedented pi - pi interaction between the metallacycles and phenyl rings. The interaction is intramolecular. (C) 2003 Elsevier Science B.V. All rights reserved.

A novel copper(I) complex that is a monomeric single helix in solid state but a dimeric double helix in solution

Single helical [(CuL)-L-I]ClO4.12CH(2)Cl(2) (L=1:2 condensate of benzil dihydrazone and 2-acetylpyridine) unfolds and coils up in CH2Cl2 solution to generate double helical [(Cu2L2)-L-I](2+).

Imidazole-imidazole stacking in some inorganic complexes

Reaction of CuCl2 center dot 2H(2)O with the 1:1 condensate (L) of 2-(2-aminoethyl) pyridine and 1-methyl-2-imidazolecarboxaldehyde in methanol yields monomeric CuLCl2 center dot H2O (1). Recrystallisation of 1 from aqueous methanol medium containing excess of PF6- affords the 1D coordination polymer [CuLCl](n)(PF6)(n) (2). A chloride bridge results in the coordination polymer. A face-to-face interaction is observed between the imidazole rings in 2. The interaction influences the structure and magnetic properties of 2 markedly. The complex 2 is ferromagnetic with a J value of 1.79 +/- 0.01 cm (1). The imidazole fragments in 2 are coordinated to the metal. In mononuclear [HgL2 ''](ClO4)(2), where L '' is the 1:2 condensate of ethylenediamine and 1-methyl-2-imidazolecarboxaldehyde, the imidazolyl moieties are not under the direct influence of the metal. Here the imidazole-imidazole interaction is angular and more distant. (C) 2009 Elsevier B.V. All rights reserved.

Substituent effects in single helix-double helix interconversions in copper(I) complexes

The copper(I) complex of L, the 1:2 condensate of benzil dihydrazone and 2-formylpyridine, exists as single, helical [CuL](+) and double helical [Cu2L2](2+) in dichloromethane solution but crystallizes only as the double helicate [Cu2L2](ClO4)(2). In contrast, earlier [New J Chem, 27 (2003) 193] it has been found that with L', the 1:2 condensate of benzil dihydrazone and 2-acetylpyridine, only the single helical monomeric species [CuL'](+) is isolable as solid. This contrasting behaviour of the copper(I) complexes of L and L' are scrutinised here by density functional calculations.

Solid state annular tautomerism in a molecule containing two imidazole moieties

The X-ray crystal structure of the 1:2 condensate (1) of hydrazine hydrate and 4-methyl-imidazole-5-carboxaldehyde has been determined. The molecule is centrosymmetric crystallising in the space group Fddd with cell dimensions: a = 10.557(14), b = 17.062(22), c = 24.759(27) angstrom. Fourier map shows that the NH hydrogen atom of each imidazole moiety has equal possibility of occupying any of its two ring N atoms. This poses the possibility of finding three tautomers in 1 in the solid state. Consideration of the H-bonding pattern observed in 1 and related B3LYP/6-311+G(2d, p) calculations show that only two tautomers are present in the solid state. The situation is compared with that in the structure of 4(5)-nitro-5(4)-methoxy-imidazole reported previously by Kubicki.

An unprecedented mononuclear double helicate with a square planar metal ion

Reactions of the 1:2 condensate (L) of benzil dihydrazone and 1-methyl-2-imidazole carboxaldehyde with Cd(ClO4)(2)center dot xH(2)O and CdI2 yield [CdL2]( ClO4)(2) (1) and LCdI2 (2), respectively. The yellow ligand L, and its yellow complexes 1 and 2 are characterized by NMR and single crystal X-ray diffraction. Though L contains four N-donor centers, 1 is found to be a four-coordinate double helicate with a square planar Cd(II)N-4 core and 2 a spiral coordination polymer with tetrahedral Cd(II)N2I2 moieties. The bidentate nature of L and the occurrence of the square planar coordination of Cd( II) is explained by DFT calculations. (c) 2007 Elsevier B. V. All rights reserved.

Stereochemically non-rigid helical mercury(II) complexes

Reactions of the 1: 2 condensate (L) of benzil dihydrazone and 2-acetylpyridine with Hg(ClO4)(2) center dot xH(2)O and HgI2 yield yellow [HgL2](ClO4)(2) (1) and HgLI2 (2), respectively. Homoleptic 1 is a 8-coordinate double helical complex with a Hg(II)N-8 core crystallising in the space group Pbca with cell dimensions: a = 16.2250(3), b = 20.9563(7), c = 31.9886(11) angstrom. Complex 2 is a 4-coordinate single helical complex having a Hg(II)N2I2 core crystallising in the space group P2(1)/n with cell dimensions a = 9.8011(3), b = 17.6736(6), c = 16.7123(6) angstrom and b = 95.760(3). In complex 1, the N-donor ligand L uses all of its binding sites to act as tetradentate. On the other hand, it acts as a bidentate N-donor ligand in 2 giving rise to a dangling part. From variable temperature H-1 NMR studies both the complexes are found to be stereochemically non-rigid in solution. In the case of 2, the solution process involves wrapping up of the dangling part of L around the metal. (C) 2008 Elsevier B.V. All rights reserved.

Observation of carbonyl oxygen-pi interaction in a metal complex

X-ray crystallography shows that [Ag2L2(H2O)(2)](BF4)(2) where L is a 1:1 condensate of 1,2-diphenylethane-1,2-dione and 2-(2-aminoethyl pyridine), contains an Ag(I)-Ag(I) bond of length 2.979(2) angstrom and an angular, intraligand interaction of the keto O with the pi cloud of the pyridine moiety (O-pyridine centroid = 3.12 angstrom). Model MP2/6-311++G(d,p) calculations indicate that the observed lone pair-pi type interaction is stabilising and not merely a tolerated short contact. (C) 2008 Elsevier B.V. All rights reserved.

A monoaqua zinc complex. Unique acid dissociation behaviour

Using the I : 2 condensate of benzil dihydrazone and 2-acetylpyridine as the ligand L, two complexes of zinc, [ZnL(CH3COO)]PF6 (1) and [ZnL(H2O)CIO4]CIO4 H2O (2), are synthesised from Zn(CH3COO)(2).2H(2)O and Zn(CIO4)(2).6H(2)O, respectively. From X-ray crystallography, both the complexes are found to be single helical with the metal in distorted octahedral N4O2 environment. In 1, the two oxygen atoms come from the bidentate acetate while 2 is a monoaqua complex with a perchlorate anion bound to the metal in monodentate fashion. The perchlorate in 2 is not at all weakly bound [Zn-O(perchlorate) 2.256(4) A]. Still in acetonitrile solution, the coordinated perchlorate ion dissociates upon deprotonation [reaction (i)].

An eight-coordinate mononuclear double helical complex

From the reaction of Cd(CH3COO)(2)(.)2H(2)O with the 1:2 condensate (L) of benzil dihydrazone and 2-acetylpyridine, [CdL(CH3COO)(H2O)]PF(6)(.)3H(2)O (1) is isolated by adding NH4PF6. L reacts with Cd(ClO4)(2)(.)xH(2)O to yield [CdL2](ClO4)(2). 0.5H(2)O (2). The yellowish complexes 1 and 2 are characterized by NMR and single-crystal X-ray diffraction. 1 is found to be a seven-coordinate single helical complex having a (CdN4O3)-N-II core and homoleptic 2 an eight-coordinate double helical complex with a (CdN8)-N-II core. (c) Wiley-VCH Verlag GmbH & Co.