Biogenic isoprene plays an important role in tropospheric chemistry. We use HCHO column measurements by the Global Ozone Monitoring Experiment (GOME) to constrain isoprene emissions. Using the global Goddrad Earth Observing SystemChemistry (GEOS-Chem) as the forward model, a Bayesian inversion of GOME HCHO observations from September 1996 to August 1997 is conducted. Column contributions to HCHO from 12 sources including 10 terrestrial ecosystem groups, biomass burning, and industry are considered and inverted for 8 geographical regions globally. The a posteriori solution reduces the model biases for all regions, and estimates the annual global isoprene emissions of 566 Tg C yr-1, ~50% larger than the a priori estimate. Compared to the Global Emissions Inventory Activity (GEIA) inventory (~500 Tg C yr-1), the a posteriori isoprene emissions are generally higher at mid latitudes and lower in the tropics. This increase of global isoprene emissions significantly affects tropospheric chemistry, decreasing the global mean OH concentration by 10.8% to 0.95106 molecules/cm3. The atmospheric lifetime of CH3CCl3 increases from 5.2 to 5.7 years. Positive matrix factorization (PMF), an advanced method for source apportionment, is applied to TRAnsport of Chemical Evolution over the Pacific (TRACE-P) measurements and it is found that cyanogenesis in plants over Asia is likely an important emission process for CH3COCH3 and HCN. This approach also is applied to estimate source contributions to the tropospheric ozone (O3) with Tropospheric Ozone Production about the Spring Equinox (TOPSE) and TRACE-P measurements. The corresponding GEOS-Chem simulations are applied to the same factor-projected space in order to evaluate the model simulations. Intercontinental transport of pollutants is most responsible for increasing trend of springtime O3, while stratospheric influence is the largest contributions to troposperic O3 variability at northern middle and high latitudes. On the other hand, the overall tropospheric contributions to O3 variability are more important at northern low latitudes by long-range transport, biomass burning, and industry/urban emissions. In general, the simulated O3 variabilities are comparable with those of observations. However, the model underestimates the trends of and the contributions to O3 variability by long-range transport of O3 and its precursors at northern middle and high latitudes.

Die vorliegende Arbeit beschäftigt sich mit der Modellerstellung und Technologie eines gravimetrischen Gassensors für organische Gase. Die Besonderheit liegt in dem verwendeten Resonatortyp. Es handelt sich um einen lateral elektrostatisch angeregten quadratischen Plattenresonator, der mit einer Rezeptorschicht versehen wird. Mit Hilfe von FEM-Berechnungen werden die Eigenfrequenzen und Eigenformen berechnet. Für die untersuchte Lamé- und Square-Mode wird die Sensorgüte unter Berücksichtigung des "Squeeze-Film-Damping" sowie der viskoelastischen Rezeptorschichteigenschaften bestimmt. Die Sensormoden werden durch ein Feder-Masse-Modell mit einem Freiheitsgrad modelliert und durch ein elektrisches Ersatzschaltbild repräsentiert. Die berechneten Nachweisgrenzen für Oktan und Toluol bei 6-facher Rauschgrenze liegen im zweistelligen ppb-Bereich. Für die technologische Umsetzung werden SOI-Wafer verwendet. Die ≤ 100 nm betragenden Spaltbreiten zwischen Elektroden und Resonator werden durch das RIE-Ätzen von Siliziumgräben mit senkrechten Seitenwänden, der Abscheidung von SiO2 als Opferschicht und dem Füllen der Gräben mit hochdotiertem Polysilizium hergestellt. Die Kontaktierung der Resonatoren erfolgt über einen leitenden Stamm, der aufgrund von selbstjustierenden Prozessen die Resonatorplatte zentriert einspannt. / The following work is concerned with the modelling and fabrication technology of a gravimetric sensor for volatile organic compounds (VOC). Novelty is the combination of a lateral electrostatic driven square plate resonator with a gas sensitive detection layer. The eigenfrequencies and -modes are calculated with FEM simulations. Especially suited for gas sensors are the Lamé- and Square eigenmodes which are studied more closely. The quality factor is determined considering "squeeze film damping" and the viscoelastic properties of the gas sensitive detection layer. To present the sensor oscillation modes a spring mass model with one degree of freedom is determined and extended by an equivalent circuit diagram. The calculated limits of detections for octane and toluene are in the binary ppb-range, working with six times the limit of frequency noise. SOI-wafers are the base material for the sensor process flow. Electrode gaps ≤100 nm, essential for the electrostatic drive, are fabricated by RIE-etching vertical trenches into the device layer down to the buried oxide and by depositing a silicon dioxide as sacrifical layer and by refilling the trenches with highly doped polysilicon. The electrical contact of the resonator plate is ensured through an electrical conducting polysilicon stem. The developed process flow enables a self alignment ot the stem, clamping the plate centered.

Στην παρούσα διατριβή µελετάται η ανάπτυξη υποστηριγµένων καταλυτών Pt και καταλυτών (σύνθετων και απλών) µεταλλικών οξειδίων υποστηριγµένων σε γ-Al2O3 για την αντίδραση της οξείδωσης του τολουολίου σε χαµηλές θερµοκρασίες καθώς και η κινητική της εν λόγω αντίδρασης. Τα πειράµατα πραγµατοποιήθηκαν στην θερµοκρασιακή περιοχή 100-500oC µε τροφοδοσία αποτελούµενη από µίγµα 0.1% C7H8 σε αέρα. Η καταλυτική ενεργότητα των καταλυτών Pt/MxOy εξαρτάται από την φύση του φορέα (CeO2, TiO2, SiO2, Al2O3, La2O3, κ.λ.) µε το Pt/CeO2 να παρουσιάζει την µεγαλύτερη ενεργότητα σε χαµηλές θερµοκρασίες. H αύξηση της ποσότητας του Pt από 0.5% έως 5.0% οδηγεί σε σηµαντική µετατόπιση της καµπύλης µετατροπής του τολουολίου προς χαµηλότερες θερµοκρασίες, ενώ η συχνότητας αναστροφής του τολουολίου (TOF) δεν εξαρτάται από τη φόρτιση σε µέταλλο, τουλάχιστον για καταλύτες Pt. Τα αναγώγιµα µεταλλικά οξείδια, όπως η δηµήτρια, είναι ενεργά για την οξείδωση του τολουολίου και η καταλυτική τους ενεργότητα αυξάνεται µε αύξηση της ειδικής επιφάνειας. Ωστόσο, ο εγγενής ρυθµός ανά m2 επιφάνειας καταλύτη παραµένει ο ίδιος για όλα τα δείγµατα που δοκιµάστηκαν. Μελετήθηκε η καταλυτική συµπεριφορά διάφορων µεταλλικών οξειδίων υποστηριγµένων σε γ-Al2O3 (MxOy/Al2O3). Τα αποτελέσµατα δείχνουν ότι η διασπορά των MxOy σε αδρανή φορέα υψηλής επιφάνειας, όπως γ-Al2O3, οδηγεί σε καταλύτες που χαρακτηρίζονται από σχετικά µεγάλη καταλυτική δραστικότητα, η οποία είναι σηµαντικά υψηλότερη για τα αναγώγιµα από ότι για τα µη-αναγώγιµα. Η καταλυτική συµπεριφορά µπορεί να βελτιωθεί µε την κατάλληλη επιλογή της ποσότητας φόρτισης σε MxOy. Καλύτερη απόδοση σε αυτή την σειρά καταλυτών παρουσιάζουν οι καταλύτες 60%MnOx, 90%CeO2 και 5%CuO υποστηριγµένοι σε Al2O3, οι οποίοι, κάτω από τις παρούσες συνθήκες αντίδρασης, είναι ικανοί να επιτυγχάνουν ολική µετατροπή τολουολίου σε θερµοκρασίες χαµηλότερες από 350oC. Η προσθήκη του Pt σε MxOy/Al2O3 βελτιώνει σηµαντικά την καταλυτική συµπεριφορά των µη-αναγώγιµων MxOy, αλλά δεν µεταβάλλει, ουσιαστικά, την ενεργότητα των αναγώγιµων MxOy. Προκειµένου να βελτιωθεί περαιτέρω η καταλυτική συµπεριφορά µελετήθηκε η καταλυτική ενεργότητα σύνθετων οξειδίων µετάλλων (MxOy = CuO, CeO2, MnOx)διεσπαρµένων σε γ-Al2O3 για την αντίδραση της οξείδωση του τολουολίου. Τα αποτελέσµατα των πειραµάτων που πραγµατοποιήθηκαν στη θερµοκρασιακή περιοχή 150-450οC έδειξαν ότι η ενεργότητα των σύνθετων καταλυτών εξαρτάται σηµαντικά από τη φύση, τη φόρτιση και την αναγωγιµότητα των επιµέρους οξειδίων. Βέλτιστη καταλυτική συµπεριφορά παρατηρήθηκε για µικτά οξείδια 10%CuO-60%MnOx, 15%CuO-75%CeO2 και 30%MnOx-50%CeO2 σε γ-Al2O3, η ενεργότητα των οποίων είναι συγκρίσιµη µε τους καταλύτες διασπαρµένων ευγενών µετάλλων. Η συµπεριφορά των βέλτιστων σύνθετων καταλυτών σε σύγκριση µε τα επιµέρους απλά µεταλλικά οξείδια υποστηριγµένα στον ίδιο φορέα (γ-Al2O3) µελετήθηκε περαιτέρω. Μετρήσεις του εγγενούς ρυθµού που πραγµατοποιήθηκαν σε διαφορικές συνθήκες αντίδρασης έδειξαν ότι η ενεργότητα αυτών των υλικών είναι περισσότερο από µία τάξη µεγέθους υψηλότερη από αυτή των αντίστοιχων απλών οξειδίων, υποδεικνύοντας την ύπαρξη φαινοµένων συνέργειας. Τα αποτελέσµατα πειραµάτων XRD που ελήφθησαν από τους σύνθετους καταλύτες δεν έδειξαν το σχηµατισµό κάποιας καινούργιας φάσης σε σύγκριση µε τα αντίστοιχα απλά οξείδια. Οι αλληλεπιδράσεις µεταξύ των ενεργών φάσεων και του φορέα εξετάστηκαν µέσω τεχνικών TPD και TPO. Στα πειράµατα TPD παρατηρήθηκε ότι οι πιο ενεργοί καταλύτες είναι αυτοί που εκροφούν µεγαλύτερες ποσότητες τολουολίου και παραγάγουν περισσότερο CO2 ή/και σε χαµηλότερη θερµοκρασία. Τα πειράµατα TPO έδειξαν ότι οι βέλτιστοι καταλύτες παράγουν µικρότερες ποσότητες CO2. Η επίδραση της παρουσίας δεύτερου VOC (προπανίου) ή υδρατµών στην τροφοδοσία µελετήθηκε στους βέλτιστους σύνθετους καταλύτες. Τα αποτελέσµατα δείχνουν ότι η παρουσία του νερού ή του προπανίου επιδρά παρεµποδιστικά στην καύση του τολουολίου, η παρουσία του οποίου, γενικά, δεν επηρεάζει σηµαντικά την οξείδωση του προπανίου στους τρεις βέλτιστους καταλύτες. Η επίδραση της µερικής πίεσης του τολουολίου στον εγγενή ρυθµό της αντίδρασης µελετήθηκε µε χρήση των τριών βέλτιστων σύνθετων καταλυτών στην θερµοκρασιακή περιοχή 270-320oC. Η χρησιµοποιούµενη τροφοδοσία αποτελείται από 0.036– 0.341 (% κ.ο.) C7H8 και σταθερή συγκέντρωση οξυγόνου (20.9 κ.ο % O2). Τα αποτελέσµατα δείχνουν ότι ο ρυθµός της αντίδρασης αυξάνεται, άλλα όχι πολύ σηµαντικά, µε αύξηση της µερικής πίεσης του τολουολίου. Τα κινητικά αποτελέσµατα προσαρµόστηκαν σε εµπειρική εκθετική εξίσωση (Power Law), από την οποία προέκυψαν οι τάξεις των αντιδρώντων, η φαινόµενη ενέργεια ενεργοποίησης της αντίδρασης καθώς και η αντίστοιχη εξίσωση ρυθµού. Συµπεραίνεται ότι κατάλληλος συνδυασµός οξειδίων µετάλλων διεσπαρµένων σε γ-Al2O3 µπορεί να οδηγήσει στην ανάπτυξη καταλυτών µε ενεργότητα συγκρίσιµη µε αυτή των υποστηριγµένων καταλυτών ευγενών µετάλλων. / Volatile organic compounds (VOCs) present at low concentrations in industrial waste streams are considered as significant air pollutants due to their toxic and malodorous nature, as well as their contribution to the formation of photochemical smog. Catalytic combustion over supported noble metal catalysts provides an effective method for the elimination of VOCs in exhaust gases and this technology seems to be able to satisfy strict emission standards. Efforts in this field are currently directed toward the development of cheaper, noble metal-free catalytic materials characterized by high activity at low temperatures and long-term stability under reaction conditions. In the present thesis, oxidation of toluene has been investigated over supported platinum catalysts as well as over single and mixed metal oxide (MxOy) catalysts dispersed on high surface γ-Al2O3. Catalysts were characterized with respect to their specific surface area (BET), metal dispersion (selective chemisorption of CO), phase composition and MxOy crystallite size (XRD) and reducibility (H2-TPR, CO-TPR). Catalytic performance for the title reaction was investigated in the temperature range of 100-500oC, using a feed composition consisting of 0.1% toluene in air. For Pt/MxOy catalysts, it has been found that catalytic performance depends on the nature of the support, with Pt/CeO2 being the most active catalyst at low temperatures. The intrinsic reaction rate per surface platinum atom does not depend on Pt loading (0.5-5 wt.%), at least for Pt/Al2O3 catalyst, but the global reaction rate increases with increase of exposed metallic surface area. Reducible metal oxides, such as ceria, are active for the title reaction and catalytic performance is improved significantly with increase of specific surface area (SSA). However, the intrinsic reaction rate per unit surface area is the same regardless of SSA. Dispersion of MxOy on high surface inert supports, such as Al2O3, results in materials with relatively high catalytic activity, which is considerably higher for reducible, compared to irreducible metal oxides. Catalytic performance of MxOy/Al2O3 catalysts can be optimized by proper selection of MxOy loading. Best performing catalysts of this series include 60%MnOx, 90%CeO2 and 5%CuO on Al2O3 which, under the present experimental conditions, are able to completely convert toluene toward CO2 at temperatures lower than 350oC. Dispersion of Pt on MxOy/Al2O3 catalysts improves significantly the catalytic performance of irreducible MxOy but does not alter appreciably activity of reducible MxOy/Al2O3 catalysts. The catalytic oxidation of toluene has been investigated also over single and composite metal oxide catalysts supported on γ-Al2O3. Catalysts were synthesized with the impregnation method and were characterized with respect to their specific surface area (BET method), crystalline mode and mean crystallite size (XRD technique), as well as with respect to their reducibility (temperature programmed reduction with H2 or CO). The effects of the nature, loading and composition of catalytic materials on their performance for VOC combustion has been investigated. Optimal results were obtained over Al2O3-supported CuO, CeO2, MnO2 catalysts and their mixtures. For certain metal oxide combinations, e.g., 10%CuO-60%MnOx, 15%CuO-75%CeO2 and 30%MnOx-50%CeO2, activity was found to be comparable to that of supported noble metal catalysts. Measurements of reaction rates under differential reaction conditions showed that specific activity of these materials was up to one order of magnitude higher, compared to that of the corresponding single metal oxides, implying that synergistic effects are operable. Results of XRD experiments did not show formation of new phases, but mixed oxide catalysts were found to exhibit a higher reducibility compared to catalysts consisting of the corresponding single metal oxides. The synergic effect of metal oxides interaction on the oxidation reaction was studied employing TPD and TPO techniques. The more active catalyst, the higher the amount of desorbed toluene and the higher the amount of CO2 production in the in the TPD experiments. The TPO experiments indicate that the optimized composite catalysts produce lower amounts of CO2 at lower temperature, compared to the corresponding single metal oxides. The influence of the presence of a second VOC (propane) or of water on the oxidation of toluene was also investigated. Results showed that the presence of water or propane in the feed results in a decrease of catalytic activity, while the presence of toluene doesn’t have any influence in the catalytic oxidation of propane over the optimized composite catalysts. The effect of partial pressure of toluene on the kinetic reaction rate has been investigated over the optimum composite catalysts in the 270–320oC range using a feed stream consisting of 0.036– 0.341 vol%C7H8 and a constant concentration of oxygen (20.9 vol% O2). Result showed that increasing the partial pressure of toluene leads to an increase of the reaction rate. The orders of the reaction with respect to reactants for the optimized catalysts were determined by fitting the experimental data to an empirical power-law rate expression according to which the reaction rate is given by the following relationships: 2.abtolOrkPp= (1) .0.aERTkke= (2) Results of the present study show that the catalytic performance of certain Al2O3-supported composite metal oxide catalysts is comparable to that of conventional supported noble metal catalysts. These materials could provide the basis for the development of cost-effective catalysts for combustion of VOCs present in waste gas streams.

The research focuses on the environmental problem of volatile organic compounds in ambient air of petrol filling stations. The literature review of the issues, arising from petrol-related VOCs, with actual and proposed VOC emissions trends in Europe, have been performed. Besides petrol filling station’s typical technology layout, petrol nature and composition, applicable petrol vapour recovery solutions and their efficiency were examinated. The volatile organic compounds’ experimental research in two petrol stations of typical technology layout in Vilnius city under similar extreme meteorological conditions (VOC air pollution episodes with low winds, stable stratification and suspended photochemical removal) is done. The emitted from petrol stations VOC experiment is based on air pumped sampling in glass gas pipette and further determination using gas chromatography with flame ionization detector. The experimental results, presented by means of tables and diagrams, are analysed and discussed. The available results of the experiment are loaded into the environmental model “ALOHA” for air pollution evaluation and concentrations prediction in the ambient air under different meteorological conditions and technological emergency situations (petrol spillage) at petrol filling station. The research is summarized in conclusions and recommendations. / Tyrimas skirtas aplinkos oro taršos problemai lakiaisiais organiniais junginiais, išsiskiriančiais nuo benzino degalinių. Atlikta svarstomos aplinkosauginės problemos literatūros apžvalga. Apžvelgti oro taršos pasekmės skatinamos LOJ išsiskyrimų nuo benzino degalinių, aktualios ir numatomos LOJ emisijų tendencijos Europoje, tipinis benzino degalinės technologijos išsidėstymas, benzino sudėtis ir svarbiausios LOJ garų formavimui benzino savybės, taikomi garų grąžinimo sprendiniai ir jų efektyvumas. Detaliai aprašytas LOJ eksperimentinis tyrimas, atliktas dviejose Vilniaus miesto tipinės technologijos degalinėse esant panašioms kraštutinėms (LOJ taršos epizodai prie silpnų vėjų, stabilios stratifikacijos ir suspenduoto fotocheminio šalinimo) meteorologiniams sąlygoms. LOJ mėginių ėmimui panaudotas aktyvus metodas su aspiracija į dujines pipetes, LOJ koncentracijos nustatytos dujinės chromatografijos su liepsnos jonizacijos detektoriumi metodu. Tyrimo rezultatai, pateikti lentelių ir diagramų pavidalu, aptarti ir įvertinti. Eksperimento duomenys įkelti į oro kokybės modelį “ALOHA”, siekiant nustatyti LOJ pernašą ir sudaryti LOJ koncentracijų prognozė benzino degalinių aplinkos ore prie skirtingų meteorologinių parametrų ir avarinių technologinių situacijų (benzino išsiliejimas). Tiriamąjį darbą reziumuoja išvados ir rekomendacijos.

Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-04-23T14:07:51Z No. of bitstreams: 1 Thalita Silva.pdf: 824830 bytes, checksum: 144a9fb3d8d0b2ef49b28207c4f7d487 (MD5) / Made available in DSpace on 2013-04-23T14:07:52Z (GMT). No. of bitstreams: 1 Thalita Silva.pdf: 824830 bytes, checksum: 144a9fb3d8d0b2ef49b28207c4f7d487 (MD5) Previous issue date: 2007 / O consumo de frituras é significativo no hábito dos brasileiros e tem aumentado nos últimos anos, isto por ser este um método rápido de preparação e por conferir características agradáveis de aroma e sabor aos alimentos fritos. Durante o processo de fritura, os óleos vegetais são continuamente ou repetidamente expostos a temperaturas elevadas, na presença de oxigênio atmosférico, levando os mesmos à degradação por diferentes tipos de reação. Alguns dos produtos de degradação formados, como por exemplo compostos carbonílicos, como formaldeído, acetaldeído e acroleína, podem ter efeitos adversos sobre a saúde humana. Neste trabalho determinou-se as taxas de emissão de compostos carbonílicos (CC), produzidos por óleos de dendê e soja quando submetidos a aquecimento a 180°C e exposição ao ar por diferentes intervalos de tempo, em processos contínuo e descontínuo e diferentes razões superfície:volume (S/V). Os CC foram coletados e derivatizados em cartuchos de sílica funcionalizados com C18 e impregnados com solução ácida de 2,4-DNPH, sendo a seguir extraídos e analisados por CLAE-DAD e, em alguns casos, CLAE-EM com ionização por eletrospray. Dentre os CC identificados nas emissões, destacaram - se no óleo de dendê, formaldeído; acetaldeído; acroleína; propanal; butanal; pentanal; hexanal; (E)-2-heptenal; heptanal; (E)-2-octenal; octanal; nonanal e (E)-2-decenal, enquanto no óleo de soja destacaram-se formaldeído; acetaldeído; acroleína; hexanal e (E)-2-heptenal. Dentre os quantificados, o que apresentou as maiores taxas de emissão nos dois óleos, nas três relações S/V estudadas, foi a acroleína, emitida em maiores taxas pelo óleo de soja. Em seguida, vieram o hexanal e o (E)-2- heptenal. No estudo da influência da relação S/V, as taxas de emissão estiveram, em geral, diretamente relacionadas à razão superfície/volume de óleo utilizado, embora CC saturados e insaturados tenham se comportado de maneira diferente frente à oxidação. Durante aquecimento descontínuo, houve uma tendência ao aumento nas taxas de emissão, ao longo do tempo, para os aldeídos saturados. Aldeídos insaturados, ao contrário, tiveram uma diminuição ao longo do tempo, devida provavelmente à alta reatividade da dupla ligação presente nestes compostos. Outros compostos orgânicos voláteis (COV) foram avaliados qualitativamente por extração do headspace e análise por CGAR-EM. As principais classes de compostos identificadas foram, mais uma vez, aldeídos alifáticos saturados e insaturados, embora também álcoois insaturados, ácidos carboxílicos e o 2-pentil-furano, todos provenientes de degradação lipídica. Finalmente, esse estudo mostra que a relação superfície/volume, o tempo de fritura, a forma de aquecimento (contínua ou descontínua), o tipo de óleo utilizado e a presença ou não de antioxidantes são fatores importantes na degradação dos óleos vegetais. Vale ressaltar que embora as emissões de acroleína e de outros aldeídos possam ser elevadas mesmo após períodos curtos de aquecimento do óleo, isso não corresponde necessariamente à altas exposições pelos trabalhadores em cozinha, uma vez que essas vão ser afetadas por outros fatores, tais como o grau de ventilação/exaustão do ar no ambiente. Todavia, elas podem servir como alerta para ações de prevenção. / Salvador

Neste trabalho foi estudado o tratamento simultâneo por biofiltração de emissões de compostos orgânicos voláteis, COV e gás sulfídrico, H2S, em estações de tratamento de despejos industriais, de refinaria de petróleo, ETDI. A biofiltração dos gases emanados da EDTI mostrou ser uma técnica de alta eficiência, atingindo valores de 95 a 99 % para tratamento simultâneo de COV e H2S em concentrações de 1000 e 100 ppmv, respectivamente. Foram realizados testes em 95 dias consecutivos de operação, em uma planta piloto instalada na Superintendência da Industrialização do Xisto, SIX, em São Mateus do Sul, Paraná, de março a agosto de 2006. O biofiltro foi do tipo fluxo ascendente, com 3,77 m3 de leito orgânico, composto de turfa, carvão ativado, lascas de madeira, serragem brita fina além de outros componentes menores. Foi realizada inoculação biológica com lodo filtrado de estação de tratamento de esgoto sanitário. As vazões de gás aplicadas variaram de 85 a 407 m3/h, resultando em taxas de carga de massa de 11,86 a 193,03 g de COV/h.m3 de leito e tempos de residência de 24 segundos a 6,5 minutos, com tempo ótimo de 1,6 minutos. A capacidade máxima de remoção do sistema encontrada, nas condições testadas, foi de 15 g de COV/h. m3, compatível com os valores encontrados na literatura para depuração biológica de COV na escala praticada. Também foi verificada a redução de componentes específicos de BTX, demonstrando boa degradabilidade dos compostos orgânicos. Finalmente o biofiltro demonstrou boa robustez biológica diante dos desvios operacionais intencionalmente provocados, tais como falta de umidade do leito, baixa temperatura, alta vazão, falta de carga de COV e baixo pH do leito. Depois de retomada a condição de operação estável, a biofiltração rapidamente atingiu o estado de equilíbrio, assegurando o uso eficiente e confiável da técnica no tratamento de gases de EDTI na indústria do hidrocarbonetos ou em refinarias de petróleo. / In this project the biofiltration technique was applied as air pollution control technology to treat simultaneously emissions containing volatile organic compounds, VOC and hydrogen sulfide, H2S, in hydrocarbon processing industries and oil refinery Waste Water Treatment Plant, WWTP. The technique demonstrated high biological efficiency up to 95 and 100 % of simultaneous biofiltration of VOC and H2S, with inicial concentration of 1000 and 100 ppmv, respectively. Tests were conducted at UN-SIX/ Petrobras Oil Shale Processing Unit facilities through 95 consecutives days, from March to August 2006. The chosen reactor model was an up stream system, pilot plant scale with volume of 3.77 m3 of an organic compost media made out a blend of peat, rotten wood chips, activated carbon, lime, among other minor components. The biological inoculation was done with sanitary sludge from WWTP. The pilot plant capacity was able to treat from 85 to 480 m3/h of WWTP off-gas, resulting COV application rate from 11.86 to 193.03 g VOC/ h. m3 of media, and residence time from 24 sec to 6.5 minutes, with optimum value at 1.6 minutes. The system maximum elimination rate was about 15 g VOC/h. m3, value comparable to ones presented in open literature. The specific BTX compounds depuration was observed, demonstrating relevant media specificity to treat organic compounds. Finally the biofiltration systems demonstrated good biological toughness considering the operational provoked upsets, as lack of media bed humidity, low biofiltration temperature, high flow rate, lack of VOC flow and acid pH. After normal operational conditions were retaken all process characteristics and efficiency [was] reached the correspondent values, showing reliable and efficient use of the technique to treat off gases in WWTP of hydrocarbon processing industries and Oil Refineries.

Made available in DSpace on 2014-12-17T14:19:46Z (GMT). No. of bitstreams: 1 DanielGM.pdf: 464208 bytes, checksum: 2046b6946316d59fe079319ca41a554c (MD5) Previous issue date: 2008-07-25 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The present work aims at investigating the role of Voc? S/A magazine within the ?rea of administrative discourses. The idea is to investigate the constituting variances in such market, presenting its working logics and its historical pathway that promoted its structure as we nowadays know. Furthermore, thought must be put into considering how the constituting agents of this market legitimize such practice. The understanding of this whole context will allow the explanation of the role of Voc? S/A magazine in this market and how the magazine is related to other area agents. The work is justified by casting light over a phenomena much neglected by the academy, which is the business press and the dissemination of social stock of knowledge developed from the new administrative discourses. The methodology used was the content analysis on published articles by the magazine, being preceded by the historical backtracking of the structuring of the investigated market. The research took into consideration the following results: the business press, in general, and the Voc? S/A in particular, presented themselves to be just one more tool for readers to increase their social stock of knowledge, as to be inserted into contemporary organizations. An enormous public arena in which the people interested in the diffusion of certain managing packages may spread such practices and earn economic capital with them / O presente trabalho tem como objetivo investigar o papel desempenhado pela Revista Voc? S/A no mercado de discursos administrativos. A id?ia ? investigar quais s?o as nuances constitutivas desse mercado, apresentando sua l?gica de funcionamento e o percurso hist?rico que promoveu a sua estrutura??o, tal como se conhece contemporaneamente. Al?m disso, deve-se pensar como os agentes que constituem esse mercado atuam e legitimam suas pr?ticas. A compreens?o de todo esse contexto permitir? explicar qual o papel desempenhado pela Revista Voc? S/A nesse mercado e como ela se relaciona com os demais agentes constitutivos do campo. O trabalho se justifica por trazer luz a um fen?meno t?o negligenciado pela academia, que ? a imprensa de neg?cios e a dissemina??o desempenhada por ela dos estoques sociais de conhecimento provindos dos novos discursos administrativos. A metodologia empregada foi a de an?lise de conte?do sobre as mat?rias publicadas pela revista, sendo precedida pela constru??o hist?rica da estrutura??o do mercado investigado. A pesquisa levou aos seguintes resultados: a imprensa de neg?cios, em geral, e a Revista Voc? S/A, em particular, se apresentam como mais uma ferramenta para que os leitores aumentem o estoque social de conhecimentos, para se inserir nas organiza??es contempor?neas. Legitima-se, tamb?m, como uma arena p?blica na qual os interessados na difus?o de determinados pacotes gerenciais possam difundir tais pr?ticas e ganhar capital econ?mico com elas

Neste trabalho foi estudado o tratamento simultâneo por biofiltração de emissões de compostos orgânicos voláteis, COV e gás sulfídrico, H2S, em estações de tratamento de despejos industriais, de refinaria de petróleo, ETDI. A biofiltração dos gases emanados da EDTI mostrou ser uma técnica de alta eficiência, atingindo valores de 95 a 99 % para tratamento simultâneo de COV e H2S em concentrações de 1000 e 100 ppmv, respectivamente. Foram realizados testes em 95 dias consecutivos de operação, em uma planta piloto instalada na Superintendência da Industrialização do Xisto, SIX, em São Mateus do Sul, Paraná, de março a agosto de 2006. O biofiltro foi do tipo fluxo ascendente, com 3,77 m3 de leito orgânico, composto de turfa, carvão ativado, lascas de madeira, serragem brita fina além de outros componentes menores. Foi realizada inoculação biológica com lodo filtrado de estação de tratamento de esgoto sanitário. As vazões de gás aplicadas variaram de 85 a 407 m3/h, resultando em taxas de carga de massa de 11,86 a 193,03 g de COV/h.m3 de leito e tempos de residência de 24 segundos a 6,5 minutos, com tempo ótimo de 1,6 minutos. A capacidade máxima de remoção do sistema encontrada, nas condições testadas, foi de 15 g de COV/h. m3, compatível com os valores encontrados na literatura para depuração biológica de COV na escala praticada. Também foi verificada a redução de componentes específicos de BTX, demonstrando boa degradabilidade dos compostos orgânicos. Finalmente o biofiltro demonstrou boa robustez biológica diante dos desvios operacionais intencionalmente provocados, tais como falta de umidade do leito, baixa temperatura, alta vazão, falta de carga de COV e baixo pH do leito. Depois de retomada a condição de operação estável, a biofiltração rapidamente atingiu o estado de equilíbrio, assegurando o uso eficiente e confiável da técnica no tratamento de gases de EDTI na indústria do hidrocarbonetos ou em refinarias de petróleo. / In this project the biofiltration technique was applied as air pollution control technology to treat simultaneously emissions containing volatile organic compounds, VOC and hydrogen sulfide, H2S, in hydrocarbon processing industries and oil refinery Waste Water Treatment Plant, WWTP. The technique demonstrated high biological efficiency up to 95 and 100 % of simultaneous biofiltration of VOC and H2S, with inicial concentration of 1000 and 100 ppmv, respectively. Tests were conducted at UN-SIX/ Petrobras Oil Shale Processing Unit facilities through 95 consecutives days, from March to August 2006. The chosen reactor model was an up stream system, pilot plant scale with volume of 3.77 m3 of an organic compost media made out a blend of peat, rotten wood chips, activated carbon, lime, among other minor components. The biological inoculation was done with sanitary sludge from WWTP. The pilot plant capacity was able to treat from 85 to 480 m3/h of WWTP off-gas, resulting COV application rate from 11.86 to 193.03 g VOC/ h. m3 of media, and residence time from 24 sec to 6.5 minutes, with optimum value at 1.6 minutes. The system maximum elimination rate was about 15 g VOC/h. m3, value comparable to ones presented in open literature. The specific BTX compounds depuration was observed, demonstrating relevant media specificity to treat organic compounds. Finally the biofiltration systems demonstrated good biological toughness considering the operational provoked upsets, as lack of media bed humidity, low biofiltration temperature, high flow rate, lack of VOC flow and acid pH. After normal operational conditions were retaken all process characteristics and efficiency [was] reached the correspondent values, showing reliable and efficient use of the technique to treat off gases in WWTP of hydrocarbon processing industries and Oil Refineries.

Cabines de veículos automotores recém-manufaturados podem ser consideradas críticas quando se avalia a qualidade do ar interno, pois concentrações de compostos orgânicos voláteis encontram-se em níveis mais altos que os ambientes externos. Determinadas substâncias presentes no ar da cabine podem ser prejudiciais ao ser humano em função da sua toxicidade, pricipalmente nos grandes centros urbanos. A avaliação do ar da cabine automotiva se faz necessária. Nesse estudo, foi feita uma avaliação da qualidade do ar interno da cabine de 7 veículos populares recém-manufaturados contendo materiais de acabamento interno iguais. Um total de 46 compostos orgânicos voláteis foi identificado, sendo que 14 deles são compostos carbonílicos e 32 são hidrocarbonetos alifáticos e aromáticos, compostos halogenados e um nitrogenado. Os compostos carbonílicos foram identificados e quantificados por cromatografia a líquido e os outros VOCs apenas identificados por GC-MS. No ar interno da cabine dos veículos estudados, as concentrações médias encontradas para os compostos carbonílicos (µg/m3) em ordem decrescente foram: formaldeído (165,3); acetona (67,5); acetaldeído (56,8); isovaleraldeído (40,8); propionaldeído (21,1); butiraldeído (17,9); crotonaldeído (14,9); hexaldeído (14,9) valeraldeído (9,8); 2.5- dimetilbenzaldeído (9,3); otolualdeído (8,4); p/m tolualdeído (6,8); acroleína (4,2) e benzaldeído (3,8). Com relação aos outros VOCS foram identificados o metilbutano, que apresentou a maior porcentagem de abundância relativa, 8,5%, seguido de outros hidrocarbonetos com abundância relativa entre 5 e 2% , como, 2,7,10-trimetildodecano, 2,2,6-trimetildecano, ciclopentano, 2,3,4-trimetildecano, n-pentano, 3,6-dimetilundecano, 4-metildodecano, 4,6- dimetildodecano, 3,6-dimetildecano e 1,2-dimetilbenzeno. Dois derivados de hidrocarbonetos halogenados também foram encontrados, sendo que o triclorofluormetano foi o majoritário com 5,7%, e um composto nitrogenado, a acetonitrila com 5,4%. Os compostos derivados do benzeno identificados foram: 1,2-dimetilbenzeno, etilbenzeno, metilbenzeno, 1-etil-3- metilbenzeno, 1-etil-3-metilbenzeno e 1,3,5-trimetilbenzeno que perfazem 6,6 % de abundância relativa. O mais abundante entre os aromáticos foi o 1,2-dimetilbenzeno (2,5%). Os resultados experimentais revelaram também a liberação de VOCs pelos materiais de acabamento interno dos veículos automotores recém-manufaturados. / New motor vehicles cabins may be critical when considering the internal air quality, because concentrations of volatile organic compounds are at levels higher than the outdoors. Certain substances present in the cabin air can be harmful to humans according to their toxicity, mainly in the big cities. Assessment of the cabin air becomes necessary. In this study, cabin air quality was assessed and 7 popular new vehicles containing same interior trim materials were evaluated. A total of 46 volatile organic compounds were identified, with 14 of them were carbonylic compounds and 32 are aliphatic and aromatic hydrocarbons, halogenated compounds and a nitrogenated compound. The carbonylic compounds were identified and quantified by the liquid chromatography and other VOCs only identified by GC-MS. Cabin air vehicles studied showed the following average concentrations found for carbonylic compounds ( µg/m3) in a descending order: formaldehyde (165.3), acetone (67.5); acetaldehyde (56.8); Isovaleraldehyde ( 40.8); propionaldehyde (21.1); butyraldehyde (17.9); crotonaldeído (14.9); hexaldeído (14.9) Valeraldehyde (9.8); dimetilbenzaldeído-2.5 (9.3); the - tolualdeído (8.4), p / m - tolualdeído (6.8); acrolein (4.2) and benzaldehyde (3.8). Concerning the other VOCs the following compounds were identified: methylbutane, which had the highest percentage of relative abundance, 8.5%, followed by other hydrocarbons with relative abundance between 5 and 2%, 2,7,10-trimetildodecano, 2.2 ,6- Trimetildecano, ciclopentano, 2,3,4-trimetildecano, n-pentane, 3.6-dimetilundecano, 4- metildodecano, dimetildodecano-4.6, 3.6 and 1.2-dimetildecano-dimetilbenzeno. Two halogenated hydrocarbons were also found, and triclorofluormetano had the biggest relative abundance percentage 5.7%, and a nitrogen compound, the acetonitrile with 5.4%. The benzene compounds identified were: 1.2-dimetilbenzeno, ethylbenzene, methylbenzene, 1- ethyl-3-methyl, ethyl-1-and 3-methyl 1,3,5-trimethylbenzene which comprise 6.6% of relative abundance. 1.2-dimetilbenzeno was the most abundant aromatic compound with relative abundance 2.5%. Results also showed that VOCs were released by studied vehicles interior trim materials.

Les travaux dont les résultats sont présentés dans ce manuscrit ont été menés dans le but de préparer des matériaux catalytiques à base de métaux nobles pour l'élimination de certains composés organiques volatils (COV). Différents catalyseurs à base de platine ont ainsi été préparés et leurs performances catalytiques évaluées pour l'oxydation de deux polluants : le n-butanol et l'acide acétique. Une première étude sur l'élimination oxydative et non-oxydative du n-butanol sur des catalyseurs à base de platine supportés sur alumine a été menée. Ce travail a porté essentiellement sur l'étude de l'effet des différents paramètres intervenant dans la réaction (oxygène, eau, métal). Le phénomène d'adsorption-désorption du polluant à la surface du catalyseur a également été étudié. S'inspirant des données de la littérature sur les propriétés redox particulières de la cérine, les travaux ont ensuite porté sur l'effet de l'ajout de CeO2 à des catalyseurs de type Pt/Al2O3 pour l'oxydation du n-butanol et de l'acide acétique. La modification des propriétés redox et acido-basiques ainsi que celle des performances catalytiques du matériau observées avec l'ajout de CeO2 a permis d'établir une corrélation entre activité catalytique en oxydation, capacité de stockage de l'oxygène et basicité. Cette corrélation a été confirmée dans la dernière étude menée sur des catalyseurs mis en forme de type monolithes enduits avec différents matériaux (Pt/Al2O3, Pt/CeO2, Pt/ZrO2, Pt/Al2O3-CeO2, Pt/Al2O3-ZrO2 et Pt/CeO2-ZrO2). / The results presented in this manuscript have aimed at preparing catalytic materials based on noble metals for the removal of volatile organic compounds (VOC). Thus, different platinum based catalysts have been prepared and their catalytic performances have been evaluated for n-butanol and acetic acid oxidation. A first study on oxidative and non-oxidative removal of n-butanol over alumina supported platinum based catalysts has been performed. This work focused on the study of the effect of the different parameters involved in the reaction (oxygen, water, metal). The adsorption-desorption phenomenon of the pollutant on the catalyst surface has also been studied.Inspired by the literature on the specific redox properties of ceria, the work was then focused on the effect of the addition of CeO2 to Pt/Al2O3 catalysts for n-butanol and acetic acid oxidation. The modification of the redox and acid-base properties as well as that of the catalytic performances of the material with the addition of CeO2 allowed to establish a relationship between catalytic oxidation activities, oxygen storage capacity and basicity. This correlation has been confirmed in the last study performed on the monolithic catalysts coated with different materials (Pt/Al2O3, Pt/CeO2, Pt/ZrO2, Pt/Al2O3-CeO2, Pt/Al2O3-ZrO2 and Pt/CeO2-ZrO2).