Entwicklung einer Impulsmethode zur Ermittlung thermodynamischer und reaktionskinetischer Parameter in der heterogenen Katalyse

Heterogeneous catalysis, homogeneous catalysis, adsorption equilibrium, reaction kinetics, impulse method, hydrolysis of methyl formate, production of formic acid

Assessment of particulate exposure and surface characteristics in association with urinary levels of 8-hydroxy-2'-deoxyguanosine, considered as marker of oxidative stress

Epidemiological studies have demonstrated that exposure to fine particles is associated to adverse health effects, including cancer, respiratory and cardiovascular diseases. However, mechanisms by which particles induce health effects remain unclear. According to one of the most investigated hypotheses, particles cause adverse effects through the production of reactive oxygen species (ROS), which are very hazardous compounds able to attack directly biological structures, including the DNA strand or the lipid bilayer of the cells. If the defense mechanisms, constituted of antioxidants, are not able to counter ROS, then these compounds will cause in the body a range of oxidation reactions called "oxidative stress". The aim of the present research project was to better understand mechanisms by which exposure to fine particles induces oxidative stress. The first point of this project was to check whether exposure to high levels of fine particles is directly linked to oxidative stress, and whether this oxidative stress is accompanied by the activation of the defense mechanisms (antioxidants). The second point was to study the role played by the particle surface characteristics in the oxidative stress process. For that purpose, a study was conducted in bus depots with the participation of 40 mechanics. First, occupational exposure to particles (PM4) and to other pollutants (NOx, O3) was measured over a two-day period. Then, urine samples of mechanics were collected in order to measure levels of 8-hydroxy-2'-deoxyguanosine (8OHdG) and antioxidants. 8OHdG is a molecule formed by the oxidation of DNA and allowing to assess the oxidative stress status of the mechanics. Finally, particles were collected on filters, and functional groups located on the particle surface were analyzed in the laboratory using a Knudsen flow reactor. This technique allows not only to quantify functional groups on the particle surface, but also to measure the reaction kinetics. Results obtained during the field campaign in bus depots showed that mechanics were exposed to rather low levels of PM4 (20-85 μg/m3) and of pollutants (NOx: 100-1000 ppb; O3: <15 ppb). However, despite this low exposure, urinary levels of the oxidative stress biomarker (8OHdG) increased significantly for non-smoking workers over a two-day period of shift. This oxidative stress was accompanied by an increase of antioxidants, indicating the activation of defense mechanisms. On the other hand, the analysis of functional groups on the particle surface showed important differences, depending on the workplace, the date and the activities of workers. The particle surface contained simultaneously antagonistic functional groups which did not undergo internal reactions (such as acids and bases), and was usually characterized by a high density of carbonyl functions and a low density of acidic sites. Reaction kinetics measured using the Knudsen flow reactor pointed out fast reactions of oxidizable groups and slow reactions of acidic sites. Several exposure parameters were significantly correlated with the increase of the oxidative stress status: the presence of acidic sites, carbonyl functions and oxidizable groups on the particle surface; reaction kinetics of functional groups on the particle surface; particulate iron and copper concentrations; and NOx concentration.

Nucleation and growth of metamorphic minerals in contact aureoles

THESIS ABSTRACT Nucleation and growth of metamorphic minerals are the consequence of changing P-T-X-conditions. The thesis presented here focuses on processes governing nucleation and growth of minerals in contact metamorphic environments using a combination of geochemical analytics (chemical-, isotope-, and trace element composition), statistical treatments of spatial data, and numerical models. It is shown, that a combination of textural modeling and stable isotope analysis allows a distinction between several possible reaction paths for olivine growth in a siliceous dolomite contact aureole. It is suggested that olivine forms directly from dolomite and quartz. The formation of olivine from this metastable reaction implies metamorphic crystallization far from equilibrium. As a major consequence, the spatial distribution of metamorphic mineral assemblages in a contact aureole cannot be interpreted as a proxy for the temporal evolution of a single rock specimen, because each rock undergoes a different reaction path, depending on temperature, heating rate, and fluid-infiltration rate. A detailed calcite-dolomite thermometry study was initiated on multiple scales ranging from aureole scale to the size of individual crystals. Quantitative forward models were developed to evaluate the effect of growth zoning, volume diffusion and the formation of submicroscopic exsolution lamellae (<1 µm) on the measured Mg-distribution in individual calcite crystals and compare the modeling results to field data. This study concludes that Mg-distributions in calcite grains of the Ubehebe Peak contact aureole are the consequence of rapid crystal growth in combination with diffusion and exsolution. The crystallization history of a rock is recorded in the chemical composition, the size and the distribution of its minerals. Near the Cima Uzza summit, located in the southern Adamello massif (Italy), contact metamorphic brucite bearing dolomite marbles are exposed as xenoliths surrounded by mafic intrusive rocks. Brucite is formed retrograde pseudomorphing spherical periclase crystals. Crystal size distributions (CSD's) of brucite pseudomorphs are presented for two profiles and combined with geochemistry data and petrological information. Textural analyses are combined with geochemistry data in a qualitative model that describes the formation periclase. As a major outcome, this expands the potential use of CSD's to systems of mineral formation driven by fluid-infiltration. RESUME DE LA THESE La nucléation et la croissance des minéraux métamorphiques sont la conséquence de changements des conditions de pression, température et composition chimique du système (PT-X). Cette thèse s'intéresse aux processus gouvernant la nucléation et la croissance des minéraux au cours d'un épisode de métamorphisme de contact, en utilisant la géochimie analytique (composition chimique, isotopique et en éléments traces), le traitement statistique des données spatiales et la modélisation numérique. Il est montré que la combinaison d'un modèle textural avec des analyses en isotopes stables permet de distinguer plusieurs chemins de réactions possibles conduisant à la croissance de l'olivine dans une auréole de contact riche en Silice et dolomite. Il est suggéré que l'olivine se forme directement à partir de la dolomie et du quartz. Cette réaction métastable de formation de l'olivine implique une cristallisation métamorphique loin de l'équilibre. La principale conséquence est que la distribution spatiale des assemblages de minéraux métamorphiques dans une auréole de contact ne peut pas être considérée comme un témoin de l'évolution temporelle d'un type de roche donné, puisque chaque type de roche suit différents chemins de réactions, en fonction de la température, la vitesse de réchauffement et le taux d'infiltration du fluide. Une étude thermométrique calcite-dolomite détaillée a été réalisée à diverses échelles, depuis l'échelle de l'auréole de contact jusqu'à l'échelle du cristal. Des modèles numériques quantitatifs ont été développés pour évaluer l'effet des zonations de croissance, de la diffusion volumique et de la formation de lamelles d'exsolution submicroscopiques (<1µm) sur la distribution du magnésium mesuré dans des cristaux de calcite individuels. Les résultats de ce modèle ont été comparés ä des échantillons naturels. Cette étude montre que la distribution du Mg dans les grains de calcite de l'auréole de contact de l'Ubehebe Peak (USA) résulte d'une croissance cristalline rapide, associée aux processus de diffusion et d'exsolution. L'histoire de cristallisation d'une roche est enregistrée dans la composition chimique, la taille et la distribution de ses minéraux. Près du sommet Cima Uzza situé au sud du massif d'Adamello (Italie), des marbres dolomitiques à brucite du métamorphisme de contact forment des xénolithes dans une intrusion mafique. La brucite constitue des pseudomorphes rétrogrades du périclase. Les distributions de taille des cristaux (CSD) des pseudomorphes de brucite sont présentées pour deux profiles et sont combinées aux données géochimiques et pétrologiques. Les analyses textorales sont combinées aux données géochimiques dans un modèle qualitatif qui décrit la formation du périclase. Ceci élargit l'utilisation potentielle de la C5D aux systèmes de formation de minéraux controlés par les infiltrations fluides. THESIS ABSTRACT (GENERAL PUBLIC) Rock textures are essentially the result of a complex interaction of nucleation, growth and deformation as a function of changing physical conditions such as pressure and temperature. Igneous and metamorphic textures are especially attractive to study the different mechanisms of texture formation since most of the parameters like pressure-temperature-paths are quite well known for a variety of geological settings. The fact that textures are supposed to record the crystallization history of a rock traditionally allowed them to be used for geothermobarometry or dating. During the last decades the focus of metamorphic petrology changed from a static point of view, i.e. the representation of a texture as one single point in the petrogenetic grid towards a more dynamic view, where multiple metamorphic processes govern the texture formation, including non-equilibrium processes. This thesis tries to advance our understanding on the processes governing nucleation and growth of minerals in contact metamorphic environments and their dynamic interplay by using a combination of geochemical analyses (chemical-, isotope-, and trace element composition), statistical treatments of spatial data and numerical models. In a first part the thesis describes the formation of metamorphic olivine porphyroblast in the Ubehebe Peak contact aureole (USA). It is shown that not the commonly assumed succession of equilibrium reactions along a T-t-path formed the textures present in the rocks today, but rather the presence of a meta-stable reaction is responsible for forming the olivine porphyroblast. Consequently, the spatial distribution of metamorphic minerals within a contact aureole can no longer be regarded as a proxy for the temporal evolution of a single rock sample. Metamorphic peak temperatures for samples of the Ubehebe Peak contact aureole were determined using calcite-dolomite. This geothermometer is based on the temperature-dependent exchange of Mg between calcite and dolomite. The purpose of the second part of this thesis was to explain the interfering systematic scatter of measured Mg-content on different scales and thus to clarify the interpretation of metamorphic temperatures recorded in carbonates. Numerical quantitative forward models are used to evaluate the effect of several processes on the distribution of magnesium in individual calcite crystals and the modeling results were then compared to measured field. Information about the crystallization history is not only recorded in the chemical composition of grains, like isotope composition or mineral zoning. Crystal size distributions (CSD's) provide essential information about the complex interaction of nucleation and growth of minerals. CSD's of brucite pseudomorphs formed retrograde after periclase of the southern Adamello massif (Italy) are presented. A combination of the textural 3D-information with geochemistry data is then used to evaluate reaction kinetics and to constrain the actual reaction mechanism for the formation of periclase. The reaction is shown to be the consequence of the infiltration of a limited amount of a fluid phase at high temperatures. The composition of this fluid phase is in large disequilibrium with the rest of the rock resulting in very fast reaction rates. RESUME DE LA THESE POUR LE GRAND PUBLIC: La texture d'une roche résulte de l'interaction complexe entre les processus de nucléation, croissance et déformation, en fonction des variations de conditions physiques telles que la pression et la température. Les textures ignées et métamorphiques présentent un intérêt particulier pour l'étude des différents mécanismes à l'origine de ces textures, puisque la plupart des paramètres comme les chemin pression-température sont relativement bien contraints dans la plupart des environnements géologiques. Le fait que les textures soient supposées enregistrer l'histoire de cristallisation des roches permet leur utilisation pour la datation et la géothermobarométrie. Durant les dernières décennies, la recherche en pétrologie métamorphique a évolué depuis une visualisation statique, c'est-à-dire qu'une texture donnée correspondait à un point unique de la grille pétrogénétique, jusqu'à une visualisation plus dynamique, où les multiples processus métamorphiques qui gouvernent 1a formation d'une texture incluent des processus hors équilibre. Cette thèse a pour but d'améliorer les connaissances actuelles sur les processus gouvernant la nucléation et la croissance des minéraux lors d'épisodes de métamorphisme de contact et l'interaction dynamique existant entre nucléation et croissance. Pour cela, les analyses géochimiques (compositions chimiques en éléments majeurs et traces et composition isotopique), le traitement statistique des données spatiales et la modélisation numérique ont été combinés. Dans la première partie, cette thèse décrit la formation de porphyroblastes d'olivine métamorphique dans l'auréole de contact de l'Ubehebe Peak (USA). Il est montré que la succession généralement admise des réactions d'équilibre le long d'un chemin T-t ne peut pas expliquer les textures présentes dans les roches aujourd'hui. Cette thèse montre qu'il s'agirait plutôt d'une réaction métastable qui soit responsable de la formation des porphyroblastes d'olivine. En conséquence, la distribution spatiale des minéraux métamorphiques dans l'auréole de contact ne peut plus être interprétée comme le témoin de l'évolution temporelle d'un échantillon unique de roche. Les pics de température des échantillons de l'auréole de contact de l'Ubehebe Peak ont été déterminés grâce au géothermomètre calcite-dolomite. Celui-ci est basé sur l'échange du magnésium entre la calcite et la dolomite, qui est fonction de la température. Le but de la deuxième partie de cette thèse est d'expliquer la dispersion systématique de la composition en magnésium à différentes échelles, et ainsi d'améliorer l'interprétation des températures du métamorphisme enregistrées dans les carbonates. Des modèles numériques quantitatifs ont permis d'évaluer le rôle de différents processus sur la distribution du magnésium dans des cristaux de calcite individuels. Les résultats des modèles ont été comparés aux échantillons naturels. La composition chimique des grains, comme la composition isotopique ou la zonation minérale, n'est pas le seul témoin de l'histoire de la cristallisation. La distribution de la taille des cristaux (CSD) fournit des informations essentielles sur les interactions entre nucléation et croissance des minéraux. La CSD des pseudomorphes de brucite retrograde formés après le périclase dans le sud du massif Adamello (Italie) est présentée dans la troisième partie. La combinaison entre les données textorales en trois dimensions et les données géochimiques a permis d'évaluer les cinétiques de réaction et de contraindre les mécanismes conduisant à la formation du périclase. Cette réaction est présentée comme étant la conséquence de l'infiltration d'une quantité limitée d'une phase fluide à haute température. La composition de cette phase fluide est en grand déséquilibre avec le reste de la roche, ce qui permet des cinétiques de réactions très rapides.

Ion-exchange resins as stationary phase in reactive chromatography

Dynamic behavior of bothisothermal and non-isothermal single-column chromatographic reactors with an ion-exchange resin as the stationary phase was investigated. The reactor performance was interpreted by using results obtained when studying the effect of the resin properties on the equilibrium and kinetic phenomena occurring simultaneously in the reactor. Mathematical models were derived for each phenomenon and combined to simulate the chromatographic reactor. The phenomena studied includes phase equilibria in multicomponent liquid mixture¿ion-exchange resin systems, chemicalequilibrium in the presence of a resin catalyst, diffusion of liquids in gel-type and macroporous resins, and chemical reaction kinetics. Above all, attention was paid to the swelling behavior of the resins and how it affects the kinetic phenomena. Several poly(styrene-co-divinylbenzene) resins with different cross-link densities and internal porosities were used. Esterification of acetic acid with ethanol to produce ethyl acetate and water was used as a model reaction system. Choosing an ion-exchange resin with a low cross-link density is beneficial inthe case of the present reaction system: the amount of ethyl acetate as well the ethyl acetate to water mole ratio in the effluent stream increase with decreasing cross-link density. The enhanced performance of the reactor is mainly attributed to increasing reaction rate, which in turn originates from the phase equilibrium behavior of the system. Also mass transfer considerations favor the use ofresins with low cross-link density. The diffusion coefficients of liquids in the gel-type ion-exchange resins were found to fall rapidly when the extent of swelling became low. Glass transition of the polymer was not found to significantlyretard the diffusion in sulfonated PS¿DVB ion-exchange resins. It was also shown that non-isothermal operation of a chromatographic reactor could be used to significantly enhance the reactor performance. In the case of the exothermic modelreaction system and a near-adiabatic column, a positive thermal wave (higher temperature than in the initial state) was found to travel together with the reactive front. This further increased the conversion of the reactants. Diffusion-induced volume changes of the ion-exchange resins were studied in a flow-through cell. It was shown that describing the swelling and shrinking kinetics of the particles calls for a mass transfer model that explicitly includes the limited expansibility of the polymer network. A good description of the process was obtained by combining the generalized Maxwell-Stefan approach and an activity model that was derived from the thermodynamics of polymer solutions and gels. The swelling pressure in the resin phase was evaluated by using a non-Gaussian expression forthe polymer chain length distribution. Dimensional changes of the resin particles necessitate the use of non-standard mathematical tools for dynamic simulations. A transformed coordinate system, where the mass of the polymer was used as a spatial variable, was applied when simulating the chromatographic reactor columns as well as the swelling and shrinking kinetics of the resin particles. Shrinking of the particles in a column leads to formation of dead volume on top of the resin bed. In ordinary Eulerian coordinates, this results in a moving discontinuity that in turn causes numerical difficulties in the solution of the PDE system. The motion of the discontinuity was eliminated by spanning two calculation grids in the column that overlapped at the top of the resin bed. The reactive and non-reactive phase equilibrium data were correlated with a model derived from thethermodynamics of polymer solution and gels. The thermodynamic approach used inthis work is best suited at high degrees of swelling because the polymer matrixmay be in the glassy state when the extent of swelling is low.

Kuplivan leijukerroksen poltto- ja lämpötekninen tarkastelu

Työn tavoitteena oli luoda menetelmä leijukerroskattilan petin lämpötilojen ja toiminta-alueen arvioimiseksi annetuilla lähtötiedoilla. Toimintatapana oli tutkia polttoaineen ominaisuuksien ja kattilan geometrian vaikutuksia petin energiataseeseen ja tätä kautta petin lämpötilaan kattilan ajotapa huomioiden. Työn teoriaosassa esitellään aluksi biopolttoaineiden ominaisuuksia ja leijukerroskattilan toimintaa petin toimintaympäristön selvittämiseksi. Teoriaosan lopussa käsitellään perusteellisesti petin hydrodynamiikkaa ja reaktiokinettikkaa sekä petin alueen mekaanista mitoitusta. Lisäksi polttoaineen syöttötapa ja palaminen petissä tuodaan esille. Tutkimusosassa selvitetään petin energiatasemallin määrittämistä teoriaan ja diplomityön aikana eri kattiloilla suoritettuihin mittauksiin perustuen. Mittauksista on erillinen selvitys seitsemännessä kappaleessa. Lopuksi kuvaillaan petin energiatasetta mallintavan menetelmän toimintaa sekä siihen syötettäviä lähtötietoja. Tuloksena on saatu suppealla alueella toimiva laajennettavissa oleva petin energiataseen malli. Menetelmän testaamiseen käytetään mittaustietoa kahdelta kattilalta, joita ei olla käytetty petin energiatasemallin virityksessä.

Kineettinen tarkastelu keskisakeusalueella toimivalle happivaiheelle

Työn tavoitteena oli tarkastella keskisakeudessa toimivan happidelignifioinnin kinetiikkaa ja vertailla sitä olemassa olevien kineettisten tutkimuksien kanssa. Lisäksi tutkittiin kuinka happivaiheen suodos vaikuttaa delignifiointiasteeseen sekä selektiivisyyteen. Työn kirjallisuusosassa perehdyttiin happidelignifioinnin kineettisiin malleihin, jotka on kehitetty ennustamaan alkalin, paineen, lämpötilan ja ajan vaikutusta ligniinin poistumiselle sekä hiilihydraattiketjujen katkeilulle. Delignifioituminen on nopeaa ensimmäisen kymmenen minuutin aikana ja hidastuu jäännösdelignifiointivaiheessa. Laboratoriotutkimuksissa selvitettiin kuinka prosessimuuttujat vaikuttavat kappaluvun ja viskositeetin muutokseen. Tuloksia tarkasteltiin lineaarisella regressioanalyysillä, jonka avulla muuttujien vaikutukset saadaan selkeästi esille. Happivaiheen ensimmäisessä vaiheessa suurin vaikutus delignifiointiasteeseen sekä viskositeetin alenemiseen on alkaliannoksella. Pienillä hapen annostuksella saavutettiin hyvä selektiivisyys, suurillakin alkaliannoksilla. Lämpötilan vaikutus on lähes olematon, kun paine on pieni. Kun paine kasvaa, kasvaa myös lämpötilan vaikutus delignifiointiasteeseen. Hiilihydraattien depolymerisoituminen lisääntyy lämpötilan kasvaessa lähes lineaarisesti, riippumatta paineesta. Hyvä loppuselektiivisyys saavutetaan kun ensimmäisen vaiheen selektiivisyys on hyvä. Ensimmäisessä vaiheessa saavutettiin hyvä selektiivisyys, kun alkali ei pääse kulumaan loppuun eikä delignifioituminen jatku liian pitkälle. Toisessa vaiheessa selektiivisyys säilyy parhaiten, kun lisättävä alkaliannos on pieni. Lämpötila ja paine vaikuttavat alkaliannokseen verrattuna hyvin vähän loppuselektiivisyyteen.

Implisiittisen kalibroinnin soveltamismahdollisuudet kemiantekniikassa

Työn taustalla oli tavoite parantaa erään teollisuusprosessin toimintaa ja sen tuottoa mallintamalla reaktiovaiheen alussa tapahtuvan välituotteen muodostumisen reaktiokinetiikka sekä perinteisellä tavalla että implisiittisellä kalibroinnilla. Toisena tavoitteena oli selvittää, kuinka implisiittistä kalibrointia voidaan yleisemmin hyödyntää kemiantekniikassa. Implisiittinen kalibrointi on menetelmä, jolla voidaan ratkaista jonkin teoreettisen mallin parametrit suoraan epäsuorasta mittausdatasta (esimerkiksi spektreistä) lähes kokonaan ilman off-line analyysejä. Tämän työn kirjallisuusosassa on esitetty implisiittisen kalibroinnin toimintaperiaate sekä lyhyesti FTIR-spektrometrian perusteita. Työn kokeellisessa osassa on estimoitu tutkitun välituotteen muodostumisen kineettiset parametrit sekä tavanomaisella parametriestimoinnilla että implisiittisellä kalibroinnilla. Lisäksi kokeellisessa osassa on selvitetty lyhyesti tutkitun prosessin FTIR-spektrien lämpötilariippuvuuksia ja esitetty neljä mahdollista uutta sovelluskohdetta implisiittiselle kalibroinnille. Tavanomaisella parametriestimoinnilla saatiin estimoitua varsin yksiselitteiset arvot kineettisille parametreille. Myös mallin sovitus koedataan on hyvä kolmessa kokeessa viidestä. Parametriestimointi implisiittisellä kalibroinnilla onnistui lupaavasti vaikka tulokset eivät ole aivan niin hyviä kuin tavanomaisessa parametriestimoinnissa. Parhaat tulokset implisiittisessä kalibroinnissa saavutettiin suoralla kalibrointitavalla GRR (Generalized Ridge Regression)-kalibrointimenetelmää käyttämällä.

Jäännöshiilen ja kalkkikiven reaktiokinetiikan mallinnus kiertoleijukattilan tulipesässä

Työn tavoitteena oli kehittää mallit jäännöshiilen ja kalkkikiven reaktiokinetiikan sekä jäännöshiilen jauhautumisen ennustamiseksi kiertoleijukattilan tulipesässä. Kehitetyt mallit toimivat tulipesämallin osamalleina. Perustuen mallinnettuihin reaktionopeuksiin ja jauhautumiskäyttäytymiseen tulipesämalli ennustaa kalkkikivihiukkasten rikinsidonnan ja jäännöshiilen jakautumisen erikokoisiksi hiukkasiksi tulipesässä ja tuhkissa. Työssä kehitetyt mallit perustuvat olemassa oleviin kalkkikiven ja polttoaineen reaktiivisuustesteihin laboratorio-kokoluokan leijukerrosreaktorissa. Mallit huomioivat myös tulipesän olosuhteet. Menetelmät kelpoistettiin onnistuneesti kaupallisen kokoluokan kiertoleijukattiloista mitattujen ja tulipesämallilla laskettujen taseiden avulla. Mallien kehittämistä tullaan jatkamaan.

Gas-phase photocatalytic oxidation of volatile organic compounds

Substances emitted into the atmosphere by human activities in urban and industrial areas cause environmental problems such as air quality degradation, respiratory diseases, climate change, global warming, and stratospheric ozone depletion. Volatile organic compounds (VOCs) are major air pollutants, emitted largely by industry, transportation and households. Many VOCs are toxic, and some are considered to be carcinogenic, mutagenic, or teratogenic. A wide spectrum of VOCs is readily oxidized photocatalytically. Photocatalytic oxidation (PCO) over titanium dioxide may present a potential alternative to air treatment strategies currently in use, such as adsorption and thermal treatment, due to its advantageous activity under ambient conditions, although higher but still mild temperatures may also be applied. The objective of the present research was to disclose routes of chemical reactions, estimate the kinetics and the sensitivity of gas-phase PCO to reaction conditions in respect of air pollutants containing heteroatoms in their molecules. Deactivation of the photocatalyst and restoration of its activity was also taken under consideration to assess the practical possibility of the application of PCO to the treatment of air polluted with VOCs. UV-irradiated titanium dioxide was selected as a photocatalyst for its chemical inertness, non-toxic character and low cost. In the present work Degussa P25 TiO2 photocatalyst was mostly used. In transient studies platinized TiO2 was also studied. The experimental research into PCO of following VOCs was undertaken: - methyl tert-butyl ether (MTBE) as the basic oxygenated motor fuel additive and, thus, a major non-biodegradable pollutant of groundwater; - tert-butyl alcohol (TBA) as the primary product of MTBE hydrolysis and PCO; - ethyl mercaptan (ethanethiol) as one of the reduced sulphur pungent air pollutants in the pulp-and-paper industry; - methylamine (MA) and dimethylamine (DMA) as the amino compounds often emitted by various industries. The PCO of VOCs was studied using a continuous-flow mode. The PCO of MTBE and TBA was also studied by transient mode, in which carbon dioxide, water, and acetone were identified as the main gas-phase products. The volatile products of thermal catalytic oxidation (TCO) of MTBE included 2-methyl-1-propene (2-MP), carbon monoxide, carbon dioxide and water; TBA decomposed to 2-MP and water. Continuous PCO of 4 TBA proceeded faster in humid air than dry air. MTBE oxidation, however, was less sensitive to humidity. The TiO2 catalyst was stable during continuous PCO of MTBE and TBA above 373 K, but gradually lost activity below 373 K; the catalyst could be regenerated by UV irradiation in the absence of gas-phase VOCs. Sulphur dioxide, carbon monoxide, carbon dioxide and water were identified as ultimate products of PCO of ethanethiol. Acetic acid was identified as a photocatalytic oxidation by-product. The limits of ethanethiol concentration and temperature, at which the reactor performance was stable for indefinite time, were established. The apparent reaction kinetics appeared to be independent of the reaction temperature within the studied limits, 373 to 453 K. The catalyst was completely and irreversibly deactivated with ethanethiol TCO. Volatile PCO products of MA included ammonia, nitrogen dioxide, nitrous oxide, carbon dioxide and water. Formamide was observed among DMA PCO products together with others similar to the ones of MA. TCO for both substances resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide and water. No deactivation of the photocatalyst during the multiple long-run experiments was observed at the concentrations and temperatures used in the study. PCO of MA was also studied in the aqueous phase. Maximum efficiency was achieved in an alkaline media, where MA exhibited high fugitivity. Two mechanisms of aqueous PCO – decomposition to formate and ammonia, and oxidation of organic nitrogen directly to nitrite - lead ultimately to carbon dioxide, water, ammonia and nitrate: formate and nitrite were observed as intermediates. A part of the ammonia formed in the reaction was oxidized to nitrite and nitrate. This finding helped in better understanding of the gasphase PCO pathways. The PCO kinetic data for VOCs fitted well to the monomolecular Langmuir- Hinshelwood (L-H) model, whereas TCO kinetic behaviour matched the first order process for volatile amines and the L-H model for others. It should be noted that both LH and the first order equations were only the data fit, not the real description of the reaction kinetics. The dependence of the kinetic constants on temperature was established in the form of an Arrhenius equation.

Filmes de óxidos anódicos de nióbio: efeito eletrocrômico e cinética da reação de eletro-intercalação

The aim of this work is to study the electrochromism and the reaction kinetics of lithium electrointercalation in anodic niobium oxide films. The oxide grown in an acid environment by application of an alternating potential shows interference colour (iridescence) and when reduced in lithium perclorate/PC solution, the intercalation of Li+ ions and electrons causes a reversible colour change (electrochromism), characterized here by electrochemical and optical measurements. A model where the reaction kinetics is dominated by diffusion of ionic pairs (Li+, e-) in the oxide film permitted the reproduction of current and absorbance temporal dependence, confirming the relationship between the electrochromic and electrochemical reactions. From the results obtained, a relation was established where the colour change is associated to the reduction of Nb+5 to Nb+4 ions with simultaneous cations injection.

Fischer-Tropsch Slurry Bubble Column Reactor Modeling

The literature part of the work reviews overall Fischer-Tropsch process, Fischer-Tropsch reactors and catalysts. Fundamentals of Fischer-Tropsch modeling are also presented. The emphasis is on the reactor unit. Comparison of the reactors and the catalysts is carried out to choose the suitable reactor setup for the modeling work. The effects of the operation conditions are also investigated. Slurry bubble column reactor model operating with cobalt catalyst is developed by taking into account the mass transfer of the reacting components (CO and H2) and the consumption of the reactants in the liquid phase. The effect of hydrostatic pressure and the change in total mole flow rate in gas phase are taken into account in calculation of the solubilities. The hydrodynamics, reaction kinetics and product composition are determined according to literature. The cooling system and furthermore the required heat transfer area and number of cooling tubes are also determined. The model is implemented in Matlab software. Commercial scale reactor setup is modeled and the behavior of the model is investigated. The possible inaccuraries are evaluated and the suggestions for the future work are presented. The model is also integrated to Aspen Plus process simulation software, which enables the usage of the model in more extensive Fischer-Tropsch process simulations. Commercial scale reactor of diameter of 7 m and height of 30 m was modeled. The capacity of the reactor was calculated to be about 9 800 barrels/day with CO conversion of 75 %. The behavior of the model was realistic and results were in the right range. The highest uncertainty to model was estimated to be caused by the determination of the kinetic rate.

Modeling of Gold Cyanidation

The chemistry of gold dissolution in alkaline cyanide solution has continually received attention and new rate equations expressing the gold leaching are still developed. The effect of leaching parameters on gold gold cyanidation is studied in this work in order to optimize the leaching process. A gold leaching model, based on the well-known shrinking-core model, is presented in this work. It is proposed that the reaction takes place at the reacting particle surface which is continuously reduced as the reaction proceeds. The model parameters are estimated by comparing experimental data and simulations. The experimental data used in this work was obtained from Ling et al. (1996) and de Andrade Lima and Hodouin (2005). Two different rate equations, where the unreacted amount of gold is considered in one equation, are investigated. In this work, it is presented that the reaction at the surface is the rate controlling step since there is no internal diffusion limitation. The model considering the effect of non-reacting gold shows that the reaction orders are consistent with the experimental observations reported by Ling et al. (1996) and de Andrade Lima and Hodouin (2005). However, it should be noted that the model obtained in this work is based on assumptions of no side reactions, no solid-liquid mass transfer resistances and no effect from temperature.

Sinkkirikasteen liukenemisnopeuteen vaikuttavat tekijät ja sinkkirikasteen suoraliuotuksen mallintaminen

Työn kirjallisuusosassa selvitettiin eri tekijöiden (lämpötila, paine, mineralogia, partikkelikoko, sekoitus, kiintoainepitoisuus, liuoksen happo-, rauta- ja happipitoisuus) vaikutusta sinkkirikasteen suoraliuotusprosessin tärkeimpiin ilmiöihin (diffuusio, aineensiirto, reaktiokinetiikka). Kirjallisuusosassa kartoitettiin myös tämän hetkistä tietämystä niistä tekijöistä, jotka ovat oleellisia, kun sinkkirikasteen suoraliuotusprosessia mallinnetaan. Näitä tekijöitä ovat: sinkkirikasteiden liuotuksen kemia, sinkkirikasteiden liuotuksen kinetiikka ja mekanismit, kaasuneste aineensiirto ja kiinteäneste aineensiirto. Lisäksi selvitettiin millä tavoin aikaisemmissa tutkimuksissa sinkkirikasteiden suoraliuotusta on mallinnettu. Mallinnusosassa käsiteltiin atmosfääristä sinkkirikasteen suoraliuotusta, jossa hapettimena toimi ferri(III)rauta. Mallintamisessa käytettiin kirjallisuudessa esitettyjä mittaustuloksia ja mallintaminen tehtiin Modest tietokoneohjelmistolla. Työssä tehty atmosfäärisen suoraliuotuksen mallintaminen labo-ratoriomittakaavassa (laimeat liuokset ja pienet kiintoainepitoisuudet) antoi lupaavia tuloksia. Ongelmia mallin ennustuksen kanssa esiintyi pienissä happopitoisuuksissa, alhaisissa lämpötiloissa sekä pienillä ja suurilla partikkeleilla. Työn kirjallisuusosassa tunnistettiin ne ongelmakohdat, jotka vaativat lisätutkimuksia, jotta sinkkirikasteen atmosfääriselle suoraliuotukselle pystytään kehittämään simulointimalli. Näitä ovat: 1. Hapen liukoisuus ja aineensiirto teollisuuden käyttämissä sinkkirikastelietteissä, 2. Sopivien mittaustulosten puuttuminen, jotta atmosfääristä suoraliuotusta, jossa O2 ja Fe3+ toimivat hapettimena voitaisiin mallintaa, 3. Kiinteäneste aineensiirron merkitys sinkkirikasteen suoraliuotuksessa. Mallinnusosassa osoitettiin, että mekanistisella mallintamisella voidaan simuloida sinkkirikasteen atmosfääristä suoraliuotusta ainakin laboratoriomittakaavassa. Työn perusteella voidaan todeta, että sinkkirikasteen atmosfääriselle suoraliuotukselle voidaan työssä ehdotettujen jatkotutkimusten avulla kehittää numeerinen mekanistinen malli, jolla atmosfääristä sinkkirikasteiden suoraliuotusprosessia voidaan simuloida eri olosuhteissa.

Hidrólise parcial da superfície do polyethylene terephthalate (PET): transformando um rejeito em um material de troca catiônica para aplicação ambiental

In this work it is proposed a simple and versatile undergraduate chemical experiment in polymer and environmental technology based on the process of polyethylene terephthalate (PET) hydrolysis. Polyethylene terephthalate from post-consume bottles is submitted to a controlled partial hydrolysis which allows the students to follow the reaction by a simple procedure. The students can explore the reaction kinetics, the effect of catalysts and the exposed polyethylene terephthalate surface area on the hydrolysis reaction. The second and innovative part of this experiment is the technological and environmental application of the hydrolyzed polyethylene terephthalate as a material with cation exchange properties. The surface hydrolyzed polyethylene terephthalate can be used as adsorbent for cationic contaminants.

Sistema RTP: uma técnica poderosa para o monitoramento da formação de nanotubos de carbono durante o processo por deposição de vapor químico

In this work, a TPR (Temperature Programmed Reduction) system is used as a powerful tool to monitor carbon nanotubes production during CVD (Chemical Vapour Deposition), The experiments were carried out using catalyst precursors based on Fe-Mo supported on Al2O3 and methane as carbon source. As methane reacts on the Fe metal surface, carbon is deposited and H2 is produced. TPR is very sensitive to the presence of H2 and affords information on the temperature where catalyst is active to form different forms of carbon, the reaction kinetics, the catalyst deactivation and carbon yields.