Yes / Three equations of state with a group contribution model for binary interaction parameters were employed to calculate the vapor-liquid equilibria of synthetic and real natural gas mixtures with heavy fractions. In order to estimate the binary interaction parameters, critical temperatures, critical pressures and acentric factors of binary constituents of the mixture are required. The binary interaction parameter model also accounts for temperature. To perform phase equilibrium calculations, the heavy fractions were first discretized into 12 Single Carbon Numbers (SCN) using generalized molecular weights. Then, using the generalized molecular weights and specific gravities, the SCN were characterized. Afterwards, phase equilibrium calculations were performed employing a set of (nc + 1) equations where nc stands for the number of known components plus 12 SCN. The equations were solved iteratively using Newton's method. Predictions indicate that the use of binary interaction parameters for highly sour natural gas mixtures is quite important and must not be avoided. For sweet natural gas mixtures, the use of binary interaction parameters is less remarkable, however.

The knowledge of the phase behaviour of heavy oils and bitumen is important in order to understand the phenomenon of coke formation. Computation of their phase behaviour, using an equation of state, faces problems due to their complex composition. Hence n-alkane binaries of polyaromatic hydrocarbons are used to approximate the phase behaviour of heavy oils and bitumen. Appropriate values of binary interaction parameters are required for an equation of state to predict the correct phase behaviour of these model binary fluids. This thesis deals with fitting of the binary interaction parameter for the Peng-Robinson equation of state using landmarks in the binary phase space such as K- and L-points. A K- or an L-point is a point in the phase space where two phases become critical in the presence of another phase in equilibrium. An algorithm to calculate K- and L-points using an equation of state was developed. The variation of calculated K- and L-points with respect to the binary interaction parameter was studied and the results were compared with the experimental data in the literature. The interaction parameter was then fitted using the best match of experimental results with the computed ones. The binary interaction parameter fitted using a K- or an L-point was then used to predict the P-T projection of the binary system in phase space. Also, the qualitative effect of the binary interaction parameter on the P-T projection was studied. A numerical and thermodynamic study of the algorithm was done. Numerical issues like the initial guesses, convergence criterion and numerical techniques were studied and the thermodynamic constraints in the generalization of the algorithm are discussed. It was observed that the binary interaction parameter not only affects the location of K- and L-points in the phase space but also affects the calculation procedure of K- and L-points. Along with the propane binaries of polyaromatic hydrocarbons, K- and L-points were also calculated for systems like methane binaries of higher n-alkanes and the ethane + ethanol binary. In the case of the ethane + ethanol system, K- and L-points, matching the experimental results were calculated with different values of the binary interaction parameter. But the Peng-Robinson equation of state was unable to predict the correct type of phase behaviour using any value of the binary interaction parameter. The Peng-Robinson equation of state was able to predict the correct type of phase behaviour with the binary interaction parameter, fitted using K- and/or L-points for methane + n-alkane systems. The systems studied were the methane binaries of n-pentane, n-hexane and n-heptane. For the propane binaries of polyaromatic hydrocarbons, no value of the binary interaction parameter was able to predict the K-point with a good accuracy. The binary interaction parameter which gave the best possible results for a K-point failed to predict the correct type of phase behaviour. The binary interaction parameter fitted using the P-T projection enabled the Peng-Robinson equation of state to give a qualitative match for the high pressure complex phase behaviour of these systems. Solid phase equilibria were not taken into consideration.

The knowledge of the phase behaviour of heavy oils and bitumen is important in order to understand the phenomenon of coke formation. Computation of their phase behaviour, using an equation of state, faces problems due to their complex composition. Hence n-alkane binaries of polyaromatic hydrocarbons are used to approximate the phase behaviour of heavy oils and bitumen. Appropriate values of binary interaction parameters are required for an equation of state to predict the correct phase behaviour of these model binary fluids. This thesis deals with fitting of the binary interaction parameter for the Peng-Robinson equation of state using landmarks in the binary phase space such as K- and L-points. A K- or an L-point is a point in the phase space where two phases become critical in the presence of another phase in equilibrium. An algorithm to calculate K- and L-points using an equation of state was developed. The variation of calculated K- and L-points with respect to the binary interaction parameter was studied and the results were compared with the experimental data in the literature. The interaction parameter was then fitted using the best match of experimental results with the computed ones. The binary interaction parameter fitted using a K- or an L-point was then used to predict the P-T projection of the binary system in phase space. Also, the qualitative effect of the binary interaction parameter on the P-T projection was studied. A numerical and thermodynamic study of the algorithm was done. Numerical issues like the initial guesses, convergence criterion and numerical techniques were studied and the thermodynamic constraints in the generalization of the algorithm are discussed. It was observed that the binary interaction parameter not only affects the location of K- and L-points in the phase space but also affects the calculation procedure of K- and L-points. Along with the propane binaries of polyaromatic hydrocarbons, K- and L-points were also calculated for systems like methane binaries of higher n-alkanes and the ethane + ethanol binary. In the case of the ethane + ethanol system, K- and L-points, matching the experimental results were calculated with different values of the binary interaction parameter. But the Peng-Robinson equation of state was unable to predict the correct type of phase behaviour using any value of the binary interaction parameter. The Peng-Robinson equation of state was able to predict the correct type of phase behaviour with the binary interaction parameter, fitted using K- and/or L-points for methane + n-alkane systems. The systems studied were the methane binaries of n-pentane, n-hexane and n-heptane. For the propane binaries of polyaromatic hydrocarbons, no value of the binary interaction parameter was able to predict the K-point with a good accuracy. The binary interaction parameter which gave the best possible results for a K-point failed to predict the correct type of phase behaviour. The binary interaction parameter fitted using the P-T projection enabled the Peng-Robinson equation of state to give a qualitative match for the high pressure complex phase behaviour of these systems. Solid phase equilibria were not taken into consideration.

No description available.

O fator de compressibilidade (Z) de gás natural é utilizado em vários cálculos na engenharia de petróleo (avaliação de formações, perda de carga em tubulações, gradiente de pressão em poços de gás, cálculos de balanço de massa, medição de gás, compressão e processamento de gás). As fontes mais comuns de valores de Z são medições experimentais, caras e demoradas. Essa propriedade também é estimada por correlações empíricas, modelos baseados no princípio dos estados correspondentes ou equações de estado (EOS). Foram avaliadas as capacidades das EOS de Soave-Redlich-Kwong (SRK), Peng-Robinson (PR), Patel-Teja (PT), Patel-Teja-Valderrama (PTV), Schmidt-Wenzel (SW), Lawal-Lake-Silberberg (LLS) e AGA-8 para previsão desta propriedade em aproximadamente 2200 pontos de dados experimentais. Estes pontos foram divididos em quatro grupos: Grupo 1 (Presença de frações C7+, Grupo 2 (temperaturas inferiores a 258,15 K), Grupo 3 (pressões superiores a 10000 kPa) e Grupo 4 (pressões inferiores a 10000 kPa). Os cálculos utilizando as equações de estado sob diferentes esquemas de previsão de coeficientes binários de interação foram cuidadosamente investigados. Os resultados sugerem que a EOS AGA-8 apresenta os menores erros para pressões de até 70000 kPa. Entretanto, observou-se uma tendência de aumento nos desvios médios absolutos em função das concentrações de CO2 e H2S. As EOS PTV e a EOS SW são capazes de predizer o fator de compressibilidade (Z) com desvios médios absolutos entre os valores calculados e experimentais com precisão satisfatória para a maioria das aplicações, para uma variada faixa de temperatura e pressão. Este estudo também apresenta uma avaliação de 224 métodos de cálculo de Z onde foram utilizadas 8 correlações combinadas com 4 regras de mistura para estimativa de temperaturas e pressões pseudorreduzidas das amostras, junto com 7 métodos de caracterização das propriedades críticas da fração C7+, quando presente na composição do gás. Em função dos resultados são sugeridas, para diferentes tipos de sistemas, as melhores combinações de correlações com regras de mistura capazes de predizer fatores de compressibilidade (Z) com os menores erros absolutos médios relativos / The compressibility factor (Z-factor) of natural gases is necessary in many petroleum engineering calculations (evaluation of formation, pressure drop through a pipe, pressure gradient in gas wells, material balance calculations, gas metering, gas compression and processing). The most common sources of Z-factor values are experimental measurements, which are expensive and time consuming. This property is also estimated from empirical correlations, corresponding state models or equations of state (EOS) when experimental data is unavailable. Capabilities of Soave-Redlich-Kwong (SRK), Peng-Robinson (PR), Patel-Teja (PT), Patel-Teja-Valderrama (PTV), Schmidt-Wenzel (SW), Lawal-Lake-Silberberg (LLS) and AGA-8 to predict this property of 2200 data points under various schemes of binary interaction numbers are thoroughly investigated. This database was split on four groups: Group 1 (presence of hydrocarbon plus fraction - C7+), Group 2 (temperatures lower than 258.15 K), Group 3 (pressures higher than 10000 kPa) e Group 4 (pressures lower than 10000 kPa). The best results were obtained from EOS AGA-8 for pressures up to 70000 kPa. However, an increasing trend in average absolute deviations was observed as a function of CO2 e H2S concentrations. EOS PTV and EOS SW are capable to predict the compressibility factor (Z) with average absolute deviation between calculated and experimental values with satisfactory accuracy for most applications for a wide range of temperature and pressure. This study also presents an evaluation of 224 possible methods of calculating the gas compressibility factor, based on 8 correlations and corresponding state models, combined with 4 mixing rule that predict the pseudo-reduced pressure and temperatures of the mixture, that were combined with 7 methods of characterizing the plus fraction critical properties when present in the gas composition. Results suggest for different systems conditions, the best correlation and mixing rule combination capable of predicting Z-factor with the least average absolute relative error

O fator de compressibilidade (Z) de gás natural é utilizado em vários cálculos na engenharia de petróleo (avaliação de formações, perda de carga em tubulações, gradiente de pressão em poços de gás, cálculos de balanço de massa, medição de gás, compressão e processamento de gás). As fontes mais comuns de valores de Z são medições experimentais, caras e demoradas. Essa propriedade também é estimada por correlações empíricas, modelos baseados no princípio dos estados correspondentes ou equações de estado (EOS). Foram avaliadas as capacidades das EOS de Soave-Redlich-Kwong (SRK), Peng-Robinson (PR), Patel-Teja (PT), Patel-Teja-Valderrama (PTV), Schmidt-Wenzel (SW), Lawal-Lake-Silberberg (LLS) e AGA-8 para previsão desta propriedade em aproximadamente 2200 pontos de dados experimentais. Estes pontos foram divididos em quatro grupos: Grupo 1 (Presença de frações C7+, Grupo 2 (temperaturas inferiores a 258,15 K), Grupo 3 (pressões superiores a 10000 kPa) e Grupo 4 (pressões inferiores a 10000 kPa). Os cálculos utilizando as equações de estado sob diferentes esquemas de previsão de coeficientes binários de interação foram cuidadosamente investigados. Os resultados sugerem que a EOS AGA-8 apresenta os menores erros para pressões de até 70000 kPa. Entretanto, observou-se uma tendência de aumento nos desvios médios absolutos em função das concentrações de CO2 e H2S. As EOS PTV e a EOS SW são capazes de predizer o fator de compressibilidade (Z) com desvios médios absolutos entre os valores calculados e experimentais com precisão satisfatória para a maioria das aplicações, para uma variada faixa de temperatura e pressão. Este estudo também apresenta uma avaliação de 224 métodos de cálculo de Z onde foram utilizadas 8 correlações combinadas com 4 regras de mistura para estimativa de temperaturas e pressões pseudorreduzidas das amostras, junto com 7 métodos de caracterização das propriedades críticas da fração C7+, quando presente na composição do gás. Em função dos resultados são sugeridas, para diferentes tipos de sistemas, as melhores combinações de correlações com regras de mistura capazes de predizer fatores de compressibilidade (Z) com os menores erros absolutos médios relativos / The compressibility factor (Z-factor) of natural gases is necessary in many petroleum engineering calculations (evaluation of formation, pressure drop through a pipe, pressure gradient in gas wells, material balance calculations, gas metering, gas compression and processing). The most common sources of Z-factor values are experimental measurements, which are expensive and time consuming. This property is also estimated from empirical correlations, corresponding state models or equations of state (EOS) when experimental data is unavailable. Capabilities of Soave-Redlich-Kwong (SRK), Peng-Robinson (PR), Patel-Teja (PT), Patel-Teja-Valderrama (PTV), Schmidt-Wenzel (SW), Lawal-Lake-Silberberg (LLS) and AGA-8 to predict this property of 2200 data points under various schemes of binary interaction numbers are thoroughly investigated. This database was split on four groups: Group 1 (presence of hydrocarbon plus fraction - C7+), Group 2 (temperatures lower than 258.15 K), Group 3 (pressures higher than 10000 kPa) e Group 4 (pressures lower than 10000 kPa). The best results were obtained from EOS AGA-8 for pressures up to 70000 kPa. However, an increasing trend in average absolute deviations was observed as a function of CO2 e H2S concentrations. EOS PTV and EOS SW are capable to predict the compressibility factor (Z) with average absolute deviation between calculated and experimental values with satisfactory accuracy for most applications for a wide range of temperature and pressure. This study also presents an evaluation of 224 possible methods of calculating the gas compressibility factor, based on 8 correlations and corresponding state models, combined with 4 mixing rule that predict the pseudo-reduced pressure and temperatures of the mixture, that were combined with 7 methods of characterizing the plus fraction critical properties when present in the gas composition. Results suggest for different systems conditions, the best correlation and mixing rule combination capable of predicting Z-factor with the least average absolute relative error

Le développement du modèle prédictif E-PPR78, basé sur une méthode de contribution de groupe, a été entrepris depuis plus de dix ans pour prédire le comportement de systèmes multiconstituants. Ce modèle repose sur l'équation d'état de Peng-Robinson dans sa version de 1978 et les règles de mélanges de Van der Waals. Il utilise un seul paramètre d'interaction binaire, kij, qui dépend de la température. Afin de permettre au modèle E-PPR78 de prédire le comportement du gaz naturel, trois nouveaux groupes sont ajoutés : le monoxyde de carbone, l'hélium et l'argon. Pour cela, il a été nécessaire de former une base de données expérimentales la plus large possible contenant les mesures d'équilibres de phase et d'enthalpies de mélange pour les systèmes binaires constitués par ces trois groupes ainsi que ceux définis dans les études précédentes et présents dans le gaz naturel. Après une description de la classification des diagrammes de phase de Van Konynenburg et Scott, le modèle E-PPR78 est présenté. La troisième partie est consacrée à l'ajout des trois nouveaux groupes au sein du modèle. Les résultats sont obtenus avec une précision satisfaisante. Il apparaît clairement que le modèle E PPR78 est capable de prédire le comportement du gaz naturel dans des conditions de températures et de pressions particulièrement larges / The development of the predictive E-PPR78 model, based on a contribution group method, has been undertaken since ten years to predict accurately the behaviour of multi-component systems. This model lies on the Peng-Robinson equation of state with classical Van der Waals mixing rules. It uses a unique binary interaction parameter, kij, which is temperature dependant. To enable the E-PPR78 model to predict the behavior of natural gases, three new groups are added: carbon monoxide, helium and argon. It was necessary to build an experimental database, as exhaustive as possible, containing phase equilibrium and enthalpies of mixing data for binary systems formed by these groups and those defined in previous studies and present in natural gases. After a description of the classification scheme of Van Konynenburg and Scott, the E-PPR78 model is described. The third part is about the addition of the three new groups to the model. It clearly appears that the E-PPR78 model is able to predict the fluid-phase behavior of natural gases over wide ranges of temperatures and pressures

Nous avons développé un modèle prédictif, utilisant le principe de contribution de groupes, pour prédire avec précision, le comportement des fluides pétroliers. Ce modèle baptisé PPR78 utilise l’équation d’état de Peng et Robinson et des règles de mélange de type Van der Waals avec un coefficient d’interaction binaire kij, dépendant de la température. De telles règles de mélange sont équivalentes à celles obtenues en combinant à compacité constante une fonction d’excès de type Van Laar et une équation d’état cubique.La première partie de cette étude a consisté à étendre le domaine d’application du modèle PPR78 aux systèmes contenant de l’eau, des alcènes et de l’hydrogène, en définissant six nouveaux groupes élémentaires. Une bonne précision du modèle est obtenue pour décrire les équilibres de phases de systèmes binaires impliquant ces constituants, notamment pour les systèmes présentant des diagrammes de phases de Type I et de Type II. Dans la deuxième partie l’ensemble des paramètres de groupes ont été réajustés, non seulement sur des données d’équilibres de phases mais également sur des données de grandeur de mélange. L’avantage de ce nouveau modèle E-PPR78 est qu’il permet de restituer les équilibres de phases avec une précision équivalente au modèle original et qu’il conduit à une très nette amélioration de la prédiction des enthalpies d’excès et des capacités calorifiques d’excès. / We have developed a predictive model, by means of a group contribution method, in order to predict with accuracy, the behavior of petroleum fluids. The model called PPR78 uses the Peng-Robinson equation of state and Van der Waals-type mixing rules with a temperature dependent binary interaction parameter kij. Such mixing rules are identical to those obtained by combining at constant packing fraction, a Van Laar-type excess function and a cubic equation of state.The first part of this study consisted in extending the application of the model PPR78 to systems containing water, alkenes and hydrogen, by defining six new elementary groups. The phase equilibria of binary systems involving these components are accurately described by the model, especially for the phase diagrams of Type I and Type II. In the second part, all the group parameters of the original model were re-fitted by using the phase equilibrium data, as well as the mixing property data. The advantage of this new model E-PPR78 is that it is capable to correlate the phase equilibria with an accuracy which is equivalent to the original model and it produces a very clear improvement in the prediction of excess enthalpies and excess heat capacities.

Le développement d'un modèle thermodynamique prédictif PPR78, basé sur le concept de contributions de groupes, a été entrepris afin de pouvoir prédire avec précision, le comportement des fluides pétroliers. PPR78 utilise l’équation d’état de Peng et Robinson et les règles de mélange de Van der Waals avec un seul coefficient d’interactions binaires kij, dépendant de la température. Cette approche est rigoureusement équivalente à l’utilisation de règles de mélange à compacité constante avec un modèle d’énergie de Gibbs molaire d’excès, gE, de type Van Laar. Pour développer ce modèle, une étude approfondie des équilibres entre phases fluides des systèmes binaires a été réalisée en deux temps. Dans un premier, une étude phénoménologique permet d'éclairer sous un jour nouveau la classification proposée par Van Konynenburg et Scott qui décrit qualitativement les comportements de ces systèmes. Dans un second temps, quelques principes généraux de calcul des diagrammes d’équilibre de phases isothermes, isobares et globaux sont exposés. L’étude de la stabilité thermodynamique globale occupe une place essentielle au sein de ces calculs. Une fois ces étapes préliminaires franchies, l’extension du modèle aux groupes CO2, N2, H2S et sulfhydryle est réalisée. Une bonne précision du modèle est obtenue pour décrire les systèmes binaires impliquant ces quatre groupes. Enfin, le comportement des fluides pétroliers est souvent prédit avec une précision de l'ordre de l'erreur expérimentale par PPR78 / A predictive thermodynamic model, based on the group contribution concept, and called PPR78, has been developed in order to be able to predict, with high accuracy, the behaviour of petroleum fluids. PPR78 uses the Peng-Robinson equation of state with Van der Waals mixing rules and a temperature dependent binary interaction parameter kij. This method is the equivalent to the constant packing fraction mixing rules with a Van Laar excess Gibbs energy model (gE). To develop the model, an in-depth study on binary systems fluid phase equilibria, was carried out. It was divided into two parts. Firstly, a phenomenological study made a reappraisal of the Van Konynenburg and Scott classification possible. Secondly, some general rules for the calculation of isothermal, isobaric and global phase equilibrium diagrams were demonstrated. It is important to note that the study of the global thermodynamic stability is essential in the calculations. Once these preliminary steps were realized, the extension of the model to the CO2, N2, H2S and sulfhydryl groups was performed. The fluid phase behaviour of binary systems involving these four groups was accurately calculated by the PPR78 model. Finally, the properties of petroleum fluids were predicted by PPR78 with an accuracy close to the experimental uncertainty

Understanding the functional impact of physical interactions between proteins and DNA on gene expression is important for developing approaches to correct disease-associated gene dysregulation. I conducted a systematic, functional genetic analysis of protein-DNA interactions in the promoter region of the yeast ribonucleotide reductase subunit gene RNR3. I measured the transcriptional impact of systematically perturbing the major transcriptional regulator, Crt1, and three X-box sites on the DNA known to physically bind Crt1. This analysis revealed interactions between two of the three X-boxes in the presence of Crt1, and unexpectedly, a significant functional role of the X-boxes in the absence of Crt1. Further analysis revealed Crt1- independent regulators of RNR3 that were impacted by X-box perturbation. Taken together, these results support the notion that higher-order X-box-mediated interactions are important for RNR3 transcription, and that the X-boxes have unexpected roles in the regulation of RNR3 transcription that extend beyond their interaction with Crt1.