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Advanced gas cooled nuclear reactors (AGRs) contain a range of alloys, selected for their physical and chemical performance in the conditions present. Carbon deposition on boiler and fuel pin heat transfer surfaces affects a reactor's efficiency and may necessitate downrating to maintain safety margins. This is believed to arise from decomposition of some of the coolant gas constituents. Deposition minimisation, while maintaining the structural integrity of the reactor, is technologically and economically important. This study has looked at deposition on a range of transition metal spinels, manganese oxides, uranium oxides and single crystal magnetite samples with a view to furthering knowledge of catalytic reactions that may occur within an AGR. In particular, the effect of mixed valency on deposition rates was studied. The spinels were successfully prepared by solid state reactions between the relevant oxides, oxalates and I or carbonates. A range of elemental and chemical analytical techniques were used to characterise the samples both before and after exposure under controlled gas and radiological conditions. Deposition was induced, to varying extents, on all the samples exposed. No filamentary deposits were observed. The spinels gave quantities of deposition in the order: Manganese spinels gave increasing deposition with increasing manganese content at 650°C, but decreasing deposition at 550°C. Iron-cobalt spinels showed no consistent increase or decrease in carbon deposition with changing composition. Nickel rich spinels were unstable in the reaction gas mixture and generated metallic nickel during exposure. At both temperatures, this gave levels of carbon deposition which increased with increasing nickel content of the original oxide. NiF~04 exposed at 550°C fragmented as it catalysed carbon formation. Manganese oxides converted to MnO during exposure, MnO proving also to be a most effective catalyst. Mn304' an Mn2+ I Mn3+ compound where the manganese ions do not form an electron exchanging octahedrally coordinated pair, did not yield large quantities of deposit. The uranium oxides examined converted to the interacting mixed valence U409' which gave copious carbon deposition. The U4+ I U6+ non interacting mixed valence Ot-U30 S gave the least deposition. Magnetite slices gave laminar carbon deposits, but no filamentary growth. Structured deposit was seen in two cases, including on one face oriented approximately parallel to the [111] plane, the plane previously expected to catalyse deposition most effectively.

Dry reforming of methane (DRM) is an attractive and promising process for the conversion of methane and carbon dioxide which are the most abundant carbon sources into valuable syngas. The produced syngas, which is a mixture of hydrogen and carbon monoxide, can be used as intermediates in the manufacture of numerous chemicals. To achieve high conversion, DRM reaction is operated at high temperatures (700-900 °C) that can cause major drawbacks of catalyst deactivation by carbon deposition, metal sintering or metal oxidation. Therefore, the primary goal is to develop a metal based catalyst for DRM that can completely suppress carbon formation by designing the catalyst composition. The strategy of this work was to synthesize Ni-based catalysts all of which prepared by homogeneous deposition precipitation method (HDP) to produce nanoparticles with narrow size distribution. In addition, control the reactivity of the metal by finely tuning the bimetallic composition and the reaction conditions in terms of reaction temperature and pressure. The highly endothermic dry reforming of methane proceeds via CH4 decomposition to leave surface carbon species, followed by removal of C with CO2-derived species to give CO. Tuning the reactivity of the active metal towards these reactions during DRM allows in principle the catalyst surface to remain active and clean without carbon deposition for a long-term. The initial attempt was to improve the resistance of Ni catalyst towards carbon deposition, therefore, a series of 5 wt.% bimetallic Ni9Pt1 were supported on various metal oxides (Al2O3, CeO2, and ZrO2). The addition of small amount of noble metal improved the stability of the catalyst compared to their monometallic Ni and Pt catalysts, but still high amount of carbon (> 0.1 wt.%) was formed after 24 h of the reaction. The obtained results showed that the catalytic performance, particle size and amount of deposited carbon depends on the nature of support. Among the tested catalysts, Ni9Pt1/ZrO2 showed high stability with the least carbon amount (0.55 wt.%). On the other hand, mono- and bimetallic Co-Ni/ZrO2 were then prepared following the same synthesis protocol. The ZrO2 support was chosen because of its high thermal stability and absence of mixed oxide formation with the active metals. It was demonstrated that on monometallic Co catalyst, the kinetic analysis showed first-order in CH4 and negative-order in CO2 on the DRM rate. The Co catalyst deactivated without forming carbon deposits. On contrary, on monometallic Ni catalyst, the DRM rate was proportional to CH4 pressure but insensitive to CO2 pressure. The Ni surface provides comparatively higher rates of CH4 decomposition and the resultant DRM than the Co catalyst but leaves some deposited carbon on the catalyst surface. In contrast, the bimetallic CoNi catalyst showed kinetics resembling the Co catalyst, i.e., the first-order with respect to CH4 pressure and the negative-order with respect to CO2 pressure on the DRM rate. Noticeably, the stability of CoNi catalyst was drastically improved over the monometallic counterparts and no deposited carbon was detected after the DRM reaction. The results suggest that for an appropriate Co/Ni ratio, the bimetallic CoNi/ZrO2 catalyst exhibits intermediate reactivity towards CH4 and CO2 between Co and Ni producing negligible carbon deposition by balancing CH4 and CO2 activation.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17890号 / 工博第3799号 / 新制||工||1581(附属図書館) / 30710 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The goal of current solid oxide fuel cell (SOFC) research is to design electrode materials and other system components that permit the fuel cell to be operated in the 400-700ºC range. Cell performance in this lower temperature range is limited by the oxygen reduction process at the SOFC cathode and by multiple contamination processes. The work presented demonstrates that Raman spectroscopy, a form of vibrational spectroscopy, can provide structural and compositional information complementary to that from traditional characterization methods. Initial experiments into the oxygen reduction mechanism on SOFC cathodes were unable to detect surface oxygen species on selected perovksite-based SOFC cathode materials. However, the Raman signal from the cathode surface was able to be enhanced by depositing silver or gold nanoparticles on the cathode, creating the so-called surface-enhanced Raman scattering (SERS) effect. The Raman sample chamber was also used to study two possible electrode contamination processes. First, the deposition of carbon on nickel and copper anodes was observed when exposed to different hydrocarbon fuel gases. Second, the poisoning of an SOFC cathode by chromium-containing vapor (usually generated by stainless steel SOFC system components) was monitored. Overall, Raman spectroscopy was shown to be useful in many areas crucial to the development of practical, cost-effective SOFCs. The techniques developed here could also be applied to other high temperature electrochemical and catalytic systems.

La croissance de nanotubes de carbone (NTC) sur particules micrometriques d'alumine (Al2O3) permet d'obtenir une dispersion uniforme des NTC dans des matrices sans enchevêtrement de NTC. Ce type de structure hybride NTC-Al2O3 fournit également une solution prometteuse au problème de sécurité de NTC car ils intègrent NTC avec des particules micrométriques, étendant la dimension des NTC à partir de nano-échelle au micro-échelle. Cependant, l'adhérence entre les NTC et les Al2O3 particules ne permet pas de fixer efficacement les NTC. Par ailleurs, une autre préoccupation essentielle de NTC est de savoir comment créer une forte adhésion interfaciale entre les NTC et les matrices polymères pour obtenir de bonnes propriétés mécaniques et de ne pas diminuer la conductivité électrique de NTC. Motivé par ces considérations, cette thèse vise à proposer plusieurs techniques concernant le dépôt d'une nano-couche conductrice sur la surface des structures hybrides NTC-Al2O3. De plus, les impacts de la nano-couche déposée sur la fixation des NTC à la surface d’Al2O3, sur la conductivité électrique des hybrides NTC-Al2O3, et sur l'adhésion interfaciale des systèmes NTC-Al2O3/epoxy composites sont étudiés en détail. / Growth of carbon nanotubes (CNTs) on micro-sized alumina (Al2O3) particles helps to achieve a uniform dispersion of CNTs in matrices without CNT entanglement. This kind of CNT-Al2O3 hybrids also provides a promising solution to the CNT safety problem since they integrate CNTs with micrometric particles, extending dimension of CNT fillers from nano-scale to micro-scale. However, the adhesion between the CNTs and the Al2O3 particles doesn’t sufficiently enable to fix the CNTs firmly and stably. Besides, another crucial concern of CNTs is how to create a strong interfacial adhesion between CNTs and polymer matrices for good mechanical properties and meanwhile not to degrade CNTs’ electrical conductivity. Motivated by these considerations, this PhD thesis aims to establishing several techniques for deposition of an electrically conductive nano-layer on the surface of CNT-Al2O3 hybrids. And the impacts of the deposited nano-layer on the fixing the CNTs on the Al2O3 surface, on bulk electrical conductivity of the CNT-Al2O3 hybrids, and on the interfacial adhesion of CNT-Al2O3/epoxy composite systems are investigated in detail.

This study aims to find how density affects the reduction extent and reduction rate. H2-CO gas mixture is used as reducing agent. Five groups of different density pellets were reduced at four different temperatures. Light optical microscope (LOM) and scanning electron microscope with energy dispersive X-ray spectroscopy (SEM-EDS) used to detect completely and partially reduced pellets to investigate how density affects the reduction mechanisms. Results illustrate that density affects reduction extent and reduction rate a lot. However, when reaction temperature is 1123 K, density has less influenc on reduction extent. The carbon deposition occurred for high density pellets at 973 K and 1023 K. The reduction process cannot be described by a single rate controlling step. Reduced layer is denser compared with unreduced layer. Reaction at initial stages goes much faster than later stages.

This report deals with the mathematical model of the transient behaviour of an existing ethane dehydrogenation furnace which is composed of two main sections: a preheating convection section and a radiant-heated section. The correlation of pressure drop with time has been found from the available data. The fractional carbon deposition and the multiplier coefficient of a pressure drop equation have been determined by the direct search optimization technique of Hooke and Jeeves. An optimal policy for the cyclic operation of the furnace was determined by considering plant temperature profile and hydrocarbon/ steam ration as parameters for maximizing average ethylene produced per day. The effect of temperature profile on the distribution of carbon deposited along the reactor was also predicted and discussed. / Thesis / Master of Engineering (ME)