Studio sperimentale di una pompa di calore elio-assistita a CO2 per la climatizzazione e la produzione di acqua calda sanitaria

Il seguente lavoro di tesi ha come obiettivo lo studio delle prestazioni energetiche di una pompa di calore elio-assistita, reversibile e multi-sorgente, la quale combina la tecnologia delle pompe di calore aria-acqua con quella dei collettori solari ibridi termo-fotovoltaici. L’impianto oggetto di studio è situato presso il centro di ricerca ENEA Casaccia ed è stato sviluppato con lo scopo di soddisfare la richiesta di riscaldamento/raffrescamento e produzione di acqua calda di un edificio residenziale o commerciale. In questo elaborato si è analizzato il funzionamento invernale della pompa di calore finalizzato alla produzione di acqua calda sanitaria, confrontando due modalità operative differenti con diverse impostazioni di lavoro della frequenza del compressore e della valvola di laminazione. L’elemento distintivo delle due modalità operative è il componente avente la funzione di evaporatore in quanto in una modalità è stata impiegata una batteria alettata con ventilazione forzata, mentre nell’altra un campo di pannelli termo-fotovoltaici. I risultati ottenuti dalle prove sperimentali hanno evidenziato migliori prestazioni della pompa di calore con i collettori ibridi termo-fotovoltaici, in caso di presenza di elevati valori di irraggiamento solare. Elemento di innovazione dell’impianto sperimentale è l’utilizzo del fluido naturale R744 (CO2) come refrigerante il quale viene sfruttato anche per raffreddare le celle fotovoltaiche comportando in questo modo, un doppio effetto utile all’impianto stesso: miglioramento del rendimento elettrico dei collettori solari e contemporaneamente un incremento della temperatura di evaporazione con conseguente beneficio sulle prestazioni della pompa di calore.

Studio dell’idrogenazione della CO2 a MeOH mediante catalizzatori a base di Cu/In/Al

Ad oggi, l’aumento delle emissioni di gas serra, principalmente di CO2, dovuto alle attività antropiche, ha portato ad un aumento delle temperature medie globali. La sintesi del metanolo da CO2 ha attirato molto l’interesse della ricerca e attualmente il catalizzatore Cu/ZnO/Al2O3, sviluppato per la produzione di metanolo da gas di sintesi si dimostra il più utilizzato. Tuttavia, alcune sue problematiche, legate alla bassa selettività rispetto a MeOH all’aumentare della temperatura, per via della reazione concorrente di RWGS e problemi di disattivazione per sinterizzazione relazionati con l’acqua prodotta, hanno portato allo studio di nuovi catalizzatori. Recentemente, catalizzatori a base di In2O3 hanno catturato molto l’attenzione già che hanno una elevata selettività in metanolo. Lo scopo della tesi si è basato sullo studio di catalizzatori a base di Cu/In/Al per l’idrogenazione della CO2 a MeOH. Una volta sintetizzati e caratterizzati i catalizzatori sono stati messi a confronto con un catalizzatore commerciale (Cu/ZnO/Al2O3). Sono stati investigati gli effetti del contenuto di Cu, metodo di preparazione e temperatura di riduzione nelle prestazioni catalitiche (conversione, selettività  e resa spazio-temporale). I valori di conversione e selettività  dipendono del contenuto di Cu, raggiungendo il massimo con un contenuto intermedio di Cu (30 % rapporto atomico), tuttavia i risultati sono inferiori a quelli ottenuti con il catalizzatore commerciale. La temperatura di riduzione più adatta è stata 300 °C. Riguardo al metodo di preparazione, non sembra modificare significativamente le prestazioni catalitiche. Saranno necessari ulteriori studi su altre formulazioni di catalizzatori per migliorare sia la attività che la selettività.

Remediation Of 17-α-ethinylestradiol Aqueous Solution By Photocatalysis And Electrochemically-assisted Photocatalysis Using Tio2 And Tio2/wo3 Electrodes Irradiated By A Solar Simulator.

TiO2 and TiO2/WO3 electrodes, irradiated by a solar simulator in configurations for heterogeneous photocatalysis (HP) and electrochemically-assisted HP (EHP), were used to remediate aqueous solutions containing 10 mg L(-1) (34 μmol L(-1)) of 17-α-ethinylestradiol (EE2), active component of most oral contraceptives. The photocatalysts consisted of 4.5 μm thick porous films of TiO2 and TiO2/WO3 (molar ratio W/Ti of 12%) deposited on transparent electrodes from aqueous suspensions of TiO2 particles and WO3 precursors, followed by thermal treatment at 450 (°)C. First, an energy diagram was organized with photoelectrochemical and UV-Vis absorption spectroscopy data and revealed that EE2 could be directly oxidized by the photogenerated holes at the semiconductor surfaces, considering the relative HOMO level for EE2 and the semiconductor valence band edges. Also, for the irradiated hybrid photocatalyst, electrons in TiO2 should be transferred to WO3 conduction band, while holes move toward TiO2 valence band, improving charge separation. The remediated EE2 solutions were analyzed by fluorescence, HPLC and total organic carbon measurements. As expected from the energy diagram, both photocatalysts promoted the EE2 oxidation in HP configuration; after 4 h, the EE2 concentration decayed to 6.2 mg L(-1) (35% of EE2 removal) with irradiated TiO2 while TiO2/WO3 electrode resulted in 45% EE2 removal. A higher performance was achieved in EHP systems, when a Pt wire was introduced as a counter-electrode and the photoelectrodes were biased at +0.7 V; then, the EE2 removal corresponded to 48 and 54% for the TiO2 and TiO2/WO3, respectively. The hybrid TiO2/WO3, when compared to TiO2 electrode, exhibited enhanced sunlight harvesting and improved separation of photogenerated charge carriers, resulting in higher performance for removing this contaminant of emerging concern from aqueous solution.

Separation Of Glycosidic Catiomers By Twim-ms Using Co2 As A Drift Gas.

Traveling wave ion mobility mass spectrometry (TWIM-MS) is shown to be able to separate and characterize several isomeric forms of diterpene glycosides stevioside (Stv) and rebaudioside A (RebA) that are cationized by Na(+) and K(+) at different sites. Determination and characterization of these coexisting isomeric species, herein termed catiomers, arising from cationization at different and highly competitive coordinating sites, is particularly challenging for glycosides. To achieve this goal, the advantage of using CO2 as a more massive and polarizable drift gas, over N2 , was demonstrated. Post-TWIM-MS/MS experiments were used to confirm the separation. Optimization of the possible geometries and cross-sectional calculations for mobility peak assignments were also performed. Copyright © 2015 John Wiley & Sons, Ltd.

Supercritical CO2 recovery of caffeine from green coffee oil: new experimental solubility data and modeling

The caffeine solubility in supercritical CO2 was studied by assessing the effects of pressure and temperature on the extraction of green coffee oil (GCO). The Peng-Robinson¹ equation of state was used to correlate the solubility of caffeine with a thermodynamic model and two mixing rules were evaluated: the classical mixing rule of van der Waals with two adjustable parameters (PR-VDW) and a density dependent one, proposed by Mohamed and Holder² with two (PR-MH, two parameters adjusted to the attractive term) and three (PR-MH3 two parameters adjusted to the attractive and one to the repulsive term) adjustable parameters. The best results were obtained with the mixing rule of Mohamed and Holder² with three parameters.

Avaliação citométrica dos adipócitos localizados no tecido subcutâneo da parede anterior do abdome após infiltração percutânea de CO2

OBJETIVO: Avaliar os efeitos da infiltração de dióxido de carbono em adipócitos presentes na parede abdominal. MÉTODOS: Quinze voluntárias foram submetidas a sessões de infusão de CO2 durante três semanas consecutivas (duas sessões por semana com intervalos de dois a três dias entre cada sessão). O volume de gás carbônico infundido por sessão, em pontos previamente demarcados, foi sempre calculado com base na superfície da área a ser tratada, com volume infundido fixo de 250 mL/100cm² de superfície tratada. Os pontos de infiltração foram demarcados respeitando-se o limite eqüidistante 2cm entre eles. Em cada ponto se injetou 10mL, por sessão, com fluxo de 80mL/min. Foram colhidos fragmentos de tecido celular subcutâneo da parede abdominal anterior antes e após o tratamento. O número e as alterações histomorfológicas dos adipócitos (diâmetro médio, perímetro, comprimento, largura e número de adipócitos por campos de observação) foram mensurados por citometria computadorizada. Os resultados foram analisados com o teste t de Student pareado, adotando-se nível de significância de 5% (p<0,05). RESULTADOS: Encontrou-se redução significativa no número de adipócitos da parede abdominal e na área, diâmetro, perímetro, comprimento e largura após o uso da hipercapnia (p=0,0001). CONCLUSÃO: A infiltração percutânea de CO2 reduz a população e modifica a morfologia dos adipócitos presentes na parede abdominal anterior.

Dosimetria esporular: Bacillus subtilis TKJ6312 como biossensor de radiação solar biologicamente ativa

Since 2000, spore dosimetry and spectral photometry have been performed in parallel at the Southern Space Observatory, São Martinho da Serra (Southern Brazil). A comparative study involving data from Punta Arenas - Chile (53.2º S), São Martinho da Serra (29.5º S), Padang - Indonesia (0.9ºS), Brussels - Belgium (50.9º N) and Kiyotake - Japan (31.9º N) from 2000 to 2006 is presented. The Spore Inactivation Doses presented the higher values in summer (973 ± 73 for Punta Arenas and 4,369 ± 202 for São Martinho da Serra, as well 1,402 ± 170 and 3,400 ± 1,674 for Brussels and Kiyotake, respectively). The simplicity, robustness and high resistance of bacterial spores makes the biosensor an potential biological tool for UV-B monitoring.

Crise financeira, energia e sustentabilidade no Brasil

A recente crise financeira global traz consigo efeitos como a redução da atividade econômica e, consequentemente, do consumo de energia. Essa pode ser uma importante oportunidade para reorganizar o sistema energético em bases mais sólidas e sustentáveis: a eficiência, a maior participação das fontes renováveis e a descentralização da produção de energia. O Brasil e outros países em desenvolvimento podem aproveitar a experiência dos países desenvolvidos em eficiência energética, complementando com um programa vigoroso em energias renováveis, particularmente as "modernas" (eólica, solar, biomassa e pequenas hidrelétricas). Entretanto, preocupa o cenário inercial nacional, baseado num aumento da participação das fontes fósseis de energia na matriz, na priorização dos recursos à exploração de petróleo e gás natural e na manutenção de padrões insustentáveis de produção e consumo.

Effect of CO2 and 1-octen-3-ol attractants for estimating species richness and the abundance of diurnal mosquitoes in the southeastern Atlantic forest, Brazil

Studies have shown that both carbon dioxide (CO2) and octenol (1-octen-3-ol) are effective attractants for mosquitoes. The objective of the present study was to evaluate the attractiveness of 1-octen-3-ol and CO2 for diurnal mosquitoes in the southeastern Atlantic forest. A Latin square experimental design was employed with four treatments: CDC-light trap (CDC-LT), CDC-LT and 1-octen-3-ol, CDC-LT and CO2 and CDC-LT with 1-octen-3-ol and CO2. Results demonstrated that both CDC-CO2 and CDC-CO2-1-octen-3-ol captured a greater number of mosquito species and specimens compared to CDC-1-octen-3-ol; CDC-LT was used as the control. Interestingly, Anopheles (Kerteszia) sp. was generally attracted to 1-octen-3-ol, whereas Aedes serratus was the most abundant species in all Latin square collections. This species was recently shown to be competent to transmit the yellow fever virus and may therefore play a role as a disease vector in rural areas of Brazil.

Turbulent magnetic pumping in a Babcock-Leighton solar dynamo model

Context. The turbulent pumping effect corresponds to the transport of magnetic flux due to the presence of density and turbulence gradients in convectively unstable layers. In the induction equation it appears as an advective term and for this reason it is expected to be important in the solar and stellar dynamo processes. Aims. We explore the effects of turbulent pumping in a flux-dominated Babcock-Leighton solar dynamo model with a solar-like rotation law. Methods. As a first step, only vertical pumping has been considered through the inclusion of a radial diamagnetic term in the induction equation. In the second step, a latitudinal pumping term was included and then, a near-surface shear was included. Results. The results reveal the importance of the pumping mechanism in solving current limitations in mean field dynamo modeling, such as the storage of the magnetic flux and the latitudinal distribution of the sunspots. If a meridional flow is assumed to be present only in the upper part of the convective zone, it is the full turbulent pumping that regulates both the period of the solar cycle and the latitudinal distribution of the sunspot activity. In models that consider shear near the surface, a second shell of toroidal field is generated above r = 0.95 R(circle dot) at all latitudes. If the full pumping is also included, the polar toroidal fields are efficiently advected inwards, and the toroidal magnetic activity survives only at the observed latitudes near the equator. With regard to the parity of the magnetic field, only models that combine turbulent pumping with near-surface shear always converge to the dipolar parity. Conclusions. This result suggests that, under the Babcock-Leighton approach, the equartorward motion of the observed magnetic activity is governed by the latitudinal pumping of the toroidal magnetic field rather than by a large scale coherent meridional flow. Our results support the idea that the parity problem is related to the quadrupolar imprint of the meridional flow on the poloidal component of the magnetic field and the turbulent pumping positively contributes to wash out this imprint.

New constraints on the chemical evolution of the solar neighbourhood and Galactic disc(s) Improved astrophysical parameters for the Geneva-Copenhagen Survey

We present a re-analysis of the Geneva-Copenhagen survey, which benefits from the infrared flux method to improve the accuracy of the derived stellar effective temperatures and uses the latter to build a consistent and improved metallicity scale. Metallicities are calibrated on high-resolution spectroscopy and checked against four open clusters and a moving group, showing excellent consistency. The new temperature and metallicity scales provide a better match to theoretical isochrones, which are used for a Bayesian analysis of stellar ages. With respect to previous analyses, our stars are on average 100 K hotter and 0.1 dex more metal rich, which shift the peak of the metallicity distribution function around the solar value. From Stromgren photometry we are able to derive for the first time a proxy for [alpha/Fe] abundances, which enables us to perform a tentative dissection of the chemical thin and thick disc. We find evidence for the latter being composed of an old, mildly but systematically alpha-enhanced population that extends to super solar metallicities, in agreement with spectroscopic studies. Our revision offers the largest existing kinematically unbiased sample of the solar neighbourhood that contains full information on kinematics, metallicities, and ages and thus provides better constraints on the physical processes relevant in the build-up of the Milky Way disc, enabling a better understanding of the Sun in a Galactic context.

The radius and mass of the close solar twin 18 Scorpii derived from asteroseismology and interferometry

The growing interest in solar twins is motivated by the possibility of comparing them directly to the Sun. To carry on this kind of analysis, we need to know their physical characteristics with precision. Our first objective is to use asteroseismology and interferometry on the brightest of them: 18 Sco. We observed the star during 12 nights with HARPS for seismology and used the PAVO beam-combiner at CHARA for interferometry. An average large frequency separation 134.4+/-0.3 mu Hz and angular and linear radiuses of 0.6759 +/- 0.0062 mas and 1.010 +/- 0.009 R(circle dot) were estimated. We used these values to derive the mass of the star, 1.02 +/- 0.03 M(circle dot).

Solar twins in M 67: evolutionary status and lithium abundance

Aims. We determine the age and mass of the three best solar twin candidates in open cluster M 67 through lithium evolutionary models. Methods. We computed a grid of evolutionary models with non-standard mixing at metallicity [Fe/H] = 0.01 with the Toulouse-Geneva evolution code for a range of stellar masses. We estimated the mass and age of 10 solar analogs belonging to the open cluster M 67. We made a detailed study of the three solar twins of the sample, YPB637, YPB1194, and YPB1787. Results. We obtained a very accurate estimation of the mass of our solar analogs in M 67 by interpolating in the grid of evolutionary models. The three solar twins allowed us to estimate the age of the open cluster, which is 3.87(-0.66)(+0.55) Gyr, which is better constrained than former estimates. Conclusions. Our results show that the 3 solar twin candidates have one solar mass within the errors and that M 67 has a solar age within the errors, validating its use as a solar proxy. M 67 is an important cluster when searching for solar twins.

Transiting exoplanets from the CoRoT space mission XIII. CoRoT-13b: a dense hot Jupiter in transit around a star with solar metallicity and super-solar lithium content

We announce the discovery of the transiting planet CoRoT-13b. Ground-based follow-up in CFHT and IAC80 confirmed CoRoT's observations. The mass of the planet was measured with the HARPS spectrograph and the properties of the host star were obtained analyzing HIRES spectra from the Keck telescope. It is a hot Jupiter-like planet with an orbital period of 4.04 days, 1.3 Jupiter masses, 0.9 Jupiter radii, and a density of 2.34 g cm(-3). It orbits a G0V star with T(eff) = 5 945 K, M(*) = 1.09 M(circle dot), R(*) = 1.01 R(circle dot), solar metallicity, a lithium content of +1.45 dex, and an estimated age of between 0.12 and 3.15 Gyr. The lithium abundance of the star is consistent with its effective temperature, activity level, and age range derived from the stellar analysis. The density of the planet is extreme for its mass, implies that heavy elements are present with a mass of between about 140 and 300 M(circle plus).

uvby-beta photometry of solar twins The solar colors, model atmospheres, and the T(eff) and metallicity scales

Aims. Solar colors have been determined on the uvby-beta photometric system to test absolute solar fluxes, to examine colors predicted by model atmospheres as a function of stellar parameters (T(eff), log g, [Fe/H]), and to probe zero-points of T(eff) and metallicity scales. Methods. New uvby-beta photometry is presented for 73 solar-twin candidates. Most stars of our sample have also been observed spectroscopically to obtain accurate stellar parameters. Using the stars that most closely resemble the Sun, and complementing our data with photometry available in the literature, the solar colors on the uvby-beta system have been inferred. Our solar colors are compared with synthetic solar colors computed from absolute solar spectra and from the latest Kurucz (ATLAS9) and MARCS model atmospheres. The zero-points of different T(eff) and metallicity scales are verified and corrections are proposed. Results. Our solar colors are (b - y)(circle dot) = 0.4105 +/- 0.0015, m(1,circle dot) = 0.2122 +/- 0.0018, c(1,circle dot) = 0.3319 +/- 0.0054, and beta(circle dot) = 2.5915 +/- 0.0024. The (b - y)(circle dot) and m(1,circle dot) colors obtained from absolute spectrophotometry of the Sun agree within 3-sigma with the solar colors derived here when the photometric zero-points are determined from either the STIS HST observations of Vega or an ATLAS9 Vega model, but the c(1,circle dot) and beta(circle dot) synthetic colors inferred from absolute solar spectra agree with our solar colors only when the zero-points based on the ATLAS9 model are adopted. The Kurucz solar model provides a better fit to our observations than the MARCS model. For photometric values computed from the Kurucz models, (b - y)(circle dot) and m(1,circle dot) are in excellent agreement with our solar colors independently of the adopted zero-points, but for c(1,circle dot) and beta circle dot agreement is found only when adopting the ATLAS9 zero-points. The c(1,circle dot) color computed from both the Kurucz and MARCS models is the most discrepant, probably revealing problems either with the models or observations in the u band. The T(eff) calibration of Alonso and collaborators has the poorest performance (similar to 140 K off), while the relation of Casagrande and collaborators is the most accurate (within 10 K). We confirm that the Ramirez & Melendez uvby metallicity calibration, recommended by Arnadottir and collaborators to obtain [Fe/H] in F, G, and K dwarfs, needs a small (similar to 10%) zero-point correction to place the stars and the Sun on the same metallicity scale. Finally, we confirm that the c(1) index in solar analogs has a strong metallicity sensitivity.