<p>Catalytic combustion is an environmentally benign technologywhich has recently reached the stage of commercialization.Palladium is the catalyst of choice when considering gasturbines fuelled with natural gas because of its superioractivity for methane oxidation. Several fundamental issues arestill open and their understanding would result in animprovement of the technology. Hence, the work presented inthis thesis aims at the identification of some of theparameters which govern the combustion activity ofpalladium-based catalysts.</p><p>The first part of this work gives a background to catalyticcombustion and a brief comparison with other existingtechnologies. Paper I reviews some of the issues related tomaterial development and combustor design.</p><p>The second part of this thesis consists of an experimentalinvestigation on palladium-based catalysts. The influence ofthe preparation method onthe properties of these catalystmaterials is investigated in Paper II. Paper III examines theactivity of the following catalysts: Pd/Al2O3, Pd/Ba-Al2O3 andPd/La-Al2O3. Specific attention is given to the metal-supportinteraction which strongly affects the combustion activity ofpalladium. The effect of doping of the support by addition ofcerium is reported in Paper IV.</p><p>Finally, the deactivation of combustion catalysts isconsidered. The various deactivation processes which may affecthigh temperature combustion catalysts are reviewed in Paper V.Paper VI focuses on the poisoning of supported palladiumcatalysts by sulphur species. Palladium exhibits a higherresistance to sulphur poisoning than transition metals.Nevertheless, the nature of the support material plays animportant role and may entail a severe loss of activity whensulphur is present in the fuel-air mixture entering thecombustion chamber.</p><p><b>Keywords</b>: catalytic combustion, gas turbine, methane,palladium, alumina, barium, lanthanum, oxidation, preparation,temperature-programmed oxidation (TPO), decomposition,reoxidation, X-ray photoelectron spectroscopy (XPS),metal-support interaction, deactivation, sulphur, poisoning.The cover illustration is a TEM picture of a 100 nm palladiumparticle supported on alumina</p>

Roofing foils are known for several years as building material for roof hydro insulation but their life service is not yet fully known. This thesis is focused on problematics of life service of roofing foils. In theoretical part there is discribed structure of foils and impacts which assist degradation processes. Practical part modifies the methodology artificial aging which is simulated in QUV tester and Q-SUN XE3 tester lumber-rooms. The thesis is trying reach with the results to natural aging as close as possible. The testing captures attributes which are more prone to degradation.

Catalytic combustion is a promising combustion technique in gas turbines, which results in ultra low levels of NOx, CO and unburned hydrocarbons. Due to the low combustion temperature achieved in catalytic combustion almost no thermal NOx is formed. The focus in this thesis will be on the first stage in a catalytic combustion chamber, i.e. the ignition catalyst. The catalyst used for this application is often a supported palladium-based catalyst due to its excellent activity for methane combustion. However, this type of catalyst has a serious drawback; the methane conversion decreases with time during operation. The unstable activity will result in increasing difficulties to ignite the fuel. The objective of the work presented in this thesis has been to improve the catalytic performance of supported palladium catalysts, with focus on stabilizing the methane conversion. The first part gives a general background to gas turbines and catalytic combustion. The second part concerns the monometallic palladium catalysts; their behaviour during methane combustion is addressed. The third part describes different bimetallic catalysts, which all have palladium as one of the active components. Results from the activity tests of methane combustion showed that it is possible to stabilize the activity by adding certain co-metals into the palladium catalyst. The morphology of the various bimetallic catalysts has been studied to gain a better understanding of the various combustion behaviours. Finally, the influence of pressure on the catalytic performance is evaluated. The catalysts were tested under more realistic conditions for gas turbines, with elevated pressure, in a high-pressure test facility with a 100 kW fuel power.

京都大学 / 0048 / 新制・論文博士 / 博士(医学) / 乙第13159号 / 論医博第2146号 / 新制||医||1029(附属図書館) / (主査)教授 河本 宏, 教授 前川 平, 教授 髙折 晃史 / 学位規則第4条第2項該当 / Doctor of Medical Science / Kyoto University / DFAM

Heavy-duty diesel truck engines are routinely idled at standstill to provide cab heating or air conditioning, and in addition to supply electricity to comfort units such as radio and TV. Idling is an inefficient and unfavorable process resulting in increased fuel consumption, increased emissions, shortened engine life, impaired driver rest and health, and elevated noise. Hydrogen-fueled, polymer-electrolyte fuel-cell auxiliary power unit (PEFC-APU) as a silent external power supply, working independently of the main engine, is proposed as viable solution for better fuel economy and abatement of idling emissions. In a diesel PEFC-APU, the hydrogen storage problem is circumvented as hydrogen can be generated onboard from diesel by using a catalytic reformer. In order to make catalytic diesel PEFC-APU systems viable for commercialization research is still needed. Two key areas are the development of reforming catalyst and reformer design, which both are the scope of this thesis. For diesel-reforming catalysts, low loadings of Rh and RhPt alloys have proven to exhibit excellent reforming and hydrogen selectivity properties. For the development of a stable reforming catalyst, more studies have to be conducted in order to find suitable promoters and support materials to optimize and sustain the long-term performance of the Rh catalyst. The next step will be full-scale tests carried out at realistic operating conditions in order to fully comprehend the overall reforming process and to validate promising Rh catalysts. This thesis can be divided into two parts; the first part addresses the development of catalysts in the form of washcoated cordierite monoliths for autothermal reforming (ATR) of diesel. A variety of catalyst compositions were developed containing Rh or RhPt as active metals, CeO2, La2O3, MgO, Y2O3 as promoters and Al2O3, CeO2-ZrO2, SiO2 and TiO2 as support materials. The catalysts were tested in a bench-scale reactor and characterized by using N2-BET, XRD, H2 chemisorption, H2-TPR, O2-TPO, XPS and TEM analyses. The second part addresses the development and testing of full-scale reformers at various realistic operating conditions using promising Rh catalysts. The thesis shows that a variety of Rh on alumina catalysts was successfully tested for ATR of diesel (Papers I-IV). Also, zone-coating, meaning adding two washcoats on specific parts of the monolith, was found to have beneficial effects on the ATR catalyst performance (Paper II). In addition, RhPt supported on CeO2-ZrO2 was found to be one of the most active and promising catalyst candidates for ATR of diesel. The superior performance may be attributed to higher reducibility of RhiOx species and greater dispersion of Rh and Pt on the support (Paper IV). Finally, two full-scale diesel reformers were successfully developed and proven capable of providing high fuel conversion and hydrogen production from commercial diesel over selected Rh catalysts (Papers II-III, V-VI). / QC 20110418

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The work described in this thesis focuses on the effects that adsorption processes on catalytic surfaces pose in controlling key steps that can affect and control reaction pathways. To that, the development of Nuclear Magnetic Resonance (NMR) relaxometry methods and the comparison with traditional catalytic was performed with a series of C5 and C6 unsaturated hydrocarbons on two different alumina supports, γ- and θ-Al2O3. The developed techniques were applied in the study of liquid phase selective hydrogenation of citral on 5% Pt/SiO2. Infrared (IR) spectroscopy, volumetric adsorption isotherms, dynamic isotherms via a Tapered Element Oscillating Microbalance (TEOM), temperature programmed desorption (TPD) as well as 13C T1 NMR and 1H 2D T1-T2 relaxometry methods were employed. Energies of adsorption as a function of coverage were obtained via adsorption isotherms and the particular surface adsorbate interactions were described with IR spectroscopy. For example, 1-pentyne showed the strongest interaction with the alumina (94 kJ mol-1) while 1-pentene presented a weaker interaction (46 kJ mol-1) on θ-Al2O3. Desorption energies obtained from TPD ranged 85 – 130 kJ mol-1, irrespective of the adsorbate. Reactivity of the aluminas was captured with TPD, TEOM and NMR relaxometry. Interaction of adsorbates with hydrocarbon occurred predominantly on weak adsorption sites. 13C NMR T1 relaxometry provided in addition atom-specific adsorbate-adsorbent interaction strengths, showing the molecular geometry of adsorption, and applied in co adsorption measurements. The selective hydrogenation of citral as a model α,β-unsaturated aldehyde and the effect of different solvents on the activity and product distribution was studied at 298 and 373 K. A series of polar protic, polar aprotic and non polar solvents was investigated. Results showed higher initial reaction rates in non polar solvents but higher selectivities towards desired products on polar protic solvents. Solvent used also affected by product formation. The strong variations in reaction rates and selectivities reported were related with adsorbate catalyst interactions, as well as solvent reactant interactions. For example, adsorption isotherms showed that ethanol notably reduced the adsorption capacity of citral as compared with hexane, related with the rate differences observed. ATR-IR measurements indicated solvent citral interactions were solely present in polar protic solvents in line with higher yields of geraniol and nerol. Finally, 13C T1 NMR and 1H 2D T1-T2 correlation experiments determined that the geometry of adsorption of citral, influenced by solvent, affected product selectivity, and that product adsorption affected selectivity and deactivation.

(ENGLISH) Hematopoiesis is dependent on the actions of hematopoietic stem cells (HSCs). This process is tightly controlled through a complex array of extrinsic and intrinsic factors. Even though the hematopoiesis seems to be well conserved across the disparate vertebrate animals, erythroid and thrombocytic differentiation have changed during the evolution of mammals. Specifically, adult mammalian red blood cells have the unique feature of being enucleated, and mammalian thrombocytes are not individual cells, but fragments of megakaryocytes, instead. It is likely that these enhancements provided a survival advantage to early mammalian species; however, they also bring up the question of evolutionary origin of these cells that studied using zebrafish (Danio rerio) model. First, it was necessary to generate a toolbox of a recombinant cytokines and optimized culture media that allowed us to manipulate zebrafish hematopoietic cells ex vivo in liquid and clonal cultures. Interestingly, teleost species underwent an extra duplication event during their evolution and as a result, two copies (paralogs) of some of the genes are present in zebrafish. This was also the case for majority of the cytokines from our toolbox and here, we provide functional characterization of these paralogs. Strikingly, our results...

This master's thesis deals with the comparison of export support systems in the Czech Republic and Austria. In the first chapter, the terms "export support" and "export credit agencies" are defined and instruments of export supporting policies as well as their positive and negative aspects are listed and EU regulation and policies in this field are briefly described. A short description of the Czech Republic and Austria follows. Special attention is paid to the following analysis of export strategies and export credit agencies in both economies. This descriptive theoretical part is complemented by a practical case study carried out in cooperation with TOSHULIN, a.s. -- a successful producer and exporter of machinery. Both systems of export support are evaluated from the point of view of the company's sales department. The thesis concludes with an evaluation of the topic, a comparison of the effectiveness of both export support systems, and the author's suggestions for potential innovation and improvement in this area.