Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-02-03T12:08:21Z No. of bitstreams: 0 / Made available in DSpace on 2016-02-03T12:08:21Z (GMT). No. of bitstreams: 0 / O crescimento anual no número de procedimentos realizados em Medicina Nuclear se deve em primeiro lugar à vantagem de não serem invasivos. Cerca de 80% dos diagnósticos realizados em Medicina Nuclear utilizam radiofármacos preparados com tecnécio-99m devido a suas características físicas ideais, disponibilidade e baixo custo. Dentre os radiofármacos utilizados para identificar processos de infecção e inflamação estão os leucócitos marcados com tecnécio-99m, considerado o padrão ouro e o citrato de gálio (67 Ga), atualmente comercializado no Brasi. Os leucócitos marcados possuem a desvantagem da técnica laboriosa de marcação nem sempre disponível nos centros de Medicina Nuclear, enquanto o citrato de gálio (67 Ga) não é específico e possui energias desfavoráveis para a dosimetria do paciente e para a aquisição de imagens. Neste cenário, novas moléculas para diagnóstico de focos de infecção têm sido pesquisadas, particularmente envolvendo biomoléculas, como os peptídeos antimicrobianos. Nesta categoria, a Ubiquicidina na forma de um fragmento sintético (UBI 29-41) despertou o interesse de pesquisadores que estudaram a marcação com tecnécio-99m utilizando métodos direto e indireto. Um reagente liofilizado de UBI 29-41descrito na literatura demonstrou eficácia no diagnóstico de focos de infecção utilizando-se imagens cintilográficas, porém o produto não está disponível no Brasil. O objetivo deste trabalho foi estudar a marcação do fragmento de UBI 29-41 com tecnécio-99m por método direto e avaliar a utilização de soluções tampão no procedimento de marcação, de modo a flexibilizar o volume da solução de pertecnetato de sódio a ser utilizado, o que constitui aspecto de ineditismo deste trabalho. O fragmento foi radiomarcado com diferentes volumes de soluções tampão alcalinas (carbonato e fosfato) e a utilização dos tampões em substituição à solução de hidróxido de sódio possibilitou realizar a marcação com diferentes volumes da solução de pertecnetato de sódio, sem comprometimento do rendimento de marcação. Uma formulação liofilizada foi avaliada, demonstrando estabilidade por período de 12 meses, viabilizando a produção rotineira do agente de marcação. Os estudos de biodistribuição das preparações efetuadas com os diferentes tampões demonstraram que os complexos formados apresentam características gerais de biodistribuição semelhantes ao composto padrão descrito na literatura, incluindo rápido clareamento sanguíneo e alta captação renal, condizente com a eliminação do produto por esta via. Entretanto, as preparações estudadas apresentaram captação hepática maior e captação renal menor que o composto padrão. As preparações estudadas captaram no foco de infecção provocado por S.aureus e demonstraram potencial para aplicação clínica no diagnóstico em Medicina Nuclear. Como pré-requisito para a realização de estudos clínicos de um novo composto foi realizado estudo de cito e genotoxicidade, cujos resultados demonstraram a segurança das preparações estudadas. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

The purpose of this study is to develop catalysts for conversion of synthesis gas (H₂ and CO) to higher alcohols, primarily ethanol and propanol. Crude oil is consumed at a rate of more than 20 million barrels a day in the United States, mainly for producing fuels and chemical feedstocks. However, the total amount of crude oil is limited, and alternative ways of producing alcohols as precursors for chemical feedstocks are desirable. In this study, using a known K/MoS₂/metal oxide catalyst as the starting point, two different approaches were explored to improve catalytic properties: 1) Co promotion on K/MoS₂/mixed metal oxide (MMO) catalysts, and 2) Preparation of K/MoS₂/metal oxide catalysts with molybdenum carbide as a precursor, instead of molybdenum oxide. With respect to Co promotion on K/MoS₂/MMO catalysts, the effect of varying the Co content in the K/Mo-Co/MMO catalysts prepared by a co-impregnation method did not produce significant changes in catalytic acitivities or selectivities. It was due to the premature precipitation of cobalt molybdate during synthesis. Cobalt molybdate precipitation can generally be prevented by using water as a solvent, but this approach is not appropriate for this study because of the use of hydrotalcite-derived mixed metal oxide as the support. Co loadings on K/Mo/MMO-Co catalysts did not change selectivities significantly, either. However, they changed catalytic activities, represented by gas hourly space velocity (GHSV) required to obtain 8% conversion while maintaining high selectivities for higher alcohols. As a result, C ₂₊ alcohol productivities reached 0.01g(alcohol)/g(catalyst)/hr with Co loadings higher than 8%. With respect to using Mo2C as the precursor of Mo species instead of MoO3, comparisons between catalysts with different precursors for Mo species and different pretreatments were investigated. In this study, both K/Mo catalysts supported on MgO and α-Al₂O₃ showed similar tendencies of catalytic activities and selectivities. The highest C₂₊ alcohol selectivities and productivities were obtained on presulfided MoO₃ catalysts on both supports. In comparison of K/Mo ₂C catalysts with different pretreatments, higher C₂₊ alcohol selectivities and lower MeOH selectivities were obtained on presulfided catalysts compared to non-pretreated catalysts.

Thesis (M.S.); Submitted to Central Missouri State University, Warrensburg, MO (US); 17 Dec 2004. / Published through the Information Bridge: DOE Scientific and Technical Information. Kerr, Kent. NNSA Kansas City Site Office (US) NNSA Kansas City Site Office. 12/17/2004. Report is also available in paper and microfiche from NTIS.

>Magister Scientiae - MSc / Chemical speciation and the evaluation of species distribution is the key to understanding the potential of brines to form scale or corrode the water circuit as well as the potential of mobility and release trends of the pollutants into the environment. It is important to identify highly soluble free ions in water chemistry because toxicity of ions is related to mobility and consequently bioavailability. The chemical composition, character and chemical speciation modelling of saline effluents (brines) at Tutuka Power Station and Sasol Synthetic Fuels Complex in Secunda were studied. The form in which chemical species exist (chemical speciation) and the physical and chemical interactions of species in saline effluents at these two study sites is not fully understood. This study investigated how pH, temperature, alkalinity and chemical composition influenced chemical speciation, species distribution, scale forming and corrosion potentials of the different saline effluent streams at the two sites using computer programs PHREEQC and Aq.QA. Characterizations of the results were presented in Stiff and Piper diagrams generated by the Aq.QA computer software. Chemical speciation modelling of the brines showed that scale-forming minerals aragonite, calcite, hematite, anhydrite and gypsum have positive saturation indices between 0 and 20 in mine water, RO brine at Tutuka and Sasol Secunda, EDR brine at Sasol Secunda and VC brine at Tutuka Power Station. The water types at Tutuka Power Station were found to be mainly Na-S04 water types and those at Sasol Secunda were a mixture of Na-Cl and Na-S04 water types. Water treatment chemicals playa major role in increase were absent in the intake water. It was found that Sasol Secunda water streams are much more heavily contaminated than Tutuka water streams. The study also found that the mine water utilised at Sasol Secunda is two-fold more polluted than the mine water utilised at Tutuka although these sites are a mere 40 km apart. The sodium adsorption ratios showed that all the saline effluent streams at Tutuka and Sasol Secunda were unsuitable for irrigation, except for desalination product waters. Chemical speciation showed that the predominant species in the most concentrated saline effluent (VC brine) at Tutuka were the free cr ion at approximately 100 % with very minute quantities of FeCI+ and ZnCI+ and the predominant sodium species were the free Na+ ion which existed at 85 %. Magnesium species had the predominant form as the ionic compound MgS04 at 73 % and the carbonates were mainly in the form of NaC03- (53 %), HC03- (28 %) and CO{(7 %). The most concentrated brine analysed at Sasol Secunda was the TRO brine. PHREEQC did not predict the precipitation of CaC03 from the TRO brine at Sasol Secunda. The most abundant calcium species were Ca2+(59 %) ions and CaS04 (40 %). The brine was at a pH of 5.76 with dissolved CO2 at 73 % of the carbonate species. Trace elements were evaluated and the toxic trace elements varied from 0.07 mg/L (As) to 26.75 mg/L (Sr) at Sasol Secunda. At Tutuka Power Station the toxic trace elements in brines varied from 0.02 mg/L (As/Se) to 16.85 mg/L (Sr). Sr and B were found to be the most highly concentrated toxic elements. The major and trace ion chemistry, alkalinity, pH, sodium adsorption ratios, change in concentration of the water streams and the brine chemical composition after contact with ash was also evaluated. When saline effluents at Tutuka Power Station and Sasol Secunda are combined with ash, pH, Ca content and alkalinity of the resulting solution increased. The chemical composition of saline effluents can be influenced by the ingress of CO2 from the atmosphere. The study shows conclusively that brine composition and concentration is highly variable at these South African power utilities and processes such as RO, contact with ash and C02 ingress can have an impact upon the overall brine quality. Aq.QA was found to be a more accurate tool for classifying waters according to dominant ions than Stiff diagrams but Stiff diagrams still have the superior advantage of being a mapping tool to easily identify samples of similar composition as well as quickly identify what has been added or what has been removed from a water stream. Chemical speciation could identify effluent streams where C02 dissolution had taken place.

[ES] Históricamente, el sector del transporte de servicio mediano y pesado ha sido desafiado por las regulaciones de emisiones que se han impuesto a lo largo de los años, lo que requirió intensificar el esfuerzo de investigación con el objetivo de avanzar en el desarrollo tecnológico para ofrecer una opción que cumpla con las normas a un precio similar para el propietario. No obstante, la reciente introducción de la normativa EUVI ha requerido la adición de un complejo sistema de postratamiento, agregando nuevos costes fijos al producto, así como costes operativos con el consumo de urea. Este avance fue necesario debido a la limitación de la combustión diésel convencional que no puede desacoplar las altas emisiones de NOx y la eficiencia. Esta limitación tecnológica ha impulsado la investigación sobre diferentes conceptos de combustión que podrían mantener niveles de eficiencia similares a los de la combustión diésel controlando la formación de emisiones durante el proceso de combustión. Entre las diferentes soluciones que han ido apareciendo a lo largo de los años, se demostró que la Ignición por Compresión Controlada por Reactividad (RCCI por sus siglas en inglés) tiene una ventaja competitiva debido a su mejor controlabilidad, alta eficiencia y bajas emisiones de hollín y NOx. A pesar de sus beneficios, la extensión de RCCI a la operación de mapa completo ha indicado limitaciones importantes como gradientes de presión excesivos a alta carga, o alta inestabilidad de combustión y productos no quemados a baja carga del motor. Recientemente, se introdujo el concepto de combustión Dual-Mode Dual-Fuel (DMDF) como un intento de resolver los inconvenientes de la combustión RCCI manteniendo sus ventajas. Los resultados preliminares obtenidos en un motor mono cilíndrico (SCE por sus siglas en inglés) han demostrado que el DMDF puede alcanzar niveles de eficiencia similares a los de la combustión diésel convencional al mismo tiempo que favorece niveles ultra bajos de hollín y NOx. Si bien, los requisitos de la condición límite son difíciles de encajar en el rango operativo de sistema de gestión de aire, así como inconvenientes como el exceso de HC y CO que aún persiste en la zona de baja y media carga, lo que puede ser un desafío para el sistema de postratamiento. Además, las futuras regulaciones a corto plazo exigirán una reducción del 15 % de las emisiones de CO2 en 2025, reto que la literatura sugiere que no se logrará fácilmente solo mediante la optimización del proceso de combustión. En este sentido, esta tesis tiene como objetivo general la implementación del concepto de combustión DMDF en un motor multicilindro (MCE por sus siglas en inglés) bajo las restricciones de las aplicaciones reales para realizar una combustión limpia y eficiente en el mapa completo a la vez que brinda alternativas para reducir la concentración de HC y CO y lograr un ahorro de CO2. Este objetivo se logra mediante un primer extenso procedimiento de calibración experimental que tiene como objetivo trasladar las pautas de la combustión DMDF del SCE al MCE respetando los límites operativos del hardware original, evaluando su impacto en los resultados de combustión, rendimiento y emisiones en condiciones estacionarias y condiciones de ciclo de conducción. A continuación, se realizan estudios específicos para abordar el problema relacionado con la concentración excesiva de productos no quemados mediante investigaciones experimentales y simulaciones numéricas para comprender las consecuencias del uso de combustibles con diferente reactividad en la eficiencia de conversión del catalizador de oxidación original y su capacidad para lograr emisiones en el escape menores que el límite EUVI. Finalmente, se busca la reducción de CO2 a través de la modificación del combustible, investigando tanto la mejora del proceso de combustión como el equilibrio entre el ciclo de vida del combustible. / [CA] Històricament, el sector del transport de servei mitjà i pesat ha sigut desafiat per les regulacions d'emissions que s'han imposat al llarg dels anys, la qual cosa va requerir intensificar l'esforç d'investigació amb l'objectiu d'avançar en el desenvolupament tecnològic per a oferir una opció que complisca amb les normes a un preu similar per al propietari. No obstant això, la recent introducció de la normativa EUVI ha requerit l'addició d'un complex sistema de postractament, agregant nous costos fixos al producte, així com costos operatius amb el consum d'urea. Aquest avanç va ser necessari a causa de la limitació de la combustió dièsel convencional que no pot desacoblar les altes emissions de NOx i l'eficiència. Aquesta limitació tecnològica ha impulsat la investigació sobre diferents conceptes de combustió que podrien mantindre nivells d'eficiència similars als de la combustió dièsel controlant la formació d'emissions durant el procés de combustió. Entre les diferents solucions que han anat apareixent al llarg dels anys, es va demostrar que la Ignició per Compressió Controlada per Reactivitat (RCCI per les seues sigles en anglés) té un avantatge competitiu a causa de la seua millor controlabilitat, alta eficiència i baixes emissions de sutge i NOx. Malgrat els seus beneficis, l'extensió del RCCI a l'operació de mapa complet ha indicat limitacions importants com a gradients de pressió excessius a alta càrrega, o alta inestabilitat de combustió i productes no cremats a baixa càrrega del motor. Recentment, es va introduir el concepte de combustió Dual-Mode Dual-Fuel (DMDF) com un intent de resoldre els inconvenients de la combustió RCCI mantenint els seus avantatges. Els resultats preliminars obtinguts en un motor mono-cilíndric (SCE per les seues sigles en anglés) han demostrat que el DMDF pot aconseguir nivells d'eficiència similars als de la combustió dièsel convencional al mateix temps que afavoreix nivells ultra baixos de sutge i NOx. Si bé, els requisits de la condició límit són difícils d'encaixar en el rang operatiu de sistema de gestió d'aire, així com inconvenients com l'excés de HC i CO que encara persisteix en la zona de baixa i mitja càrrega, la qual cosa pot ser un desafiament per al sistema de postractament. A més, les futures regulacions a curt termini exigiran una reducció del 15% de les emissions de CO¿ en 2025, repte que la literatura suggereix que no s'aconseguirà fàcilment només mitjançant l'optimització del procés de combustió. En aquest sentit, aquesta tesi té com a objectiu general la implementació del concepte de combustió DMDF en un motor multi-cilindre (MCE per les seues sigles en anglés) sota les restriccions de les aplicacions reals per a realitzar una combustió neta i eficient en el mapa complet alhora que brinda alternatives per a reduir la concentració de HC i CO i aconseguir un estalvi de CO¿. Aquest objectiu s'aconsegueix mitjançant un primer extens procediment de calibratge experimental que té com a objectiu traslladar les pautes de la combustió DMDF del SCE al MCE respectant els límits operatius del motor original, avaluant el seu impacte en els resultats de combustió, rendiment i emissions en condicions estacionàries i condicions de cicle de conducció. A continuació, es realitzen estudis específics per a abordar el problema relacionat amb la concentració excessiva de productes no cremats mitjançant investigacions experimentals i simulacions numèriques per a comprendre les conseqüències de l'ús de combustibles amb diferent reactivitat en l'eficiència de conversió del catalitzador d'oxidació original i la seua capacitat per a aconseguir emissions al tub d'escapament menors que el límit EUVI. Finalment, es busca la reducció de CO2 a través de la modificació del combustible, investigant tant la millora del procés de combustió com l'equilibri entre el cicle de vida del combustible. / [EN] The medium and heavy-duty transport sector was historically challenged by the emissions regulations that were imposed along the years, requiring to step up the research effort aiming at advancing the product development to deliver a normative compliant option at similar price to the owner. Nonetheless, the recent introduction of EUVI normative have required the addition of a complex aftertreatment system, adding new fixed costs to the product as well as operational costs with the urea consumption. This breakthrough was required due to the limitation of the conventional diesel combustion which cannot decouple high NOx emissions and efficiency. This technological limitation has boosted the investigation on different combustion concepts that could maintain similar efficiency levels than the diesel combustion while controlling the emission formation during the combustion process. Among the different solutions that have appeared along the years, Reactivity Controlled Compression Ignition (RCCI) was demonstrated to have a competitive edge due to its better controllability, high efficiency and low soot and NOx emissions. Despite the benefits, the extension of RCCI to full map operation has presented significant limitations, as excessive pressure gradients at high load and high combustion instability and unburned products at low engine load. Recently, Dual-Mode Dual-Fuel (DMDF) combustion concept was introduced as an attempt of solving the drawbacks of the RCCI combustion while maintaining its advantages. The preliminary results obtained in single cylinder engine (SCE) have evidenced that DMDF can achieves similar efficiency levels than those from conventional diesel combustion while promoting ultra-low levels of soot and NOx. Albeit, the boundary condition requirements are hard to fit in the operating range of commercial air management system as well as drawbacks like excessive HC and CO that still persists from low to medium load, which can be a challenge for the aftertreatment system. Moreover, short-term future regulations will demand a 15 % reduction of CO2 emissions in 2025 which was proven in the literature to not be easily achieved only by combustion process optimization. In this sense, this thesis has as general objective the implementation of the DMDF combustion concept in a multi-cylinder engine (MCE) under the restrictions of real applications to realize clean and efficient combustion in the complete map while providing alternatives to reduce the HC and CO concentration and accomplish CO2 savings. This objective is accomplished by means of a first extensive experimental calibration procedure aiming to translate the guidelines of the DMDF combustion from the SCE to the MCE while respecting the operating limits of the stock hardware, assessing its impacts on combustion, performance, and emission results under steady and driving cycle conditions. Next, dedicated studies are performed to address the issue related with the excessive concentration of unburned products by means of experimental investigations and numerical simulations, to understand the consequences of using fuels with different reactivity in the stock oxidation catalyst conversion efficiency and its ability in achieving EUVI tailpipe emissions. Finally, CO2 reduction is explored through fuel modification, investigating both combustion process improvement and well-to-wheel balance as paths to realize CO2 abatement. / This doctoral thesis has been partially supported by the Spanish Ministry of Science Innovation and Universities under the grant:"Ayudas para contratos predoctorales para la formación de doctores" (PRE2018-085043) / Lago Sari, R. (2021). Dual Mode Dual Fuel Combustion: Implementation on a Real Medium Duty Engine Platform [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/165366 / TESIS

The increasing CO2 concentration in the atmosphere and the resulting climate change require an immediate and efficient reduction of anthropogenic carbon-dioxide emission. This target can be achieved by the usage of CO2-neutral fuels even with current technologies (Schemme et al. in Int J Hydrogen Energy 45:5395–5414, 2020). Diesel engines in particular are amongst the most efficient prime movers. Using oxymethylene-dimethyl-ether (OME) it is possible to solve the hitherto existing Soot-NOx-Trade-off. OME has bounded oxygen in the molecular chain. This reduces the formation of soot, but equally the calorific value. But in considerance of the physical and chemical properties of OME, it could be useful to optimize the standard diesel engine into an OME engine. As a result, single-cylinder tests were performed to obtain a detailed analysis of the differences between OME3-5 and commercially available DIN EN 590 Diesel. Based on the fact that OME has gravimetrically less than half the calorific value of diesel, twice the fuel mass must be injected for the same energy release in the combustion chamber. Therefore, at the beginning of the investigations, a variation of the injector flow rate was carried out by means of different nozzle hole diameters. The evaluation of the results included the fundamental differences in the combustion characteristics of both fuels and the determination of efficiency-increasing potentials in the conversion of OME3-5. Due to the lower ignition delay and the shorter combustion time of OME, potentials in the optimisation of the injection setting became apparent. Higher energy flows over the combustion chamber wall were noticeable in operation with OME. To get to the bottom of this, the single-cylinder investigations were supported by tests on the optically accessible high-pressure chamber and the single-cylinder transparent engine. The optical images showed a narrower cone angle and greater penetration depth of the OME injection jet compared to the diesel injection jet. This confirmed the results from the single-cylinder tests. This provides further potential in the design of the injector nozzle to compensate for these deficits. Overall, this work shows that operation with OME in a classic diesel engine is possible without any significant loss in efficiency and with little effort in the hardware. However, it is also possible to achieve more efficient use of the synthetic fuel with minor adjustments.