京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24712号 / エネ博第455号 / 新制||エネ||85(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 河本 晴雄, 教授 亀田 貴之, 教授 髙野 俊幸 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

The process of catalytic cracking of petroleum hydrocarbons invariably produces a carbonaceous deposit on the surface of the solid catalyst which serves to reduce the activity of the catalyst. This investigation was undertaken to determine the effect of the feed rate and the length of the cracking period on the carbon formation on the catalyst. A vertical, fixed-bed, externally heated reactor was constructed. The reactor contained a bed of synthetic silica-alumina Socony-Vacuum bead catalyst. The necessary auxiliary apparatus required to handle the feed and the products of reaction was provided. The amount of carbon deposited on the catalyst was determined by burning it and measuring the carbon dioxide thus formed. The feed material used was Esso Diesel Oil (208). It was exposed to the catalyst at a temperature of about 900 degrees Fahrenheit for a series of ten minute periods while the feed rate was varied from 0.42 to 5.55 volumes of feed per volume of catalyst per hour. Another series of tests was performed at the same temperature, the feed rate being held at approximately two volumes of feed per volume of catalyst per hour; while the length of the cracking period was varied between thirty-five seconds and thirty minutes. It was found that during the ten minute cracking periods the amount of carbon deposited on the catalyst was independent of the feed rate between the limits of 0.91 and 5.55 volumes of feed per volume of catalyst deposited on the catalyst was related to the length of the cracking period by a parabolic function. Further analysis of the data revealed that the amount of feed converted into carbon was related to the degree of conversion by a parabolic function. From the three relations mentioned above, an equation relating the conversion, the feed rate and the cracking period was derived. The form of this equation is as follows: V³⋅⁰ = (9.60 x 10⁵)/R_fv t⁰⋅⁷⁵ where V is the percent conversion, R_fv is the feed rate and t is the cracking time in minutes. It was further found that the activity of the catalyst was not materially decreased after a series of twenty-nine tests, but that the substitution of quartz chips for the catalyst in the reactor decreased the conversion obtained by 75 per cent. / M.S.

Yes / The synthesis, characterisation and evaluation of the in vitro cytotoxicity of four indole-based half-sandwich metal complexes towards two ovarian cancer cell lines (A2780 and A2780cisR) and one normal prostate cell line (PNT2) are presented herein. Although capable of inducing catalytic oxidation of NADH and able to reduce NAD+ with high turnover frequencies, in cells and in the presence of sodium formate, these complexes also strongly interact with biomolecules such as glutathione. This work highlights that efficient out-of-cells catalytic activity might lead to higher reactivity towards biomolecules, thus inhibiting the in-cells catalytic processes.

Thesis (MBA (Business Management))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: South Africa has historically benefited from its mineral wealth, building one of the leading mining industries in the world. South Africa holds the worlds largest known PGM (or precious group metals) resource base (in a geological formation known as the Bushveld Igneous Complex), with an estimated life of 230 years (at current mining rates). This precious commodity is a precious source of both the direct as well as indirect contributions into the South African economy, as well as a leading source of employment in the South African mining industry. PGMs are predominantly used in auto catalysts, with an estimated 60% of global demand emanating from this application, where the commodity is used in breaking down noxious compounds in exhaust emissions. Given the strong correlation between automotive production and platinum sales, it seems viable to assume that platinum sales will continue to grow as more stringent legislation is introduced globally to reduce automotive emissions. This can currently only be down by increasing the platinum loads in auto catalysts, as alternative technologies are not widely accepted or developed at present. Given the influence (and positive correlation between) demand and prices, it appears that PGM prices will be driven upwards as demand continues to grow. This effect may be exacerbated by the fact that the expansion in demand is likely to outgrow the expansion in supply, given that few significant platinum operations have been started in recent years. Following the strong rally of commodity prices, specifically PGM prices in mid-2008 that saw platinum at a record high of USD2276/oz, major automotive producers have indicated that they are investigating alternatives to the application of precious metals in catalytic converters, in an attempt to curtail production costs. Although no viable substitute could be developed as yet, various alternatives (such as silver alloys) have been mentioned throughout the media. The purpose of this paper is to investigate the impact of such a substitution event on South African PGM producers and its resultant effect on the South African economy. The study will attempt to determine, at a high level, the direct impact of the event, as well as the indirect consequences of the proposed substitution event. / AFRIKAANSE OPSOMMING: Die Suid-Afrikaanse ekonomie is histories op die mynbou- en landbousektore gebaseer, wat gelei het tot Suid-Afrika se wêreldklas mynbou industrie. Suid-Afrika beskik oor die wêreld se grootste PGM reserwes (in 'n geologiese formasie, ook bekend as die Bosveld Stollings Kompleks), met ‘n geskatte lewe van 230 jaar (teen huidige mynbou tempo's). Die komoditeite is verantwoordelik vir ‘n aansienlike hoeveelheid direkte en indirekte waardetoevoeging tot die Suid-Afrikaanse ekonomie. PGM’s word hoofsaaklik in katalisators in voertuie gebruik, met nagenoeg 60% van wêreldwye vraag wat uit die toepassing voortspring. PGMs word gebruik om uitlaatgasse op te breek en te verwerk in motorvoertuie. Gegewe die hoë mate van korrelasie tussen PGM en voertuigverkope, blyk dit voor die handliggend dat platinumverkope sal aanhou styg soos wat omgewingswetgeging in bepaling van toelaatbare uitlaatgasse in motorvoertuie strenger word. Die vermindering van uitlaatgasse is huidiglik slegs moontlik deur die verhoging van PGM ladings in katalisators, gegewe dat alternatiewe tegnologieë nog nie ver genoeg gevorder is om geimplementeer te word nie. Die hoë mate van korrelasie tussen PGM pryse en PGM vraag dui dat dit hoogs waarskynlik is dat die prys van edelmetaal sal aanhou styg soos wat vraag toeneem. Die verskynsel sal moontlik verder bou op die verwagting dat vraag vir die metaalaanbod oor die langtermyn sal oorskadu, siende dat geen wesenlike nuwe PGM myne onlangs oopgemaak is nie. Voertuigvervaardigers het aangedui dat hul alternatiewe tegnologieë opndersoek, nadat die platinumprys tot 'n rekord hoogtepunt van USD2276/ oz gestyg het in mid 2008. Die uitspraak is gelewer met die oog op koste kontrole in die vervaardiging van motorvoertuie. Alhoewel geen werkbare alternatief vir die edelmetale huidiglik bestaan nie, is verskeie moontlike materiale reeds in die media bespreek (byvoorbeeld verskeie silwer allooie). Die doel van die dokument is om die potensiële impak van so ‘n vervangings senario op die Suid-Afrikaanse ekonomie te ondersoek. Die studie sal poog om op ‘n hoë vlak die direkte en indirekte gevolge van die gebeurtenis te bepaal.

Aminoalcohols are very important compounds used in various asymmetric transformations as chiral ligands or chiral auxiliaries. In this thesis, four novel heterocyclic amine substituted chiral 1,4-aminoalcohols were synthesized. In the synthetic strategy, amide esters were synthesized from (2S, 3R)-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene-2-carboxylic acid by DCC coupling method. Subsequent reduction of these amide esters lead to target 1,4-aminoalcohols. The activities of these novel chiral 1,4-aminoalcohols were tested in enantioselective diethylzinc addition, Mukaiyama aldol and Diels-Alder reactions. The enantioselectivities were measured by HPLC. All the products were identified by H NMR and C NMR spectroscopy

The aim of the work was to develop an understanding of the phenomenon of rate enhancement observed when a heterogeneous catalytic reaction system is irradiated by ultrasound. The system under investigation was the catalytic hydrogenation of an a, B - unsaturated ketone, using zinc dust and aqueous nickel chloride as a source of hydrogen. When a slurry of zinc particles and aqueous nickel chloride is stirred or sonicated, nickel deposits in the form of patches on the surface of the zinc particles and simultaneously, zinc dissolves into the solution in the form of zinc ions, a process called pitting corrosion. Hydrogen atoms are formed when hydrogen ions diffuse from the bulk, adsorb onto the nickel surface and take up electrons generated by the dissolution of zinc. Once the atoms are formed on the surface, the atoms combine to form hydrogen molecules, which desorb in the form of hydrogen gas. When ketone is added to this slurry, the hydrogen atom formed on the surface of nickel is used as the source of hydrogen for the hydrogenation reaction. In these processes, nickel serves as catalyst. The ketone first has to diffuse to the bulk, adsorb onto the surface of nickel and undergo reduction by the hydrogen atoms to form the product. The product then has to desorb from the surface and diffuse into the bulk, in order to create vacant sites on the nickel surface for the adsorption of more ketone. Experiments dealing with measurements of hydrogen evolution rates pointed out that hydrogen is not a limiting reactant, since evolution was sustained for long periods of time. The evolution rates versus time data revealed that the nature of the plots for both, the stirred and sonicated systems were similar. These facts lead us to infer that the basic mechanism of nickel deposition, pitting corrosion, etc. was similar for the two cases. To study the hydrogenation reaction, experiments were first conducted keeping the nickel catalyst surface area constant. The results of these experiments showed that the hydrogenation reaction can be explained by a first order mechanism. Changing the speed of the stirrer did not effect the rate of the reaction; hence it was inferred that the reaction was not external mass transfer controlled. It was also seen that there was an no significant difference in reaction rates between the stirred and sonicated systems. Hence we conclude that sonication does not effect any process involved in the actual process of hydrogenation, i.e., adsorption, desorption, surface reaction, etc., do not get effected. It was concluded that the observed rate enhancements of similar compounds in the same system occur only when nickel catalyst is being continuously formed. This is possible only if irradiation with ultrasound enhances the rate of formation of the surface area of the nickel deposit. To study this phenomena, experiments were conducted with continuous formation of nickel catalyst. These experiments were conducted in three ways - stirring with zinc dust, sonication with zinc dust and stirring with presonicated zinc dust. For the first two kinds of experiments, the rates were low, increased to a maximum value and then decreased, but the nature of the third kind of experiments were different. The initial rates were very high as compared to either of the other two kinds of experiments but the rate rapidly reduces and becomes comparable to the rates obtained by stirring with zinc dust. We conclude that sonication creates many active sites on the surface of the zinc particles in the form of crystal defects, which are perhaps necessary for the deposition of nickel. When presonicated zinc particles are used, there are large numbers of these sites and these get consumed rapidly when stirred with aqueous nickel chloride solution. In this work, we do not deal with this case. In the case of sonication with zinc dust, these active sites are continuously created and are consumed by nickel deposition. For the stirred system, these sites are quite small to start with and new ones are not generated since there is no irradiation by ultrasound. Hence, the rates in the latter case are low for both nickel deposition and the hydrogenation reaction. In the model, it was assumed that the rate of increase of surface area of nickel, characterized by a specific rate term k z, was proportional to the amount of nickel in the bulk and also to the amount of free zinc surface area available. Similarly, nickel which deposits on previously deposited nickel (characterized by another specific rate constant, kn) was proportional to the amount of nickel in the bulk, the nickel area already deposited and also the free zinc surface area available. The model is in excellent agreement with the experimental data obtained. The model predicted higher values of kn and kz for the sonicated system, indicating that the rate of deposition of nickel is much higher in this case than for the stirred system. Moreover, the model also predicts that the deposit in the case of a sonicated system is thinner and flatter, since it was seen that the surface area created for the same amount of nickel deposited was much higher in this case than the stirred system.

Considerable research is being carried out into the parameters that affect catalyst performance in order to meet the latest emission regulations. The conversion efficiency and the durability of automotive catalytic converters are significantly dependent on catalyst flow performance. Related investigations are commonly conducted using CFD techniques which represent an inexpensive and fast alternative to experimental methods. This thesis focuses on the flow performance of automotive catalytic converters using both experimental and computational techniques. The work describes the effects of inlet flow conditions on catalyst performance, the application of radial vanes to catalyst systems and the refinement of the CFD flow model which increases the accuracy of the predicted catalyst flow performance. the effects of inlet flow conditions on the flow maldistribution across the catalyst face and the total pressure loss through the system were assessed using a steady air flow rig. Tests were conducted over a range of Reynolds numbers typically encountered in automotive catalytic converters using a uniform and a fully-developed inlet flow condition. The results showed that the flow maldistribution significantly increases with Reynolds number notably in wide-angled diffusers. The catalyst flow performance is considerably improved when the inlet flow is uniform rather than fully-developed, the non-dimensional total pressure loss is reduced by 8% at Re=60000 and the flow maldistribution across the catalyst face is decreased by 12.5% and 15% respective Reynolds numbers of 30000 and 60000 when using a 60 degree diffuser. The total pressure loss through the system was found to be mostly associated with the monolith brick resistance. When the flow maldistribution is approximately 2, the pressure loss across the monolith brick represents 80% of the system pressure loss. The flow maldistribution across the catalyst face was improved by locating a system of radial splitters in the diffuser. The optimum flow performance was found to be a complex function of the vane design. A maximum improvement in the flow maldistrution indices M and Mi of 25% and 50% respectively was achieved at the expense of an increase in total pressure loss of 13.5% at Re = 60000. Both CFD and flow visualisation techniques were used as an aid to interpreting the flow field in the diffuser. Although a qualitative agreement was obtained using CFD, the flow maldistribution across the catalyst face was underpredected by up to 20%. The accuracy of the flow predictions was significantly improved by investigating the flow field in the monolith channels. Flow recirculation occurs in the channel entry length when the flow approaches the monolith channels at an angle which induces an additional implemented into four models of the flow through axisymmetric catalyst assemblies using various diffuser geometries and inlet flow conditions. By including the flow entrance effects in the porous media approach, the flow maldistribution was predicted within 8% instead of 15% when these effects are neglected. Further investigation of the flow in the monolith channels will be required to accurately model three-dimentional flows (racetrack catalysts) and to include various channel geometries and system flow rates.

My master´s thesis deals with the problems of NOx abatement that are included in flue gas. The accent is put on flue gases treatment throug cloth filter or ceramic candles, where the deposited catalyst enables NOx reduction throug the method of selective cytalytic reduction. In thesis is also describe experimental unit which current remove gaseous pollutants (dioxin, VOC and NOX) and ash on catalytic cloth filter or catalytic ceramic candles. For experimental unit has been calculated pressure drop. Pressure drop has been calculated for nominal and maximal conditions for cloth filter and ceramic candle. Last part of thesis deals with compile a experimental schemes for different concentration of NO, flow and temperature of combustion.

This thesis deals with the reduction of oxides of nitrogen (NOx) which are part of the exhaust gas combustion devices. The focus is on reduction of NOx by selective catalytic reduction (SCR) and catalyst filtration. The first part of this work deals with the formation of NOx, their hazards and related legislation. The following is an overview of the available technologies to reduce NOx in the flue gas and comparison of this methods. The following section describes the experimental catalytic filtration unit INTEQ II, where the first real experiment selective catalytic reduction of NOx with ammonia was realized. We have verified the operability of the experimental units and achieve up to 80% efficiency SCR. The final section describes the progress of the experiment and its results. It is recommended a few minor adjustments to improve stabile operation of unit INTEQ II.

V současnosti musí velké energetické podniky k dodržení emisních předpisů, zejména pak vyžadovaných limitů NOx, uplatňovat denitrifikační metody. Tématem předkládané diplomové práce jsou moderních denitrifikační metody a jejich praktické uplatnění v lokálních poměrech uhelného kotle s parním výkonem 640 t.h-1 v elektrárně Počerady. Práce obsahuje rešerši moderních denitrifikačních metod používaných velkými uhelnými kotli se zaměřením zejména na sekundární denitrifikační metody. Jsou uvažovány dvě možné varianty denitrifikace – varianta 1 využívá selektivní katalytickou redukci (SCR) a varianta 2 selektivní nekatalytickou redukci (SNCR) společně s nízkoemisními hořáky a stupňovaným přívodem spalovacího vzduchu. Pro výběr vhodné denitrifikační metody jsou studovány investiční náklady jednotlivých variant – nižší investiční náklady (o 19.4%) slibuje varianta 2. Při srovnávání SCR se SNCR vyšlo najevo, že investiční náklady metody SNCR jsou 5krát nižší než metody SCR. V souladu s investičními náklady, s dispozicí kotle a se složitostí jeho instalace je pro navazující studium problematiky využita varianta 2. Stěžejní část práce se zabývá stanovením optimálního tzv. teplotního okna pro konkrétní metodu SNCR. Těžištěm práce je tepelný výpočet ohniště a části deskového přehříváku pro stanovený rozsah paliv a výkon kotle v rozmezí 60-100%. S uvažováním výsledků z výpočtu jsou navrženy dvě vstřikovací roviny, které mají zaručit vysokou efektivitu denitrifikačního procesu při uvažovaných provozních podmínkách kotle. Diplomová práce rovněž diskutuje obecnou vhodnost instalace SNCR a SCR ve stávajících uhelných kotlích.