Considerado a alternativa mais pesquisada para substituir o diesel, o biodiesel, oriundo da transesterificação, é cotado como a mais promissora opção de combustível obtido de fontes renováveis para o lugar dos ameaçados combustíveis de origem fóssil. A reação de transesterificação para produção do biodiesel pode ocorrer de forma catalítica, a mais utilizada atualmente, e não-catalítica, por meio de fluidos supercríticos. A grande diversidade de matérias-primas que pode ser usada na obtenção do biodiesel supercrítico é apenas um dos atrativos para sua produção, porém uma produção em larga escala esbarraria nos altos custos operacionais do processo. Devido ao potencial revelado nos processos supercríticos, o estudo do comportamento de fases dentro de um reator se mostra relevante ao domínio do processo, visto que pesquisas indicam que é possível balancear os custos de uma produção de biodiesel em condições supercríticas com os custos de uma produção de biodiesel com uso de catalisadores. Na termodinâmica, a modelagem é um método prático e rápido de se estimar o comportamento do equilíbrio líquido-vapor (ELV) do sistema e reduzir gastos com excessivos experimentos, através de um modelo termodinâmico apropriado. Para isso, os modelos testados foram obtidos pela equação de estado (EdE) de Peng-Robinson com as regras de misturas de van der Waals com um (vdW1) e dois (vdW2) parâmetros de interação binária em sistemas formados por componentes presentes na produção do biodiesel. Utilizando a abordagem phi-phi e o método de BOLHA P, sistemas binários em condições próximas ao ponto crítico e em condições supercríticas, encontrados na literatura, foram modelados. A modelagem termodinâmica foi realizada após a aplicação de um teste de consistência termodinâmica, uma vez que foram encontradas diferenças nas propriedades críticas de um mesmo composto em diferentes referências. A adequação dos modelos termodinâmicos variou de acordo com as condições do processo, o que fará necessária uma análise específica da situação de acordo com o caso em que estiver sendo empregada. Na simulação termodinâmica, as redes neurais artificiais foram utilizadas para o ajuste computacional dos dados experimentais, produzindo os melhores resultados com a introdução dos descritores moleculares, junto às variáveis independentes do processo (temperatura e composição na fase líquida), na primeira camada de neurônios nas diversas configurações analisadas dentre as arquiteturas utilizadas, demonstrando ser uma ferramenta interessante para o estudo do equilíbrio de fases. / Considered the most researched alternative to replace the diesel fuel, the biodiesel, from transesterification, is rated as the most promising fuel option from renewable sources for the place of threatened fossil fuels. The transesterification reaction for biodiesel production can occur catalytically, commonly used, and non-catalytic, through supercritical fluids. The diversity of raw materials that can be used to obtain supercritical biodiesel is only one of the attractions for its production, but a large-scale production would encounter obstacles in the high operating costs of the process. Due to the potential revealed in the supercritical processes, the study of phase behavior in a reactor is relevant for domaining the process, since researches indicates that it is possible to balance the costs of producing biodiesel in supercritical conditions with the costs of a production of biodiesel using catalysts. In thermodynamics, modeling is a quick and practical method of estimating the vapor-liquid equilibria (VLE) behavior of the system and reducing expenses with excessive experiments, using an appropriated thermodynamic model. For this, the models tested were obtained by the Peng-Robinson equation of state (EoS) with the mixture rules of van der Waals with one (vdW1) and two (vdW2) binary interaction parameters in systems formed by components present in the production of biodiesel. Using the phi-phi approach and the BOL P method, binary systems in conditions near to the critical point and under supercritical conditions, found in the literature, were modeled. The thermodynamic modeling was performed after the application of a thermodynamic consistency test, since differences were found in the critical properties of the same compound in different references. The suitability of the thermodynamic models varied according to the process conditions, which will require a specific analysis of the situation according to the case in which it is being used. In the thermodynamic simulation, the artificial neural networks were used for the computational adjustment of the experimental data, producing the best results when the molecular descriptors were used with the independent variables of the process (temperature and composition of the liquid phase) in the first layer of nodes in the different configurations analyzed among the architectures used, proving to be a tool of interest for the study of phase equilibria.

Considerado a alternativa mais pesquisada para substituir o diesel, o biodiesel, oriundo da transesterificação, é cotado como a mais promissora opção de combustível obtido de fontes renováveis para o lugar dos ameaçados combustíveis de origem fóssil. A reação de transesterificação para produção do biodiesel pode ocorrer de forma catalítica, a mais utilizada atualmente, e não-catalítica, por meio de fluidos supercríticos. A grande diversidade de matérias-primas que pode ser usada na obtenção do biodiesel supercrítico é apenas um dos atrativos para sua produção, porém uma produção em larga escala esbarraria nos altos custos operacionais do processo. Devido ao potencial revelado nos processos supercríticos, o estudo do comportamento de fases dentro de um reator se mostra relevante ao domínio do processo, visto que pesquisas indicam que é possível balancear os custos de uma produção de biodiesel em condições supercríticas com os custos de uma produção de biodiesel com uso de catalisadores. Na termodinâmica, a modelagem é um método prático e rápido de se estimar o comportamento do equilíbrio líquido-vapor (ELV) do sistema e reduzir gastos com excessivos experimentos, através de um modelo termodinâmico apropriado. Para isso, os modelos testados foram obtidos pela equação de estado (EdE) de Peng-Robinson com as regras de misturas de van der Waals com um (vdW1) e dois (vdW2) parâmetros de interação binária em sistemas formados por componentes presentes na produção do biodiesel. Utilizando a abordagem phi-phi e o método de BOLHA P, sistemas binários em condições próximas ao ponto crítico e em condições supercríticas, encontrados na literatura, foram modelados. A modelagem termodinâmica foi realizada após a aplicação de um teste de consistência termodinâmica, uma vez que foram encontradas diferenças nas propriedades críticas de um mesmo composto em diferentes referências. A adequação dos modelos termodinâmicos variou de acordo com as condições do processo, o que fará necessária uma análise específica da situação de acordo com o caso em que estiver sendo empregada. Na simulação termodinâmica, as redes neurais artificiais foram utilizadas para o ajuste computacional dos dados experimentais, produzindo os melhores resultados com a introdução dos descritores moleculares, junto às variáveis independentes do processo (temperatura e composição na fase líquida), na primeira camada de neurônios nas diversas configurações analisadas dentre as arquiteturas utilizadas, demonstrando ser uma ferramenta interessante para o estudo do equilíbrio de fases. / Considered the most researched alternative to replace the diesel fuel, the biodiesel, from transesterification, is rated as the most promising fuel option from renewable sources for the place of threatened fossil fuels. The transesterification reaction for biodiesel production can occur catalytically, commonly used, and non-catalytic, through supercritical fluids. The diversity of raw materials that can be used to obtain supercritical biodiesel is only one of the attractions for its production, but a large-scale production would encounter obstacles in the high operating costs of the process. Due to the potential revealed in the supercritical processes, the study of phase behavior in a reactor is relevant for domaining the process, since researches indicates that it is possible to balance the costs of producing biodiesel in supercritical conditions with the costs of a production of biodiesel using catalysts. In thermodynamics, modeling is a quick and practical method of estimating the vapor-liquid equilibria (VLE) behavior of the system and reducing expenses with excessive experiments, using an appropriated thermodynamic model. For this, the models tested were obtained by the Peng-Robinson equation of state (EoS) with the mixture rules of van der Waals with one (vdW1) and two (vdW2) binary interaction parameters in systems formed by components present in the production of biodiesel. Using the phi-phi approach and the BOL P method, binary systems in conditions near to the critical point and under supercritical conditions, found in the literature, were modeled. The thermodynamic modeling was performed after the application of a thermodynamic consistency test, since differences were found in the critical properties of the same compound in different references. The suitability of the thermodynamic models varied according to the process conditions, which will require a specific analysis of the situation according to the case in which it is being used. In the thermodynamic simulation, the artificial neural networks were used for the computational adjustment of the experimental data, producing the best results when the molecular descriptors were used with the independent variables of the process (temperature and composition of the liquid phase) in the first layer of nodes in the different configurations analyzed among the architectures used, proving to be a tool of interest for the study of phase equilibria.

Experimental data on the solubility of CO2 in methyl methacrylate (MMA) and butyl methacrylate (BMA) are reported at temperatures from 308 to 333 K and pressures in the range of 1 to 10 MPa. The corresponding measurements of the volumetric expansion of the liquid phase are also presented. The solubility data are correlated with the Peng-Robinson equation of state using two interaction parameters. Solubilities of CO2 as high as 80 mol% can be attained in both monomers in the range of pressure considered. A near-linear relationship is observed between pressure and liquid-phase composition. The Peng-Robinson equation of state provides a satisfactory correlation of the solubility data. The average absolute relative deviations with respect to the calculated values of pressure are less than 2%. For a given monomer, the expansion isotherms coincide when plotted as a function of the liquid - phase composition. Catalytic chain transfer (CCT) polymerisation of CO2-expanded MMA, BMA and styrene is then described. Experimental values of the chain transfer constant are determined at 323 K and 333 K and in the range of pressure from 0.1 to 6 MPa. A cobaloxime complex is used as the chain transfer catalyst. The effect of small quantities of polymer on the volumetric expansion of the corresponding monomer is considered. The chain transfer constants for the expanded monomers are significantly higher than those obtained in the bulk monomers. It is demonstrated that a linear relationship exists between the chain transfer rate coefficient and the inverse of liquid-phase viscosity. These results provide significant evidence that the rate-determining step in the CCT process is diffusion-controlled. Finally, molecular weight evolution in CCT polymerization of CO2-expanded MMA is reported. Experimental molecular weight and polydispersity index data are presented at 323 K in the range of conversion from 1 to 25%, and at pressures of 5 and 6 MPa. Both molecular weight and polydispersity increase with conversion at conditions below the homogeneous expansion limit. Predici simulations suggest that either irreversible catalyst deactivation or cobalt-carbon bond formation is the most likely mechanism for the increase in molecular weight with conversion.

Pour satisfaire aux dernières réglementations en matière d'émissions, des progrès importants sont encore attendus des moteurs à combustion interne. De plus, améliorer l'efficacité du moteur pour réduire les émissions et la consommation de carburant est devenu plus essentiel qu'auparavant. Mais, de nombreux phénomènes complexes restent mal compris dans ce domaine, tels que le processus d'injection de carburant. Nombreux logiciels pour la dynamique des fluides numérique (CFD) prenant en compte le changement de phase (comme la cavitation) et la modélisation de l’injection ont été développés et utilisés avec succès dans le processus d’injection. Néanmoins, il existe peu de codes CFD capables de simuler avec précision des conditions d’injection transcritiques, à partir d'une condition de température de carburant sous-critique vers un mélange supercritique dans la chambre de combustion. En effet, la plupart des modèles existants peuvent simuler des écoulements à phase unique, éventuellement dans des conditions supercritiques, ou des écoulements diphasiques dans des conditions sous-critiques. Par conséquent, il manque un modèle complet capable de traiter les conditions transcritiques, y compris la transition de phase possible entre les régimes souscritiques et supercritiques, ou entre les écoulements monophasiques et diphasiques, de manière dynamique. Cette thèse a pour objectif de relever ce défi.Pour cela, des modèles d'écoulement diphasique compressible de fluide réel basés sur une approche eulérienne-eulérienne avec prise en compte de l'équilibre de phase ont été développés et discutés dans le présent travail. Plus précisément, un modèle à 6-équation entièrement compressibles incluant les équations de bilan des phases liquide et gazeuse résolues séparément ; et un modèle à 4-équation qui résout les équations des bilans liquide et gazeux en équilibre mécanique et thermique sont proposés dans ce manuscrit. L’équation d’état Peng-Robinson EoS est sélectionné pour fermer les deux systèmes et pour faire face aux éventuels changements de phase et à la transition ou à la séparation des phases. En particulier, un solveur d'équilibre de phase a été développé et validé. Ensuite, une série de tests académiques 1D portant sur les phénomènes d'évaporation et de condensation effectués dans des conditions sous-critiques et supercritiques a été simulée et comparée aux données de la littérature et aux résultats académiques disponibles. Ensuite, les modèles d'écoulement en deux phases entièrement compressibles (systèmes à 6-équation et à 4- équation) ont été utilisés pour simuler les phénomènes de cavitation dans une buse 3D de taille réelle afin d'étudier l'effet de l’azote dissous sur la création et le développement de la cavitation. Le bon accord avec les données expérimentales prouve que le solveur proposé est capable de gérer le comportement complexe du changement de phase dans des conditions sous-critiques. Enfin, la capacité du solveur à traiter l’injection transcritique à des pressions et températures élevées a été validée par la modélisation réussie de l’injecteur Spray A du réseau de combustion moteur (ECN). / To satisfy latest stringent emission regulations, important progress is still be expected from internal combustion engines. In addition, improving engine efficiency to reduce the emission and fuel consumption has become more essential than before. But many complex phenomena remain poorly understood in this field, such as the fuel injection process. Numerous software programs for computational fluid dynamics (CFD) considering phase change (such as cavitation) and injection modelling, have been developed and used successfully in the injection process. Nevertheless, there are few CFD codes able to simulate correctly transcritical conditions starting from a subcritical fuel temperature condition towards a supercritical mixture in the combustion chamber. Indeed, most of the existing models can simulate either single-phase flows possibly in supercritical condition or two-phase flows in subcritical condition; lacking therefore, a comprehensive model which can deal with transcritical condition including possible phase transition from subcritical to supercritical regimes, or from single-phase to two-phase flows, dynamically. This thesis aims at dealing with this challenge. For that, real fluid compressible two-phase flow models based on Eulerian-Eulerian approach with the consideration of phase equilibrium have been developed and discussed in the present work. More precisely, a fully compressible 6-equation model including liquid and gas phases balance equations solved separately; and a 4-equation model which solves the liquid and gas balance equations in mechanical and thermal equilibrium, are proposed in this manuscript. The Peng-Robinson equation of state (EoS) is selected to close both systems and to deal with the eventual phase change or phase transition. Particularly, a phase equilibrium solver has been developed and validated. Then, a series of 1D academic tests involving the evaporation and condensation phenomena performed under subcritical and supercritical conditions have been simulated and compared with available literature data and analytical results. Then the fully compressible two-phase flow models (6-Equation and 4-Equation systems) have been employed to simulate the cavitation phenomena in a real size 3D nozzle to investigate the effect of dissolved N2 on the inception and developing of cavitation. The good agreement with experimental data proves the solver can handle the complex phase change behavior in subcritical condition. Finally, the capability of the solver in dealing with the transcritical injection at high pressure and temperature conditions has been further validated through the successful modelling of the engine combustion network (ECN) Spray A injector.

Atualmente, com tecnologias sendo desenvolvidas para que as plantas industriais se tornem cada vez mais eficientes, é necessário a compreensão e o conhecimento com grande precisão das propriedades termodinâmicas dos fluidos e compostos envolvidos em processos como a destilação, extração líquido-líquido, entre outros. Para tal, modelagens termodinâmicas são feitas visando determinar o comportamento de fases e a qualidade de misturas presentes nas etapas dos processos industriais e até mesmo do produto final. Entre os modelos termodinâmicos mais utilizados, a equação de estado de Peng-Robinson com Translação de Volume fornece ótimos resultados para o equilíbrio de fases líquido-vapor de substâncias puras e misturas. Esta equação foi utilizada, em conjunto ao método de Contribuição de Grupos, para realizar a modelagem termodinâmica de vários sistemas binários contendo componentes presentes no biodiesel, a baixas e altas pressões. Além disso, foi feita a análise experimental e o teste de consistência termodinâmica do sistema metanol + palmitato de metila à pressão constante de 1,0 bar. Os pontos experimentais deste sistema considerados termodinamicamente consistentes também foram modelados com a mesma equação de estado. Os resultados mostraram que a equação de Peng-Robinson com Translação de Volume e Contribuição de Grupos fornece baixos erros relativos, podendo ser usada em simulações de processos de produção e purificação de biodiesel. / Nowadays, with technologies being developed for industrial plants to increase their efficiency, it is necessary to understand and to know with good accuracy the thermodynamic properties of the fluids and compounds involved in processes such as distillation, liquid-liquid extraction, and others. To this purpose, thermodynamic modeling for these substances is done aiming to determine the phase behavior of mixtures present in the industrial processes and even in the final product. Among the used thermodynamic models, there is the Volume Translated Peng-Robinson equation of state, which provides good results for the liquid-vapor phase equilibrium of mixtures and pure substances. This equation was used with the Group Contribution method to model thermodynamically several binary systems containing biodiesel components at low and high pressures. In addition, the experimental analysis and the thermodynamic consistency test for the system methanol + methyl palmitate at constant pressure of 1,0 bar was done. The points of this system considered thermodynamically consistent were also modeled with the same equation of state. The results showed that the Volume Translated Peng-Robinson equation with Group Contribution provides low relative errors and can be used in simulations of biodiesel production and purification processes.

[pt] O setor da refrigeração possui um papel essencial e crescente na economia global, com um aumento na quantidade de sistemas operantes. A necessidade de desenvolver novos refrigerantes tem sido cada vez mais frequente, a fim de atender a legislações ambientais cada vez mais rigorosas. Igualmente, medidas envolvendo a introdução de novos materiais, como os nanofluidos, tem sido uma constante. Neste trabalho, um sistema de refrigeração usando uma mistura nanolubrificante POE-diamante e refrigerante R410A foi simulado. Dados experimentais cedidos pela Universidade Federal de Uberlândia (UFU) foram usados para a elaboração e validação do modelo. O simulador utiliza a equação de Peng-Robinson para o cálculo das propriedades termodinâmicas e o método de fronteira móvel para a modelagem dos trocadores. O impacto das nanopartículas em relação aos parâmetros críticos foi avaliado a partir do princípio do isomorfismo e da natureza de ambos os materiais: fluido base e nanopartículas. A convergência da simulação do ciclo de refrigeração foi obtida com o método do simplex modificado, que mostrou-se adequado para tal aplicação, apresentando convergência satisfatória em todos os casos. As temperaturas de evaporação, condensação e de descarga do compressor são obtidas a partir das condições de operação do compressor, dos dois fluidos de transferência de calor, do grau de superaquecimento no evaporador e também do grau de subresfriamento no condensador. Superfícies de resposta foram criadas a fim de avaliar o efeito de cada uma das variáveis (temperatura de evaporação, frequência do compressor e concentração de nanopartículas) utilizadas no estudo do coeficiente de performance (COP), da capacidade frigorífica e da potência do compressor. A temperatura de evaporação possui um impacto significativo sobre a capacidades frigorífica e o COP, enquanto que a potência é mais afetada pela frequência do compressor. A concentração de nanopartículas, apesar de possuir um efeito marginal, não deve ser desprezada, devido à modificação que causa sobre as propriedades termofísicas da mistura. / [en] The refrigeration sector has an essential and growing role in the global economy, with an increase in the number of operating systems. The need to develop new refrigerants has been increasingly frequent, in order to meet increasingly stringent environmental legislation. Equally, measures involving the introduction of new materials, such as nanofluids, have been a constant. In this work, a cooling system using a POE-diamond nanolubricant mixture and R410A refrigerant was simulated. Experimental data provided by the Federal University of Uberlândia (UFU) were used for the elaboration and validation of the model. The simulation uses the Peng-Robinson equation to calculate thermodynamic properties and the moving-boundary method for modeling the heat exchangers. The impact of the nanoparticles in relation to critical parameters was evaluated based on the principle of isomorphism and the nature of both materials: base fluid and nanoparticles. The convergence of the refrigeration cycle simulation was obtained with the modified simplex method, which proved to be adequate for such application, presenting satisfactory convergence in all cases. Evaporation,condensation and discharge temperatures are obtained from the operating conditions of compressor and both heat transfer fluids, the degree of superheating in the evaporator and also the degree of subcooling in the condenser. Response surfaces were created in order to evaluate the effect of each of the variables (evaporation temperature, compressor frequency and nanoparticle concentration) used in the study of the performance coefficient (COP), refrigeration capacity and compressor power. Results have shown that the evaporation temperature has a significant impact on the cooling capacity and the COP, while the power is mainly affected by the compressor frequency. The nanoparticles concentration, despite having a more attenuated effect, should not be neglected, due to the change it causes to the mixture thermophysical properties.

[pt] A determinação de parâmetros de interação precisos para equações de estado (EdE) em sistemas aquosos de aminas são cruciais para desenvolver modelos termodinâmicos em processos da engenharia química. O sistema binário de Nmetildietanolamina (MDEA) e água na purificação do biogás foi avaliado usando as abordagens 𝜑 – 𝜑 e 𝛾 – 𝜑, EdE de Peng–Robinson clássico com a regra de mistura não aleatória e EdE Peng–Robinson com a regra de mistura Wong-Sandler, para otimizar o fator acêntrico, ω, de componentes puros, e os parâmetros de interação binária, 𝑘𝑖𝑗. Os parâmetros de interação 𝑢𝑖𝑗 das EdE que incorporam o modelo UNIQUAC, como a abordagem γ – φ e a regra de mistura de Wong-Sandler também foram otimizados. Esses parâmetros foram avaliados usando um algoritmo de pressão de bolha reativa, codificação MATLAB e minimização de funções objetivas relacionadas ao desvio médio absoluto, AAD, entre dados experimentais e calculados em diferentes temperaturas. Os ω calculados de água, CO2 e MDEA foram 0,3275, 0,2039 e 1,0133, respectivamente, com AAD inferior aos valores da literatura. A abordagem 𝜑 − 𝜑 com EdE clássica de Peng–Robinson com regra de mistura Wong– Sandler foi mais adequada para o binário MDEA – H2O, resultando em 𝑢12 0 = −234.2841, 𝑢12 𝑇 = 1.0499, 𝑢21 0 = 266.4326, 𝑢21 𝑇 = 0.1966, 𝑘𝑖𝑗 = −0.0715, com pressão de vapor AAD% = 6,57% e composição AAD% = 17,51%. Devido à natureza altamente não ideal do sistema binário CO2 – H2O, nem as abordagens φ – φ ou γ – φ usando as EdE selecionadas resultaram em diagramas precisos de pressão de ponto de bolha para o equilíbrio vapor – líquido (VLE). / [en] Determining interaction parameter for equations of state (EOS) of water – amines systems are crucial to develop accurate models in chemical engineering processes. The binary system of N-methyldiethanolamine (MDEA) and water in biogas purification was evaluated using both φ – φ and γ – φ approaches, classic Peng–Robinson with the empirical “non-random” mixing rule and Peng–Robinson with the Wong-Sandler mixing rule EOS to optimize pure components acentric factor, ω, and binary interaction parameters, 𝑘𝑖𝑗. The interaction parameters 𝑢𝑖𝑗 from EOS that incorporate UNIQUAC model, such as γ – φ approach and Wong-Sandler mixing rule were optimized as well. These parameters were evaluated using a bubble pressure algorithm, MATLAB coding and minimization of objective functions related to absolute average deviation, AAD, between experimental and calculated data at different temperatures. The calculated ω of water, CO2 and MDEA were 0.3275, 0.2039 and 1.0133 respectively with lower AAD than literature values. The 𝜑−𝜑 approach classic Peng–Robinson with Wong – Sandler mixing rule EOS was better suited for the MDEA – H2O binary, resulting in as 𝑢120=−234.2841, 𝑢12𝑇=1.0499, 𝑢210=266.4326, 𝑢21𝑇=0.1966, 𝑘𝑖𝑗=−0.0715, with vapor pressure AAD% = 6.57% and composition AAD% = 17.51%. Due to the highly non-ideal nature of the CO2 – H2O binary system, neither φ – φ or γ – φ approaches using the selected EOS resulted in accurate vapor – liquid equilibrium (VLE) bubble point pressure diagrams.

Ce travail de thèse porte sur l'étude d'un procédé d'époxydation et de carbonatation par CO₂ des huiles végétales ce qui permet de valoriser à la fois les huiles et le CO₂ .Un modèle cinétique passant par la formation in situ de l'acide performique est construit pour l'époxydation de l'acide oléique et de l'huile de coton, en couplant les bilans de matière et d'énergie. Une stratégie permettant de réduire le nombre de paramètre à estimer est adoptée. Ce modèle est potentiellement transposable aux autres huiles ayant une structure similaire, car la réactivité de chaque type d'acide gras est déterminée. Pour la réaction de carbonatation, une étude cinétique est réalisée, et la solubilité et le coefficient de transfert de matière du CO₂ dans la phase liquide sont mesurés en tenant compte de la non idéalité des conditions à l'aide de l'équation d'état de Peng-Robinson. L'utilisation du carbonate obtenu est enfin examinée dans la synthèse de polyuréthanes sans isocyanates (NIPUs). / This thesis focuses on the process aspect of the first two steps in the synthesis of non-isocyanates polyurethanes (NIPUs) from vegetable oils, i.e. epoxidation and carbonation reaction. This process adds value to both vegetable oil and CO₂. A kinetic model by using performic acid formed in-situ is built for epoxidation of oleic acid and cottonseed oil, by coupling the mass balance and energy balance. This model is potentially transferable to other oils with similar structure as the reactivity of each type of fatty acid is determined. For the carbonation reaction, a kinetic study is carried out, and the solubility and the CO₂ mass transfer coefficient in the liquid phase is measured under non-ideal condition using the Peng-Robinson equation of state.

[EN] This last few years, the trend in diesel engines has been to use different kinds of fuels to identify their influence and behaviour on the emissions and performance. Among the wide variety of fuels employed are the so called Primary Reference Fuels (PRFs), which represent the behaviour of diesel and gasoline in terms of ignition properties, as they are located at both ends of the octane rating scale and also have very different cetane numbers. One of the disadvantages of using pure gasoline or diesel-gasoline blends in diesel engines is the time needed for the mixture to ignite and to completely burn the fuel. This generally requires working with partial loads or with premixed charges. In order to isolate the fuel effects on the spray processes and to be able to study the characteristic parameters of ignition delay time, lift-off length, vapour and liquid penetration, among others; different experiments under parametric variations of diesel like conditions have been performed. The tests were performed under inert and reactive conditions in a 2-stroke optical engine and a constant-pressure flow (CPF) high-pressure high-temperature vessel using single-hole nozzles, while diverse optical techniques were being employed. To study the influence of the fuel properties, different single-component fuels were employed as well as binary blends and a six-component diesel surrogate, which was also compared to conventional diesel. Additionally, the results have been contrasted with a one-dimensional model in order to further explain the values and trends found. The results presented a strong dependency on the fuel properties for the tests performed under inert and reactive conditions. The difference in physical properties of n-decane and n-hexadecane showed an almost linear reduction of the stabilized liquid penetration down to approximately 60% under some conditions. Additionally, due to the composition of the surrogate fuel, pure n-hexadecane was demonstrated to have almost identical evaporation characteristics, hence proving itself as a good candidate for a single-component surrogate of diesel fuel. In a similar way, the chemical properties of the PRFs n-heptane and iso-octane also proved to be influential on the spray development and radiation emitted. Ignition delay values up to one order of magnitude larger where obtained for both extremes of the blend range, as well as lift-off lengths up to three times longer. The radiation emitted by the soot incandescence presented the highest variations, as some conditions showed a reduction of almost four orders of magnitude among the blend range. Moreover, some cases did not present any radiation corresponding to the soot, and increasing the sensitivity of the camera only caused the chemiluminescence of the OH* radical to be captured. On a different way, the stabilized flame length determined also by the soot radiation did not present much variation as the fuel properties or the air temperature were changed; in fact, the only noticeable differences were caused by the changes in the oxygen composition of the ambient air. In conclusion, the fuel properties proved to have a significant effect on the spray processes. Lighter fuels favoured the evaporation of the spray under a range of conditions, while fuels with lower octane numbers ignited sooner and closer to the spray tip but with more soot luminosity measured. / [ES] Estos últimos años, la tendencia en motores diesel ha sido la de emplear distintos tipos de combustibles para identificar su influencia y comportamiento sobre las emisiones y rendimiento. Dentro de la amplia variedad de combustibles empleados están los llamados combustibles de referencia (PRFs ingl. Primary Reference Fuels), los cuales representan el comportamiento del diesel y la gasolina en lo que respecta a propiedades de encendido, ya que se encuentran en ambos extremos de la escala del número de octano y también poseen números de cetano muy distintos. Una de las desventajas de utilizar gasolina pura o mezclas de diesel-gasolina en motores diesel es el tiempo que toma la mezcla en encender y quemar completamente el combustible. Esto generalmente requiere trabajar con cargas parciales o cargas premezcladas. Para poder aislar los efectos del combustibles sobre los procesos de un chorro y que sea capaz estudiar los parámetros característicos de tiempo de retraso de encendido, longitud de despegue de llama, penetración de líquido y vapor, entre otros, se han realizado distintos experimentos bajo variaciones paramétricas de condiciones de motor diesel. Los ensayos han sido realizados bajo condiciones inertes y reactivas en un motor óptico de dos tiempos y una instalación de alta presión y alta temperatura de flujo continuo a presión constante (CPF ingl. Constant-Pressure Flow) empleando toberas mono-orificio, con aplicación de diversas técnicas ópticas. Para estudiar la influencia de las propiedades de los combustibles se utilizaron distintos mono-componentes, así como mezclas binarias y un sustituto de diesel conformado por seis componentes, el cual fuel comparado con diesel convencional. Adicionalmente, los resultados han sido contrastados con un modelo unidimensional para ayudar a explicar los valores y tendencias encontrados. Los resultados presentaron una fuerte dependencia de las propiedades de los combustibles en los ensayos realizados bajo condiciones inertes y reactivas. La diferencia entre las propiedades físicas del n-decano y n-hexadecano mostraron una reducción casi lineal sobre la longitud líquida estabilizada hasta aproximadamente un 60% bajo ciertas condiciones. Adicionalmente, debido a la composición del combustible de sustitución, el n-hexadecano puro demostró tener características de evaporación prácticamente idénticas, probándose a sí mismo como un buen candidato para ser un sustituto mono-componente del diesel convencional. De una manera similar, las propiedades químicas de los PRFs n-heptano e iso-octano también probaron tener influencia sobre el desarrollo del chorro y radiación emitida. Se obtuvieron valores de tiempo de retraso con diferencias de hasta un orden de magnitud entre ambos extremos del rango de las mezclas, así como longitudes de despegue de llama hasta tres veces más largas. La radiación emitida por la incandescencia del hollín presentó las variaciones más altas, ya que algunas condiciones mostraron reducciones de hasta cuatro órdenes de magnitud dentro del rango de mezclas. Es más, algunos casos no presentaron radiación correspondiente al hollín, e incrementar la sensibilidad de la cámara solo ocasionó que la quimioluminiscencia del radical OH* sea detectada. Por otro lado, la longitud estabilizada de llama calculada mediante la radiación del hollín no presentó mucha variación respecto a las propiedades del combustible o la temperatura del aire. De hecho, la única diferencia apreciable fue causada por los cambios en la composición del oxígeno del aire ambiente. En conclusión, las propiedades de los combustibles demostraron tener un efecto significativo en los procesos de un chorro diesel. Los combustibles más ligeros favorecieron la evaporación del chorro en un rango de condiciones, mientras que combustibles con números de octano más bajos encendieron más pronto y cerca de la tobera pero con mayor luminosidad del hollín medida. / [CAT] En aquests últims anys, la tendència en motors Diesel ha estat la d'emprar diferents tipus de combustibles per a identificar la seva influència i comportament sobre les emissions i rendiment. Dintre de l'àmplia varietat de combustibles emprats estan els anomenats combustibles de referència (PRFs angl. Primary Reference Fuels), els quals representen el comportament del dièsel i la gasolina pel que fa a propietats d'encesa, ja que es troben en ambdós extrems de l'escala del nombre d'octà i també posseeixen nombres de cetà molt diferents. Un dels desavantatges d'utilitzar benzina pura o barreges de Diesel-benzina en motors Diesel és el temps que pren la barreja a encendre i cremar completament el combustible. Això generalment requereix treballar amb càrregues parcials o càrregues premesclades. Per a poder aïllar els efectes del combustibles sobre els processos d'un doll i que sigui capaç estudiar els paràmetres característics de de temps de retard d'encesa, longitud d'enlairament de flama, penetració de líquid i vapor, entre altres, s'han estudiat diferents experiments sota variacions paramètriques de condicions de motor Diesel. Els assajos han estat realitzats sota condicions inertes i reactives en un motor de dos temps i una instal·lació d'alta pressió i alta temperatura de flux continu a pressió constant (CPF angl. Constant-Pressure Flow) emprant toberes mono-orifici, amb aplicació de diverses tècniques òptiques. Per a estudiar la influència de les propietats dels combustibles, van ser utilitzats distints mono-components, així com barreges binàries i un substitut de Diesel conformat per sis components, el qual fuel comparat amb Diesel convencional. Addicionalment, els resultats han estat contrastats amb un model unidimensional per a ajudar a explicar els valors i tendències trobats. Els resultats van presentar una forta dependència de les propietats dels combustibles en els assajos realitzats sota condicions inertes i reactives. La diferència entre les propietats físiques del n-decà i n-hexadecà van mostrar una reducció gairebé lineal sobre la longitud líquida estabilitzada fins a aproximadament un 60% sota certes condicions. Addicionalment, degut a la composició del combustible de substitució, el n-hexadecà pur va demostrar ser tindre característiques d'evaporació pràcticament idèntiques a aquell, demostrant ser un bon candidat per a ser un substitut mono-component del dièsel convencional. D'una manera similar, les propietats químiques dels PRFs n-heptà i iso-octà també provaren tindre influència sobre el desenvolupament del doll i la radiació emesa. Es van obtenir valors de temps de retard amb diferències de fins a un ordre de magnitud entre ambdós extrems del rang de les barreges, així com longituds d'enlairament de flama fins a tres vegades més llargues. La radiació emesa per la incandescència del sutge va presentar les variacions més grans, ja que algunes condicions van mostrar reduccions de fins a quatre ordres de magnitud dintre del rang de barreges. Encara més, alguns casos no van presentar radiació corresponent al sutge, i incrementar la sensibilitat de la càmera solament va ocasionar que la quimioluminiscència del radical OH* sigui detectada. D'altra banda, la longitud estabilitzada de flama calculada mitjançant la radiació del sutge no va presentar molta variació respecte a les propietats del combustible o la temperatura del aire. De fet, la única diferència apreciable va ser causada pels canvis en la composició del oxigen de l'aire ambient. En conclusió, les propietats dels combustibles van demostrar tenir un efecte significatiu en els processos d'un doll dièsel. Els combustibles més lleugers van afavorir l'evaporació del doll en un rang de condicions, mentres que els combustibles amb nombre d'octà més baixos van prendre més aviat i prop de la tovera però amb més lluminositat del sutge mesurat. / Vera-Tudela Fajardo, WM. (2015). An experimental study of the effects of fuel properties on diesel spray processes using blends of single-component fuels [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/58865 / TESIS

Ce travail porte sur la contribution à la modélisation thermodynamique d'un atelier de purification d'acide acrylique. Après l'identification des principaux produits intervenant dans l'étape de purification et la collecte de leurs propriétés thermodynamiques disponibles dans la littérature, nous avons effectué une série de mesures expérimentales pour un ensemble de mélanges contenant des acides carboxyliques (en particulier : diagrammes d'équilibres liquide-liquide et équilibres liquide-vapeur, enthalpies d'excès et volumes d'excès). L'ensemble des données (nos mesures et les valeurs de la littérature) a été exploité selon deux approches de modélisation des équilibres liquide-vapeur : une approche symétrique (φ-φ) appliquée aux équations d'état de Peng-Robinson (P-R) et de PC-SAFT et une approche dissymétrique (γ-φ) appliquée aux modèles de coefficients d'activité en phase liquide NRTL, UNIQUAC et Van Laar associés à diverses équations d'état en phase vapeur (gaz parfait, Viriel, Hayden et O'Connell et Nothnagel). Nous avons finalement retenu le modèle UNIQUAC associé à la corrélation de Hayden et O'Connell en phase vapeur. Des nouveaux paramètres d'interaction ont été déterminés et conduisent à des résultats homogènes et satisfaisants en comparaison avec nos mesures expérimentales et aux données de la littérature. Ils permettent également de décrire convenablement les diagrammes d'équilibres liquide-vapeur et les volatilités relatives des mélanges étudiés / This work focuses on the contribution in the thermodynamic modeling of an acrylic acid purification unit. After identifying the main products involved in the purification step and collecting their thermodynamic properties available in the literature, we conducted a series of experimental measurements for a range of mixtures containing carboxylic acids(mainly liquid-liquid equilibrium and vapor-liquid equilibrium diagrams, excess enthalpies and excess volumes).The data set-our measurements and literature values-was used according to two approaches for modeling vapor-liquid equilibrium: a symmetric approach(φ-φ) applied to the equations of state Peng-Robinson (P-R) and PC-SAFT and an asymmetrical approach (γ-φ) applied to the models of activity coefficients in the liquid phase NRTL, UNIQUAC and Van Laar associated with various equations of state in the vapor phase(ideal gas, Viriel, Hayden O'Connell and Nothnagel). We have finally chosen the UNIQUAC thermodynamic model associated with the correlation of Hayden O'Connell in vapor phase. New binary parameters were determined and led to consistent and satisfactory results in comparison with our experimental measurements and literature data. These parameters can also be used to adequately describe the diagrams of vapor-liquid equilibrium and the relative volatilities of the mixtures studied