Maximização da valorização energética em aterros sanitários recorrendo a equipamentos baseados no Ciclo Orgânico de Rankine (ORC)

Atualmente, os aterros sanitários representam uma solução para a gestão e tratamento dos resíduos sólidos urbanos. Da deposição, ocorrem duas formas de emissões ao longo do tempo, a produção de biogás e de lixiviados, que resultam sobretudo da decomposição da matéria orgânica. Um dos principais constituintes do biogás é o metano, o qual tem elevado poder calorífico. O presente trabalho aborda, a maximização da valorização energética em aterros sanitários, recorrendo a equipamentos baseados no Ciclo Orgânico de Rankine (ORC) para a produção de eletricidade. É apresentado como caso de estudo a central de valorização energética da Suldouro, em Sermonde, que produz eletricidade a partir do biogás resultante da decomposição da matéria orgânica depositada em aterro. O biogás é utilizado como combustível para os motogeradores utilizados para o seu aproveitamento energético, sendo que apenas cerca de 40% do potencial energético contido no biogás é transformado em eletricidade, registando-se perdas sobretudo nas emissões dos gases de exaustão e na água de arrefecimento dos motores. Para avaliação do potencial da recuperação energética dos gases de escape é avaliado o desempenho termodinâmico do ciclo ORC. Para tal foi desenvolvida uma ferramenta em MATLAB utilizando como modelo a configuração do ORC com recuperador de calor. O cálculo das propriedades termodinâmicas dos fluidos foi obtido através da criação de uma sub-rotina que chama o programa CoolProp. Este programa restitui propriedades como a entalpia, entropia, pressões e temperaturas em cada ponto do ciclo, permitindo assim ao utilizador otimizar o tempo na obtenção de resultados. A avaliação económica é fundamental na tomada de decisões por parte do investidor e dos financiadores do projeto. É então apresentada a análise económica e efetuada uma análise de sensibilidade, onde foram efetuadas variações nos vetores mais importantes de forma a poder avaliar-se o impacto em termos da sua rentabilidade. A ferramenta desenvolvida permite obter de forma prática, os três indicadores económicos extremamente influentes no que se refere à tomada de decisão. A utilização dos sistemas ORC e os seus benefícios não se esgotam na maximização dos aproveitamentos da valorização energética em aterros sanitários. Também a recuperação de calor para a produção de energia elétrica pode ter um impacto importante em muitos setores intensivos de energia, contribuindo significativamente para a redução do consumo e aumentando a eficiência de todo o processo de produção.

Use of quantitative structure-property relationships to study the solvation process of 18-crown-6

Solution enthalpies of 18-crown-6 have been obtained for a set of 14 protic and aprotic solvents at 298.15 K. The complementary use of Solomonov's methodology and a QSPR-based approach allowed the identification of the most significant solvent descriptors that model the interaction enthalpy contribution of the solution process (Delta H-int(A/S)). Results were compared with data previously obtained for 1,4-dioxane. Although the interaction enthalpies of 18-crown-6 correlate well with those of 1,4-dioxane, the magnitude of the most relevant parameters, pi* and beta, is almost three times higher for 18-crown-6. This is rationalized in terms of the impact of the solute's volume in the solution processes of both compounds. (C) 2015 Elsevier B.V. All rights reserved.

Study on solubility of pharmaceutical compounds in ionic liquids

Dissertation to obtain the degree of master in Chemical and Biochemical Engineering

40 K Liquid Neon Energy Storage Unit

A thermal Energy Storage Unit (ESU) could be used to attenuate inherent temperature fluctuations of a cold finger, either from a cryocooler working or due to sudden income heat bursts. An ESU directly coupled to the cold source acts as a thermal buffer temporarily increasing its cooling capacity and providing a better thermal stability of the cold finger (“Power Booster mode”). The energy storage units presented here use an enthalpy reservoir based on the high latent heat of the liquid-vapour transition of neon in the temperature range 38 - 44 K to store up to 900 J, and that uses a 6 liters expansion volume at RT in order to work as a closed system. Experimental results in the power booster mode will be described: in this case, the liquid neon cell was directly coupled to the cold finger of the working cryocooler, its volume (12 cm3) allowing it to store 450 J at around 40 K. 10 W heat bursts were applied, leading to liquid evaporation, with quite reduced temperature changes. The liquid neon reservoir can also work as a temporary cold source to be used after stopping the cryocooler, allowing for a vibration-free environment. In this case the enthalpy reservoir implemented (24 cm3) was linked to the cryocooler cold finger through a gas gap heat switch for thermal coupling/decoupling of the cold finger. We will show that, by controlling the enthalpy reservoir’s pressure, 900 J can be stored at a constant temperature of 40 K as in a triple-point ESU.

Structure-properties relationships in thermoplastic polyurethane elastomer nanocomposites: Interactions between polymer phases and nanofillers

Polyurethane thermoplastic elastomer (TPU) nanocomposites were prepared by the incorporation of 1 wt% of high-structured carbon black (HSCB), carbon nanofibers (CNF), nanosilica (NS) and nanoclays (NC), following a proper high-shear blending procedure. The TPU nanofilled mechanical properties and morphology was assessed. The nanofillers interact mainly with the TPU hard segments (HS) domains, determining their glass transition temperature, and increasing their melting temperature and enthalpy. A significant improvement upon the modulus, sustained stress levels and deformation capabilities is evidenced. The relationships between the morphology and the nanofilled TPU properties are established, evidencing the role of HS domains on the mechanical response, regardless the nanofiller type.

Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films

CH, Chitosan; HPMC, (Hydroxypropyl)methyl cellulose; FT, Freeze-thaw; SC, Solvent casting; CH:HPMC (X:Y), pH Z, FT/SC, Chitosan and (hydroxypropyl)methyl cellulose hydrogel, at X and Y proportion (0-100), at Z pH (3.0-4.0) and prepared by freeze-thaw or solvent casting techniques; DSC, Differential scanning calorimetry; MDSC, Temperature modulated Differential scanning calorimetry; Tg, glass transition temperature; ΔH, enthalpy change; TGA, Thermogravimetric Analysis; TG, Thermogravimetry; DTG, Derivative or Differential thermogravimetry; σ, Tensile strength; ε, elongation at break; DMA, Dynamic mechanical analysis; X-Ray, X-radiation, FTIR-ATR, Attenuated total reflectance Fourier transform infrared spectroscopy; SEM, Scanning electron microscopy.

Erratum to: Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films

CH, Chitosan; HPMC, (Hydroxypropyl)methyl cellulose; FT, Freeze-thaw; SC, Solvent casting; CH:HPMC (X:Y), pH Z, FT/SC, Chitosan and (hydroxypropyl)methyl cellulose hydrogel, at X and Y proportion (0-100), at Z pH (3.0-4.0) and prepared by freeze-thaw or solvent casting techniques; DSC, Differential scanning calorimetry; MDSC, Temperature modulated Differential scanning calorimetry; Tg, glass transition temperature; ΔH, enthalpy change; TGA, Thermogravimetric Analysis; TG, Thermogravimetry; DTG, Derivative or Differential thermogravimetry; σ, Tensile strength; ε, elongation at break; DMA, Dynamic mechanical analysis; X-Ray, X-radiation, FTIR-ATR, Attenuated total reflectance Fourier transform infrared spectroscopy; SEM, Scanning electron microscopy.

Influència del context geològic i hidrogeològic en l'eficiència energètica dels sistemes geotèrmics de molt baixa entalpia

L’elevat consum energètic de les societats actuals, així com la impossibilitat de sostenir-lo a llarg termini implica la cerca de noves fonts d’energia. D’aquesta manera, en el camp de la climatització residencial, l’energia geotèrmica de molt baixa entalpia es posiciona com una alternativa als recursos energètics actuals. Així, els primers metres de subsòl presenten una temperatura adequada per al seu aprofitament calorífic, mitjançant els sistemes geotèrmics de bomba de calor. Si bé a nivell energètic, són sistemes, intrínsecament, molt eficients, el seu rendiment pot patir importants variacions davant dels canvis en les condicions del medi geològic i hidrogeològic. Especialment, els col·lectors de calor verticals, treballen, amb freqüència, en el si de les formacions hidrogeològiques. En aquest sentit, els canvis del nivell hidràulic i de la temperatura de l’aigua de l’aqüífer es manifesten amb variacions de la conductivitat tèrmica equivalent i del flux subterrani d’aigua, que alhora, aquestes, es tradueixen en alteracions del flux subterrani de calor. Davant d’aquest fet, l’avaluació quantitativa de l’efecte d’aquestes fluctuacions que es presenta en aquest treball mostra petites variacions del nivell hidràulic i de la temperatura de l’aigua comporten canvis molt notables en l’eficiència dels sistemes verticals de bomba de calor geotèrmica.

Calorimetry of dehydrogenation and dangling-bond recombination in several hydrogenated amorphous silicon materials

Differential scanning calorimetry (DSC) was used to study the dehydrogenation processes that take place in three hydrogenated amorphous silicon materials: nanoparticles, polymorphous silicon, and conventional device-quality amorphous silicon. Comparison of DSC thermograms with evolved gas analysis (EGA) has led to the identification of four dehydrogenation processes arising from polymeric chains (A), SiH groups at the surfaces of internal voids (A'), SiH groups at interfaces (B), and in the bulk (C). All of them are slightly exothermic with enthalpies below 50 meV/H atoms , indicating that, after dissociation of any SiH group, most dangling bonds recombine. The kinetics of the three low-temperature processes [with DSC peak temperatures at around 320 (A),360 (A'), and 430°C (B)] exhibit a kinetic-compensation effect characterized by a linea relationship between the activation entropy and enthalpy, which constitutes their signature. Their Si-H bond-dissociation energies have been determined to be E (Si-H)0=3.14 (A), 3.19 (A'), and 3.28 eV (B). In these cases it was possible to extract the formation energy E(DB) of the dangling bonds that recombine after Si-H bond breaking [0.97 (A), 1.05 (A'), and 1.12 (B)]. It is concluded that E(DB) increases with the degree of confinement and that E(DB)>1.10 eV for the isolated dangling bond in the bulk. After Si-H dissociation and for the low-temperature processes, hydrogen is transported in molecular form and a low relaxation of the silicon network is promoted. This is in contrast to the high-temperature process for which the diffusion of H in atomic form induces a substantial lattice relaxation that, for the conventional amorphous sample, releases energy of around 600 meV per H atom. It is argued that the density of sites in the Si network for H trapping diminishes during atomic diffusion

C-H···O H-bonded complexes: how does basis set superposition error change their potential-energy surfaces?

Geometries, vibrational frequencies, and interaction energies of the CNH⋯O3 and HCCH⋯O3 complexes are calculated in a counterpoise-corrected (CP-corrected) potential-energy surface (PES) that corrects for the basis set superposition error (BSSE). Ab initio calculations are performed at the Hartree-Fock (HF) and second-order Møller-Plesset (MP2) levels, using the 6-31G(d,p) and D95++(d,p) basis sets. Interaction energies are presented including corrections for zero-point vibrational energy (ZPVE) and thermal correction to enthalpy at 298 K. The CP-corrected and conventional PES are compared; the unconnected PES obtained using the larger basis set including diffuse functions exhibits a double well shape, whereas use of the 6-31G(d,p) basis set leads to a flat single-well profile. The CP-corrected PES has always a multiple-well shape. In particular, it is shown that the CP-corrected PES using the smaller basis set is qualitatively analogous to that obtained with the larger basis sets, so the CP method becomes useful to correctly describe large systems, where the use of small basis sets may be necessary

Chemistry, isotope values (δD, δ18O, δ34S(SO4)) and temperatures of the water inflows in two Gotthard tunnels, Swiss Alps

Water inflows in the Gotthard Highway Tunnel and in the Gotthard Exploration Tunnel are meteoric waters infiltrating at different elevations, on both sides of an important orographic divide. Limited interaction of meteoric waters with gneissic rocks produces Ca-HCO3 and Na-Ca-HCO3 waters, whereas prolonged interaction of meteoric waters with the same rocks generates Na-HCO3 to Na-SO4 waters. Waters circulating in Triassic carbonate-evaporite rocks have a Ca-SO4 composition. Calcium-Na-SO4 waters are also present. They can be produced through interaction of either Na-HCO3 waters with anhydrite or Ca-SO4 waters with a local gneissic rock, as suggested by reaction path modeling. An analogous simulation indicates that Na-HCO3 waters are generated through interaction of Ca-HCO3 waters with a local gneissic rock. The two main SO4-sources present in the Alps are leaching of upper Triassic sulfate minerals and oxidative dissolution of sulfide minerals of crystalline rocks. Values of delta S-34(SO4) < <similar to>+ 9 parts per thousand, are due to oxidative dissolution of sulfide minerals, whereas delta S-34(SO4) > similar to+ 9 parts per thousand are controlled either by bacterial SO4 reduction or leaching of upper Triassic sulfate minerals. Most waters have temperatures similar to the expected values for a geothermal gradient of 22 degreesC/km and are close to thermal equilibrium with rocks. However relatively large, descending flows of cold waters and ascending flows of warm waters are present in both tunnels and determine substantial cooling and heating, respectively, of the interacting rocks. The most import upflow zone of warm, Na-rich waters is below Guspisbach, in the Gotthard Highway Tunnel, at 6.2-9.0 km from the southern portal. These warm waters have equilibrium temperatures of 65-75 degreesC and therefore constitute an important low-enthalpy geothermal resource. (C) 2001 Elsevier Science Ltd. All rights reserved.

X-ray diffraction, thermal analysis, and Raman scattering study of K2BeF4 and comparation to other member of the (beta)-K2SO4 family with ferroelectric -paraelectric transition

Thermal analysis, powder diffraction, and Raman scattering as a function of the temperature were carried out on K2BeF4. Moreover, the crystal structure was determined at 293 K from powder diffraction. The compound shows a transition from Pna21 to Pnam space group at 921 K with a transition enthalpy of 5 kJ/mol. The transition is assumed to be first order because the compound shows metastability. Structurally and spectroscopically the transition is similar to those observed in (NH4)2SO4, which suggests that the low-temperature phase is ferroelectric. In order to confirm it, the spontaneous polarization has been computed using an ionic model.

X-ray photoelectron spectroscopy analysis of ion¿beam¿induced oxidation of GaAs and AlGaAs

The oxidation of GaAs and AlGaAs targets subjected to O2+ bombardment has been analyzed, using in situ x¿ray photoelectron spectroscopy, as a function of time until steady state is reached. The oxides formed by the O2+ bombardment have been characterized in terms of composition and binding energy. A strong energy and angular dependence for the oxidation of As relative to Ga is found. Low energies as well as near normal angles of incidence favor the oxidation of As. The difference between Ga and As can be explained in terms of the formation enthalpy for the oxide and the excess supply of oxygen. In an AlGaAs target the Al is very quickly completely oxidized irrespective of the experimental conditions. The steady state composition of the altered layers show in all cases a preferential removal of As.

The Gibbs free energy of formation of a glass alloy

A simple expression for the Gibbs free energy of formation of a pure component or a eutectic alloy glass, relative to the stable crystalline phase (or phases) at the same temperature is deduced by use of thermodynamic arguments. The expression obtained is supposed to apply to both monocomponent and multicomponent liquid alloys that might become glasses from the supercooled liquid state, irrespective of the critical cooling rate needed to avoid crystallization.

Thermodynamic Characterization of Humic Acid-surfactant Interaction: New Insights into the Characteristics and Structure of Humic Acids

ABSTRACT Humic acids (HA) are a component of humic substances (HS), which are found in nearly all soils, sediments, and waters. They play a key role in many, if not most, chemical and physical properties in their environment. Despite the importance of HA, their high complexity makes them a poorly understood system. Therefore, understanding the physicochemical properties and interactions of HA is crucial for determining their fundamental role and obtaining structural details. Cationic surfactants are known to interact electrostatically and hydrophobically with HA. Because they are a very well-known and characterized system, they offer a good choice as molecular probes for studying HA. The objective of this study was to evaluate the interaction between cationic surfactants and HA through isothermal titration calorimetry in a thermodynamic manner, aiming to obtain information about the basic structure of HA, the nature of this interaction, and if HA from different origins show different basic structures. Contrary to what the supramolecular model asserts, HA structure is not loosely held, though it may separate depending on the conditions the HA are subjected to in their milieu. It did not show any division or conformational change when interacting with surfactants. The basic structure of the HA remains virtually the same regardless of the different sources and compositions of these HA.