The fouling characteristics of a desalted crude oil were investigated in a systematic investigation. There are two main parts in this study, the dry bulk tests (dehydrated crude oil) and the wet bulk tests (to which desalter brine was added). Three barrels of desalted crude oil provided by Amoco Oil Company were studied. For the dry bulk tests, no brine was added to the crude oil. The effects of fluid velocity and surface temperature on fouling were investigated. The higher the surface temperature the greater the fouling was observed. Fouling decreased with an increase of fluid velocity. Fluid velocity had a stronger effect on fouling at low surface temperatures than at high surface temperatures. It was also observed that the fouling behavior of crude oil depended on small difference in composition. The threshold surface temperatures for the initiation of fouling were 400-450 °F (3.0 ft/sec), 525-550 °F (5.5 ft/sec), 550-600 °F (8.0 ft/sec) and about 600 °F (10.0 ft/sec) for Barrel No. 2 and Barrel No. 3. For Barrel No. 1 however, the threshold surface temperatures were about 550 °F (3.0 ft/sec) and 600 °F (5.5 ft/sec). For the wet bulk tests, a certain amount desalter brine (weight percentage = 0.8%) was added to the crude oil for each run. The effects of fluid velocity, surface temperature and the presence of brine on fouling were investigated. Higher surface temperature enhanced fouling considerably. Fouling was reduced as fluid velocity was increased. It was shown that brine had a strong effect on fouling. No fouling occurred for velocities of 5.5 and 8.0 ft/sec at a surface temperature of 350 °F which was a condition for which an aqueous phase was present and the salt remained in solution. Significant fouling occurred for velocities of 5.5 and 8.0 ft/sec at a surface temperature operated at a low 400 °F (Tb = 300 °F) which was a condition for which the aqueous phase at the heat transfer surface was dissolved or boiled to extinction and the salt was deposited on the heat transfer surface. / Graduation date: 1991

Electrospray Ionization (ESI) is a technique that permits the soft ionization of large proteins and biomolecules without fragmenting them, which allows them to be characterized via Mass Spectrometry (MS). It has the potential of permitting the identification of transient intermediate products in biological processes in situ, which would provide great insight to researchers in the growing fields of proteomics and metabolomics. However, this application presents a technical challenge in that most relevant biochemistry occurs in aqueous solutions with high salt content, which makes successful identification of analytes by ESI-MS difficult. This thesis presents the design, fabrication, and characterization of a microfabricated dialysis module that could alleviate this issue by desalting samples inline between sampling and electrospraying interfaces. Its small volume (~10 nL) minimizes sample transit time and, thus, optimizes ESI-MS analysis temporal resolution. A preliminary analytical model of dialysis elucidates the key performance parameters and sets the guidelines for consideration in its design. The device is then microfabricated in a cleanroom environment using techniques that have been well established by the microelectronics industry such as E-beam evaporation and Reactive Ion Etching. The system efficiency is demonstrated experimentally by assessing its salt removal effectiveness as a function of sample residence time. Mass spectrometry analyses of proteins in solutions with high salt content further corroborate its performance.

O balanço populacional é um método comprovado de se aumentar a previsibilidade do comportamento de um sistema multifásico, e sua utilização em conjunto de técnicas de CFD tem sido cada vez maior pelo desenvolvimento constante de ambas as tecnologias. Este trabalho apresenta o equacionamento genérico do balanço populacional para sistemas bifásicos com agregação e quebra de partículas, além de uma discussão sobre a natureza de sistemas bifásicos. Métodos numéricos específicos para a resolução deste tipo de problema são discutidos, implementados e validados. Como exemplo de aplicação do equacionamento sugerido, é obtido um modelo específico para o caso de coalescência de gotas de água salgada dispersas numa fase óleo submetidas a um campo elétrico alternado, como no processo de dessalgação de petróleo. Um algoritmo baseado em autômatos celulares é utilizado como fonte de dados para validação do modelo e técnicas de CFD produzem um perfil de escoamento da emulsão. / The population balance is a proven method for increasing a multiphase systems behavior predictability, and its employment along with CFD techniques is increasing following the constant development of both technologies. This work presents the generic Population Balance Equations for two-phase systems where its particles suffer aggregation and breakage and a discussion on the nature of two-phase systems. Specific numerical methods for the solution of such problems are discussed, implemented and validated. A specific model for the coalescence of water droplets dispersed in an oily phase under the effects of an alternated electric field is obtained as an application example of the suggested equations, mimicking the oil desalting process. A cellular automata based algorithm is used as data source for the models validation and CFD techniques are used to produce the emulsions flow profile.

O balanço populacional é um método comprovado de se aumentar a previsibilidade do comportamento de um sistema multifásico, e sua utilização em conjunto de técnicas de CFD tem sido cada vez maior pelo desenvolvimento constante de ambas as tecnologias. Este trabalho apresenta o equacionamento genérico do balanço populacional para sistemas bifásicos com agregação e quebra de partículas, além de uma discussão sobre a natureza de sistemas bifásicos. Métodos numéricos específicos para a resolução deste tipo de problema são discutidos, implementados e validados. Como exemplo de aplicação do equacionamento sugerido, é obtido um modelo específico para o caso de coalescência de gotas de água salgada dispersas numa fase óleo submetidas a um campo elétrico alternado, como no processo de dessalgação de petróleo. Um algoritmo baseado em autômatos celulares é utilizado como fonte de dados para validação do modelo e técnicas de CFD produzem um perfil de escoamento da emulsão. / The population balance is a proven method for increasing a multiphase systems behavior predictability, and its employment along with CFD techniques is increasing following the constant development of both technologies. This work presents the generic Population Balance Equations for two-phase systems where its particles suffer aggregation and breakage and a discussion on the nature of two-phase systems. Specific numerical methods for the solution of such problems are discussed, implemented and validated. A specific model for the coalescence of water droplets dispersed in an oily phase under the effects of an alternated electric field is obtained as an application example of the suggested equations, mimicking the oil desalting process. A cellular automata based algorithm is used as data source for the models validation and CFD techniques are used to produce the emulsions flow profile.

The history of crude oil desalting/dehydration plant (DDP) has been marked in progressive phases-the simple gravity settling phase, the chemical treatment phase, the electrical enhancement phase and the dilution water phase. In recent times, the proper cachet would be the control-optimisation phase marked by terms such as "DDP process control", "desalter optimisation control" or "DDP automating technology". Another less perceptible aspect, but nonetheless important, has been both a punch listing of traditional plant boundaries and a grouping of factors that play the essential roles in a desalting/dehydration plant (DDP). Nowadays, modelling and optimising of a DDP performance has become more apparent in petroleum and chemical engineering, which has been traditionally concerned with production and refinery processing industries. Today's desalting/dehydration technology finds itself as an important factor in such diverse areas as petroleum engineering, environmental concerns, and advanced technology materials. The movement into these areas has created a need not only for sources useful for professionals but also for gathering relevant information essential in improving product quality and its impact on health, safety and environmental (HSE) aspects. All of the foregoing, clearly establishes the need for a comprehensive knowledge of DDP and emulsion theories, process modelling and optimisation techniques. The main objective of this work is to model and qualitatively optimise a desalting/dehydration plant. In due course, the contents of this thesis will cover in depth both the basic areas of emulsion treatment fundamentals, modelling desalting/dehydration processes and optimising the performance of desalting plants. In addition, emphasis is also placed on more advanced topics such as optimisation technology and process modifications. At the results and recommendation stage, the theme of this work-optimising desalting/dehydration plant will practically be furnished in an applicable scheme. Finally, a significant compendium of figures and experimental data are presented. This thesis, therefore, essentially presents the research and important principles of desalting/dehydration systems. It also gives the oil industry a wide breadth of important information presented in a concise and focused manner. In search of data quality and product on-line-improvement, this combination will be a powerful tool for operators and professionals in a decision support environment.

Este trabalho visa o estudo da viabilidade da redução do uso de água no processo de dessalgação em refinarias de petróleo. Em uma primeira fase, foi necessário o estudo teórico da separação das emulsões água/óleo. Em seguida, foi desenvolvido um modelo matemático baseado nas forças atuantes nas gotas de água, o que possibilitou a determinação do tempo entre as colisões de pares de gotas e o estabelecimento do critério para que ocorra o fenômeno de coalescência. Esse modelo foi empregado em um sistema desenvolvido com base em autômatos celulares, o qual possibilitou o acompanhamento do processo micro e macroscópico, através do cálculo para o conjunto das gotas, e o acompanhamento visual até a separação da fase contínua. Os experimentos de laboratório, para os quais foi usado equipamento ótico para a medição da intensidade de luz transmitida ou espalhada pelas gotas, possibilitaram avaliar a influência da qualidade da água de mistura no tempo de separação das emulsões. Na unidade industrial, foram realizados testes que permitiram analisar o desempenho das dessalgadoras em diferentes situações operacionais. Os resultados obtidos através dos experimentos de laboratório e da simulação usando o modelo matemático desenvolvido mostraram-se compatíveis com os dados obtidos nos testes na unidade industrial. O trabalho mostrou ser possível alterar os esquemas de usos de água nas dessalgadoras, aumentando a taxa de reciclagem e possibilitando a otimização do consumo de água fresca neste processo, o que resultaria em redução substancial no consumo geral de água na refinaria. / The aim of this work is the study of the reduction of water consumption in petroleum desalting processes. The study of the attraction forces acting on the droplets was necessary to know how the emulsion water/oil is separated. A mathematical model based upon these forces was built to calculate the time between each droplets collision and to establish criteria for their coalescence. This model was applied to a system developed based on cellular automata, which allows to follow the process micro and macroscopically. Computations were carried out to the ensemble of droplets and the visual progression, from the start of droplets separation of the continuous phase to the end of the process could be visualized. Laboratory experiments, in which optical equipment was used to measure the light intensity transmitted or scattered by the droplets, allowed to evaluate the influence of the type of mixing water in the separation time of the emulsions. Tests in the industrial unity allowed evaluating the performance of the desalting units at different operating conditions. Conclusions of the laboratory experiments and the results of the mathematical model were compared with results of the industrial tests, showing coherence between them. The work shows that it is possible to simulate the effect of the operating variables and to alter schemes of water use in desalting units, increasing the water recycling rate, allowing optimization of fresh water consumption in this process and reducing the total water consumption in the refinery.

Este trabalho visa o estudo da viabilidade da redução do uso de água no processo de dessalgação em refinarias de petróleo. Em uma primeira fase, foi necessário o estudo teórico da separação das emulsões água/óleo. Em seguida, foi desenvolvido um modelo matemático baseado nas forças atuantes nas gotas de água, o que possibilitou a determinação do tempo entre as colisões de pares de gotas e o estabelecimento do critério para que ocorra o fenômeno de coalescência. Esse modelo foi empregado em um sistema desenvolvido com base em autômatos celulares, o qual possibilitou o acompanhamento do processo micro e macroscópico, através do cálculo para o conjunto das gotas, e o acompanhamento visual até a separação da fase contínua. Os experimentos de laboratório, para os quais foi usado equipamento ótico para a medição da intensidade de luz transmitida ou espalhada pelas gotas, possibilitaram avaliar a influência da qualidade da água de mistura no tempo de separação das emulsões. Na unidade industrial, foram realizados testes que permitiram analisar o desempenho das dessalgadoras em diferentes situações operacionais. Os resultados obtidos através dos experimentos de laboratório e da simulação usando o modelo matemático desenvolvido mostraram-se compatíveis com os dados obtidos nos testes na unidade industrial. O trabalho mostrou ser possível alterar os esquemas de usos de água nas dessalgadoras, aumentando a taxa de reciclagem e possibilitando a otimização do consumo de água fresca neste processo, o que resultaria em redução substancial no consumo geral de água na refinaria. / The aim of this work is the study of the reduction of water consumption in petroleum desalting processes. The study of the attraction forces acting on the droplets was necessary to know how the emulsion water/oil is separated. A mathematical model based upon these forces was built to calculate the time between each droplets collision and to establish criteria for their coalescence. This model was applied to a system developed based on cellular automata, which allows to follow the process micro and macroscopically. Computations were carried out to the ensemble of droplets and the visual progression, from the start of droplets separation of the continuous phase to the end of the process could be visualized. Laboratory experiments, in which optical equipment was used to measure the light intensity transmitted or scattered by the droplets, allowed to evaluate the influence of the type of mixing water in the separation time of the emulsions. Tests in the industrial unity allowed evaluating the performance of the desalting units at different operating conditions. Conclusions of the laboratory experiments and the results of the mathematical model were compared with results of the industrial tests, showing coherence between them. The work shows that it is possible to simulate the effect of the operating variables and to alter schemes of water use in desalting units, increasing the water recycling rate, allowing optimization of fresh water consumption in this process and reducing the total water consumption in the refinery.

In the biopharmaceutical industry, identification of glycans in a glycoprotein is a regulatory requirement and is a part of the characterization of the protein. Glycans are constructed of several monosaccharides linked together. N-linked glycans, which have been studied in this project, are attached to the nitrogen atom in asparagine. A method for separating N-linked glycans by high performance anion exchange chromatography had already been developed at the department. To develop a method for identification of the N-glycans by mass spectrometry, a desalting method on porous graphitic carbon (PGC) columns was used and optimized resulting in the eluents A (0,05% TFA in ACN:water 5:95 v/v) and B (0,05% TFA in ACN:water 50:50 v/v). Also the sample introduction on the mass spectrometer was optimized and resulted in a sensitive on-line liquid chromatography mass spectrometry (LC-MS) approach which gave mass spectrometric peaks with high signal to noise ratios and with high mass accuracy. The developed procedure was then successfully used on glycans cleaved from a glycoprotein separated by high performance anion exchange chromatography with pulsed amperometric detector.

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Thesis (M. Phil.)--University of Hong Kong, 1982.