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En av de vanligaste föroreningarna i mark och grundvatten är aromatiska kolvä- ten såsom bensen, toluen, etylbensen och xylener. Dessa härstammar från ex. ben- sin och har läckt ut till omgivande miljö från drivmedelsanläggningar. I stället för schaktning och bortforsling av de förorenade jordmassorna som mest förekom- mande ex situ-saneringsmetod behövs mer forskning kring in situ-saneringsmetoder där föroreningen alltså kan angripas på plats. I denna rapport undersöks förhöjd biologisk nedbrytning genom att redogöra för de önskvärda (bio)kemiska reak- tionerna i marken, de parametrar som styr den biologiska nedbrytningen samt huruvida dessa parametrars inverkan har kunnat påvisas i tre stycken fallstu- dier där in situ-sanering utförts vid drivmedelsanläggningar. Studien kommer fram till ett antal primära (ursprungliga) variabler såsom föroreningen i fråga, jordtätheten och klimatet, samt ett antal sekundära (förändringsbara) variabler såsom oxidationsmedlet, mikroorganismerna, näringsämnena och markvattnet. Dessa presenterades sedan i en schematisk skiss som visar hur de växelverkar med parametrarna för optimal biologisk nedbrytning, vilka visade sig ha vissa optimala värden. Dessa konstaterades vara föroreningshalten (<5-10 viktprocent torr jord), pH-värdet (6-9), temperaturen (20-35◦C), vattenmättnaden (40-80%), syrehalten (> 2 500 viktprocent kolväten), C:N:P-kvoten (100:10:1) samt koncent- rationen mikroorganismer (> 103 CFU/ml). När de olika parametrarnas inverkan  i fallstudierna undersöktes kunde slutsatsen dras att det skulle behövas ytterliga- re data och mätningar vid varje sanering för att kunna garantera att parametrarna varit inom sina respektive optimala värden. / One of the many goals for a sustainable living and a healthy environment is the reduction of toxic substances in soil and groundwater. Within this ambit, one of the most common pollutants is aromatic hydrocarbons such as benzene, tolue- ne, ethylbenzene and xylenes (BTEX) which are spread from e.g. filling stations for fuel as they are constituents of petrol. These are volatile and can constitute a risk for humans and the environment as they percolate through the soil and groundwater resources as well as can exfiltrate from the ground to surrounding buildings and pollute the indoor air. Once these pollutants are present in the soil, the site needs to be remediated, something which is mainly done ex situ by exca- vating the polluted masses to be sent to a treatment facility. An alternative to this is in situ remediation where the pollution can be treated without being excavated and thus having a smaller impact on the environment.  In this report, one of these techniques called enhanced biodegradation was studied, which implies the application of oxidisers to faciliate microbial activities. It investigated (1) how this remediation technique works and what (bio)chemical reactions are desired in the soil; (2) what are the principal parameters that enable this remediation process and how do they interact with the surrounding factors, and (3) whether the impact of these parameters can be estimated in three case studies where this technique has been used. The three case studies were filling stations located in Sweden, having similar pollutants and geology, and two diffe- rent oxidisers had been used.  The study resulted in the identification of a number of primary (initial) varia- bles such as the pollutant characteristics, the soil density and the climate; as well as a number of secodnary (modifiable) variables such as the oxidiser, microorga- nisms, nutrients and soil moisture. These were then presented in a scheme which shows how their interactions with the parameters for optimal biodegradation. Each parameter was found to have a certain optimum such as the concentration of hydrocarbons (<5-10 mass percent of the dry soil) , pH value (6-9), tempe- rature (20-35◦C), soil water saturation (40-80%), oxygen concentration (> 2,500 mass percent of the hydrocarbons), C:N:P ratio (100:10:1) as well as concentration of microorganisms (> 103 CFU/ml). A negative correlation could be identified between the soil density and the oxygen concentration in the soil, as well as a po- sitive correlation between the soil water saturation in the and the soil moisture, alternatively additional water via irrigation. The impact of each parameter in the case studies of in situ remediation was assessed and the it could be concluded that they would need additional data and measurements for most parameters in order to guarantee that they are within the respective optima.

<p dir="ltr">Zeolites are microporous crystalline aluminosilicates that are widely used as catalysts for upgrading hydrocarbons and oxygenates to higher value chemicals and fuels. The substitution of tetrahedral Si⁴⁺ with Al³⁺ in a charge-neutral silica framework ([SiO_4/2]) generates anionic centers ([AlO_4/2]^-), which charge-compensate Brønsted acid protons (H⁺) that serve as active sites for catalysis. Brønsted acid sites in aluminosilicates of diverse topologies have similar acid strength, but can be located within varying intracrystalline (or internal) microporous environments (0.4‒2 nm diameter) or at extracrystalline (or external) surfaces and mesoporous environments (>2 nm diameter); yet, catalytic diversity exists, <i>even</i> for a fixed zeolite framework topology, because micropores impose constraints on molecular access to and from intracrystalline active sites and provide van der Waals contacts that influence the stabilities of reactive intermediates and transition states. Tailoring the material properties of a given zeolite framework for targeted catalytic applications requires strategies to design both the bulk crystallite properties (e.g., morphology, active site density) that influence intracrystalline diffusion and the secondary environments that surround active sites and influence intrinsic kinetics, and further necessitates molecular-level insights to elucidate the influences of bulk and active site properties on catalysis. In this work, we provide synthetic and post-synthetic strategies to respectively tune active site environments within varying micropore voids and at external surfaces of zeolites, and develop gas-phase toluene methylation and liquid-phase mesitylene benzylation as probe reactions to quantify the catalytic consequences of active site environments on aromatic alkylation catalysis.</p><p dir="ltr">The MFI framework (orthorhombic phase) consists of 12 crystallographic distinct tetrahedral-sites and 26 unique framework oxygen atoms located around channels (~0.55 nm diameter) or channel intersections (~0.70 nm diameter). The synthesis of MFI zeolites using the conventional tetra-<i>n</i>-propylammonium (TPA⁺) organic structure directing agent (OSDA) is known to place framework Al and their attendant H⁺ sites within the larger intersection environments, because electrostatic interactions are favorable between such locations of [AlO_4/2]^- and the quaternary N⁺ center in TPA⁺ that becomes positioned rigidly within channel intersections during crystallization. The methylation of toluene by dimethyl ether (DME; 403 K) on MFI-TPA zeolites of fixed active site densities (~2 Al per unit cell) result in <i>ortho</i>-xylene (<i>o</i>-X; ~65%) as the major product over <i>para</i>-xylene (<i>p</i>-X; ~27%) and <i>meta</i>-xylene (<i>m</i>-X; ~8%). In contrast, toluene methylation on MFI zeolites (~2 Al per unit cell) synthesized using non-conventional OSDAs, such as ethylenediamine (EDA) or 1,4-diazabicyclo[2.2.2]octane (DABCO), predominantly forms <i>p</i>-X (~75%) over <i>o</i>-X (~23%) and <i>m</i>-X (~2%). Within the subsets of MFI-TPA and MFI-EDA/DABCO zeolites, measured xylene formation rates and isomer selectivities are independent of crystallite sizes (0.1‒13 µm), toluene conversions (0.02‒2.0%) and external H⁺ content (up to 9% external H⁺ per total Al), indicating negligible effects of diffusion-enhanced secondary xylene isomerization reactions at intracrystalline or extracrystalline domains. The invariance of xylene isomer selectivity with reactant pressures (0.2‒9 kPa toluene, 25‒66 kPa DME) or methylating agent (1‒4 kPa methanol) indicate that differences in reactivity of toluene to form each xylene isomer reflects differences in the stabilities of their respective kinetically relevant transition states that share the same reactive intermediate. Measured xylene isomer formation rate constants and rate constant ratios, obtained from mechanism-derived rate expressions and interpreted using transition state theory formalisms, are used alongside density functional theory (DFT) calculations to reveal that intersection void environments (~0.70 nm diameter) similarly stabilize all three xylene transition states over unconfined surfaces (>2 nm diameter) without altering the established aromatic substitution patterns, while channel void environments (~0.55 nm diameter) preferentially destabilize bulkier <i>o</i>-X and <i>m</i>-X transition states thereby resulting in high intrinsic <i>p</i>-X selectivity. DFT calculations reveal that the ability of protonated DABCO complexes to reorient within MFI intersections and participate in additional hydrogen-bonding interactions with anionic Al centers during synthesis, facilitates the placement of Al in smaller channel environments that are less favored by TPA⁺. These molecular-level details, enabled by combining synthesis, characterization, kinetics and DFT, establish a mechanistic link between OSDA structure, active site placement and transition state stability, and provide active site design strategies orthogonal to crystallite design approaches that rely on complex reaction-diffusion phenomena.</p><p dir="ltr">For various reactions including toluene methylation at higher reaction temperatures (573‒773 K) and toluene conversions (>10%), extracrystalline H⁺ sites in MFI zeolites are reported to influence reactivity, selectivity, and deactivation behavior during catalysis in undesired ways. Post-synthetic chemical treatments to passivate external H⁺ sites on MFI zeolites result in unintended (but not always undesirable) changes to bulk structural properties and Al and H⁺ contents. The number of extracrystalline H⁺ sites is difficult to quantify using conventional spectroscopic or titrimetric methods, especially when present in dilute amounts on samples whose surfaces have been passivated. The systematic treatment of MFI zeolites (2.4, 5.7 and 7.1 Al per unit cell) using ammonium hexafluorosilicate (AHFS) at varying treatment duration times, AHFS concentrations and number of successive treatments resulted in MFI zeolites that retain their bulk structural properties and total Al and H⁺ contents, except for one parent MFI sample containing a significant amount of non-framework Al species. The benzylation of mesitylene by dibenzyl ether (363 K) occurs exclusively at external H⁺ sites because the bulky 1,3,5-trimethyl-2-benzylbenzene product is sterically prevented from forming at intracrystalline H⁺ sites. The intrinsic zero-order rate constant (per external H⁺) for mesitylene benzylation is extracted from rate measurements (per total Al) on a suite of untreated MFI samples with known amounts of external H⁺ sites (1‒15% external H⁺ per total Al) quantified using bulky 2,6-di-<i>tert</i>-butylpyridine base titrants. Measured zero-order rate constants on AHFS-treated MFI zeolites are used to quantify the extent to which AHFS treatments passivate external H⁺ sites, revealing efficacies that depend on the specific treatment conditions and the parent sample used. The developed kinetic methods demonstrate the utility of catalytic probes, when compared to stoichiometric probes based on spectroscopic or titration methods, in amplifying and quantifying dilute concentrations of external H⁺ sites on zeolites. The methods enable comparisons of the efficacy of various post-synthetic passivation strategies and permit rigorous assessments of the influence of external H⁺ during acid catalysis.</p><p dir="ltr">Overall, this work provides (post-)synthetic strategies to tune active site environments within intracrystalline micropores or at extracrystalline surfaces and develops quantitative kinetic probes that enable a molecular-level understanding of catalytic consequences of active site environments on aromatic alkylation reactions. Taken together, the methodology and findings of this study have broader implications in zeolite catalyst design for selectively upgrading traditional fossil feedstocks (crude oil and shale gas) and emerging feedstocks (biomass and waste plastics).</p>

Cette étude vise à mieux comprendre les réactions impliquées dans le craquage thermique des huiles en basins sédimentaires. Des pyrolyses d'octane, de toluène et de mélanges octane/toluène ont été effectuées entre 330°C et 450°C et des pressions allant de 1 bar à 700 bar. Le mécanisme radicalaire développé permet de rendre compte de l’influence de la température et de la pression sur la distribution des produits ainsi que sur la conversion jusqu'aux conditions de gisement (200°C, 150-1000 bar). Les pyrolyses du toluène pur et du mélange octane/toluène ont permis de modéliser le rôle inhibiteur des alkylaromatiques sur le craquage des hydrocarbures. Cette étude démontre l'importance des co réactions et donc de la composition des huiles sur la stabilité thermique des pétroles en gisements / This study aims at a better understanding of the reactions involved in the thermal cracking of oil within sedimentary basins. Pyrolysis of octane, toluene and mixtures of octane / toluene were performed between 330°C and 450°C and at pressures going from 1 bar to 700 bar. The constructed radical mechanism allows to report the influence of temperature and pressure on the distribution of products as well as the conversion from laboratory to reservoir conditions (200°C, 150-1000 bar). The pyrolysis of pure toluene and the octane / toluene mixture allowed to model the inhibition effect of alkylaromatics on the cracking of hydrocarbons. This study demonstrates the importance of co reactions and thus the composition of oil on the thermal stability of petroleums in reservoirs

La métrologie laser basée sur l’analyse de la fluorescence de traceurs moléculaires est devenue l’un des outils clefs pour l’étude expérimentale de la dynamique des fluides réactifs. Une étude spectroscopique des propriétés photophysiques de fluorescence dans le domaine spectral UV-visible de plusieurs molécules fluorescentes appartenant aux cétones aliphatiques et aux aromatiques mono- et bicycliques a permis d’approfondir la compréhension de l’influence de la température, de la pression et de la concentration d’oxygène sur leur fluorescence. Les résultats expérimentaux obtenus ont ensuite permis le développement d’un modèle de simulation du rendement de fluorescence pour les espèces aromatiques (naphtalène et toluène), qui fournit des résultats très proches de ceux mesurés.De ces résultats, le développement de la technique d’imagerie de fluorescence (PLIF) sur la phase vapeur d’un carburant multi-composant a conduit à étendre cette analyse spectrale de fluorescence au cas du kérosène (Jet A-1). La comparaison entre les propriétés de fluorescence du kérosène et des traceurs aromatiques étudiés a notamment permis d’établir une stratégie de mesure de la concentration de la phase vapeur du kérosène dans des environnements où la teneur en oxygène est variable. Les signaux de fluorescence provenant des espèces mono- et di-aromatiques contenues dans le kérosène soulignent des évolutions différentes avec les conditions de température et teneur en oxygène. L’utilisation de filtres optiques appropriés associés à deux caméras ICCD permet alors une mesure bidimensionnelle de la température et de la concentration de kérosène en phase vapeur. La thèse débouche finalement sur l’application de cette technique PLIF-kérosène en combinaison avec la technique PLIF du radical OH en sortie d’un système d’injection industriel multi-point de nouvelle génération intégré dans une chambre de combustion haute pression. / Planar laser-induced fluorescence (PLIF) diagnostic based on the optical excitation of fluorescence tracers has become a key tool for the experimental study of fluid dynamics in reactive flows. A spectroscopic fluorescence study of several organic molecules from aliphatic ketones and mono- and bi-cyclic aromatics in gas-phase was performed in a high-pressure high temperature optical cell. The experimental measurements allowed the understanding of the influence of temperature, pressure and oxygen concentration on the photophysics of these molecules in the UV/visible domain. These results were then used to successfully develop a model of fluorescence yield of the naphthalene and toluene aromatic molecules permitting the simulation of the fluorescence signals with temperature, pressure and species composition in large domains of temperature and pressure.This study has been extended to the case of a multi-component aeronautical fuel (kerosene – jet A1) containing natural aromatics. The comparison of the spectroscopic data recorded in the optical cell to those of the aromatic tracers initially probed has then permitted the definition of a kerosene-PLIF excitation/detection strategy for kerosene vapour concentration measurements in reactive gaseous flowfield containing variable oxygen concentration. Fluorescence signals from mono- and di-aromatic species in kerosene highlight significant differences in evolution with temperature and oxygen concentration. With appropriate optical filters applied to two ICCD cameras, the two-dimensional instantaneous distribution of temperature and concentration of kerosene vapour is then possible to measure in reactive flows. Finally, the kerosene-PLIF diagnostic has been applied at the exit of an innovative multi-point aeronautical injection system integrated to high-pressure kerosene/air combustor test rig. The kerosene-PLIF, combined with the radical OH-PLIF confirmed their implementation in realistic high-pressure flowfields and delivered experimental fruitful experimental information on the effect of the fuel/air mixing on the flame structure in the combustion chamber.

This thesis is concerned with the development and application of laser induced thermal grating spectroscopy (LITGS) as a tool for thermometry in reacting and non-reacting flows. LITGS signals, which require resonant excitation of an absorbing species in the measurement region to produce a thermal grating, are acquired for systematic measurements of temperature in high pressure flames using OH and NO as target absorbing species in the burned gas. The signal obtained in LITGS measurements appears in the form of a time-based signal with a characteristic frequency proportional to the value or the sound speed of the local medium. With knowledge of the gas composition, the temperature can be derived from the speed of sound measurement. LITGS thermometry using resonant excitation of OH in the burned gas region of in oxygen enriched CH4/O2/N2 and CH4/air laminar flames was performed at elevated pressure (0.5 MPa) for a range of conditions. Measurements were acquired in oxygen enriched flames to provide an environment in which to demonstrate LITGS thermometry under high temperature conditions (up to 2900 K). The primary parameters that influence the quality of LITGS signal were also investigated. The signal contrast, which acts as a marker for the strength of the frequency oscillations, is shown to increase with an increase in the burnt gas density at the measurement point. LITGS employing resonant excitation of NO is also demonstrated for quantitative measurements of temperature in three environments – a static pressure cell at ambient temperature, a non-reacting heated jet at ambient pressure and a laminar premixed CH4/NH3/air flame operating at 0.5 MPa. Flame temperature measurements were acquired at various locations in the burned gas close to a water-cooled stagnation plate, demonstrating the capability of NO-LITGS thermometry for measuring the spatial distribution of temperature in combustion environments. In addition, the parameters that in influence the local temperature rise due to LITGS were also investigated in continuous vapour flows of acetone/air and toluene/air mixtures at atmospheric conditions. Acetone and toluene are commonly targeted species in previous LITGS measurements due to their favourable absorption characteristics. Results indicate that LITGS has the potential to produce accurate and precise measurements of temperature in non-reacting flows, but that the product of the pump intensity at the probe volume and the absorber concentration must remain relatively low to avoid significant localised heating of the measurement region.

Les carbones poreux ont été largement utilisés et étudiés ces dernières années. Ce travail de recherche porte sur la préparation de matériaux carbonés mésoporeux modifiés ou non par de l'azote. Tout d'abord, un carbone mésoporeux pur a été synthétisé. Puis des atomes d'azote ont été introduits dans ce carbone mésoporeux par deux méthodes de dopage ("in situ" et "post-synthèse" respectivement). La comparaison des propriétés acido-basiques dans des conditions différentes pour les trois types de matériaux mésoporeux carbonés, avec ou sans diazote, a été faite grâce à des techniques calorimétriques. Ces carbones mésoporeux ont aussi été utilisés dans l'adsorption de polluants, le stockage de l'hydrogène et en tant que supports pour les métaux précieux et l'oxyde de fer en catalyse. Les différentes performances dans ces applications ont été mises en relation avec les différentes propriétés structurelles et surfaciques causées par le dopage au diazote / Porous carbon materials are widely used and studied in recent years. In this work, three kinds of mesoporous carbon materials were prepared. Firstly, cost-effective pure mesoporous carbon was synthesized. Then nitrogen atoms were introduced into the mesoporous carbon by “in situ” and “post” doping methods respectively. The comparisons of the acid-base properties in different conditions of the three kinds of mesoporous carbon materials with or without nitrogen were studied and revealed by different calorimetric techniques. The three kinds of mesoporous carbons were also applied in pollutants adsorption, hydrogen storage and as supports of precious metals and iron oxide in catalysis. The different performances in applications were related to the different structural and surface properties caused by the N-doping

The diploma thesis is focused on a detection and a laboratory control of hazardous substances’ leak into the environment. These hazardous substances are classified. Further, it aims to chemical laboratories of the fire-brigade of the Czech Republic, as well as which place they hold in the fire-brigade system, and it indicates their main duties. This diploma thesis contains a review of some essential types of devices and mediums, which are in terms of the fire-brigade of the Czech Republic usable to practice the detection, determination and assessment of the hazardous substances in various figures of the environment in terrain, i.e. filling of duties of the chemical survey. The output of this diploma thesis is simulation of leaks of the toluene diisocyanate using ALOHA software, TerEx software and Rozex Alarm software. Further on, the proposal of another methodical sheet focused on leak actions of the concrete hazardous industrial substance – toluene diisocyanate. This methodical sheet could therefore broaden pro tempore elaborated sheets for chlorine and ammonia.

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