Yes / Waxy crude oils are pumped hot but upon power cut, pumping stops, the oil cools leading below the wax appearance temperature to precipitation of the wax and the formation of a gel throughout the pipe. In such a situation, what is the minimum pressure required to restart flow, not to merely deform the gel or break it? This paper provides a solution to this problem using microscopic observations under controlled cooling conditions and rheological data conducted in constant stress mode under controlled temperature and cooling conditions and restart experiments in laboratory pipelines replicating the rheometric conditions and deviations from them to inform large diameter operation in the field. Three important findings derive from the experimental data collected: (i) A fragmentation stress , rather than the static stress that precedes it, is found to be the more accurate predictor of flow re-start pressures; (ii) Waxy crude oils gels exhibit true yield stress and yielding process but also show flow on application of the slightest stress below yielding; (iii) This flow, in the elastic region, is jagged rather than continuous suggesting a consolidation process of the crystals and their agglomerates forming the gel. In the broader context of the existence of a yield stress, the data presented here show that there is such a thing as a yield stress and the concepts of a yield stress and that everything flows are not mutually exclusive.

Waxy crude oils (1/3 of oil produced worldwide), pumping through pipelines considered risky operation due to the crude wax content (15-40 wt.%) and to the temperature at which wax supersaturates and precipitates, leading to the danger of pipe blockage, eventually resulting, in multimillion dollars loss in production and maintenance. This research undertaken to develop operational strategy of waxy crude pipelines, considering the crude and crude gel properties and flow conditions. The research problem was approached by characterizing the crude gel with and without additives using chromatography (GC), differential scanning calorimetry (DSC), cross polarised microscopy (CPM), controlled stress and oscillatory shear rheology (CSR and OSR), the principal parameters being the crude temperature and the rate at which the crude was cooled. GC and DSC were useful in establishing wax composition, content and wax appearance temperature (WAT). Control stress rheometer proved to be the most appropriate as it measured the reduction in apparent viscosity at full production (10-50 s-1 shear rate), near shutdown (1 s-1 ) and yielding when the oil was statically cooled. On this basis, it was established that the wax inhibitor was the most effective. CPM revealed that only the wax inhibitor changed the structure of the gel, disrupting its otherwise knitted crystal network. Dilution with the light crude oil merely reduced the wax content and the pour point depressant reduced the gelling temperature. OSR provided a check on CSR and confirmed the gelation temperature measured. CSR provided the yield stress measured, it also provided comprehensive data that can be used for theoretical modelling of this complex flow. / Libyan Petroleum Institute, Libya

[pt] O petróleo é uma mistura complexa de hidrocarbonetos e pode conter em sua composição parafinas que, quando submetidas a baixas temperaturas, podem precipitar e gelificar, apresentando uma Tensão Limite de Escoamento. O estudo do comportamento do petróleo nesta condição é importante para a indústria porque, uma vez que o petróleo esteja gelificado, o reinício do escoamento pode demandar a adição de energia ao sistema, cujo dimensionamento para operação com altas pressões envolve custos elevados. Os valores de pressão de reinício de escoamento do petróleo gelificado encontrados no campo são frequentemente menores em relação aos valores calculados. O presente trabalho simulou o processo de reinício de escoamento através de uma bancada experimental que reproduz o resfriamento estático sofrido pelo petróleo parafínico em um duto submarino. Além disso, são apresentados dois métodos para cálculo da contração que resulta do resfriamentoe gelificação dos óleos parafínicos, objetivando verificar se existe uma relação entre a contração do fluido e a diferença entre a Tensão Limite de Escoamento e a tensão efetiva para iniciar o seu escoamento. O primeiro método proposto é o método da Pipeta, que consiste na utilização de uma pipeta, acoplada a um recipiente com controle de temperatura, para medição do volume de líquido. O segundo método proposto é o da célula PVT, que consiste na utilização de um sistema fechado de volume conhecido em que a medição da variação do volume de líquido é estimada pela variação do volume do gás à baixa pressão com a adoção da hipótese de gás ideal. Foram utilizados fluidos sintéticos, visando representar o petróleo parafínico, com diferentes concentrações de parafina, óleo mineral e querosene. A determinação da Tensão Limite de Escoamento foi feita a partir de testes de Creep. Os resultados mostraram que a contração do fluido é uma grandeza de difícil medição, com um alto grau de incerteza, mas que é possível estimar ordem de grandeza dessa contração para os fluidos estudados. / [en] Petroleum, as it is a complex mixture of hydrocarbons, may contain paraffinic compounds which, when subjected to low temperatures, can deposit and gel. The study of the behavior of petroleum in this condition is very important for the industry because, once the waxy crude oil gels, the restart process may demand extra energy addition to the system, whose dimensioning is expensive for high operation required pressures. Restart pressure values of the gelled oil found from laboratory tests often show a significant difference from the real values found in the field. In order to compare the yield stress and the effective stress, the present work simulated the flow restarting process through an experimental rig to reproduce the static cooling applied to a pipeline with waxy crude oil. In addition, two methods are presented for calculating the thermal shrinkage formed during the cooling and gelation of the waxy crude oils, in order to verify if there is a relationship between the shrinkage and the difference between the yield stress and the effective stress to start flowing. The first method proposed is the Pipette method, which consists of the use of a pipette, coupled to a container with temperature control, to measure the volume of liquid. The second method proposed is the PVT cell method, which consists of the use of a closed system of known volume in which the measurement of the liquid volume variation is estimated by the variation of the gas volume at low pressure with the adoption of the Ideal gas hypothesis. The fluids selected for the studies to represent paraffinic oil were laboratory-synthesized fluids with different concentrations of paraffin, mineral oil and kerosene, and they were characterized rheologically by stress ramp and creep tests for the determination of the yields stress. The results showed that thermal shrinkage is a difficult quantity to measure, which gives it a high degree of uncertainty, but it is possible to estimate the magnitude order of the thermal shrinkage for the fluids studied.

Twenty years ago, Chang et al. (1998) introduced the three-yield stresses concept (dynamic, static and elastic limits) to describe yielding of waxy crude oils cooled below the wax appearance temperature (WAT). At the time, the limits in rheological instruments were such that they never actually measured the elastic-limit, a key fundamental property. Using modern instruments, this research succeeds in recording for the first time the entire yielding process down to stresses of 10-7 Pa and shear rate of 10-6 min-1 as a function of temperature, cooling rate and stress loading rate using two waxy oils of different origins and wax content. A four-yield stress model is established using derivative data (dynamic fluidity and failure acceleration). In addition, calorimetry (DSC) and microscopy (CPM) helped extract WAT, the gel and pour points and link gel crystal structure and its yielding and breakage to rheological properties. The yielding stresses measured rheologically were tested in laboratory pipelines at two diameter scales, 6.5mm and 13.5mm to compare stresses in uniform and non-uniform cooling. It is demonstrated that rheological instruments can only predict gel breaking pressure when the cooling rate is low, i.e. yielding at the pipe wall. A complementary heat transfer study was performed on a section of pipe statically cooled, both experimentally and theoretically to predict the gel front-liquid oil interface that develops in industrial pipeline where gel breaking occurs. This key information together with rheological data provide the means to predict accurately restart pressures of shut gelled pipelines that have eluded previous research. / Ministry of Higher Education of the Libyan Government

[pt] Durante a gelificação por parafina, a rede de cristais de parafina modifica o comportamento do óleo cru. Ele muda de um material newtoniano de baixa viscosidade para um material com dependência temporal e de alta viscosidade com tensão limite do escoamento. Com isto, é totalmente desafiador descobrir a pressão minima de início do fluxo de petróleo gelificado com uma microestrutura tão complexa. Através da minha dissertação de mestrado, investigamos dois materiais viscoplásticos: um gel de cabelo com uma tixotropia desprezível e uma suspensão aquosa tixotrópica 2 por cento de laponita para imitar o início de fluxo de óleos gelificados. Para ambos os materiais, o gradiente de pressão axial mínimo necessário para o início do fluxo foi medido e os valores medidos estavam de acordo com a previsão do balanço de força convencional. Por outro lado, os casos da indústria exibiram que o balanço de força mencionado acima leva a uma superestimação da pressão mínima inicial. Em alguns estudos, uma explicação elicitada é o comportamento tixotrópico do petróleo gelificado, mas nossos resultados acima mencionados serviram para refutá-lo. Durante a primeira parte da minha tese de doutorado, buscamos verificar por laboratório porque o balanço de força não se aplica ao petróleo gelificado, em seguida, buscamos uma explicação fisicamente adequada para essa discrepância e também uma maneira confiável de prever a pressão mínima de início do escoamento. Nesta linha, mostramos o efeito do encolhimento do petróleo gelificado na discordância entre a tensão limite estática de escoamento e o gradiente de pressão mínimo necessário para iniciar o fluxo, através da reometria e do fluxo de fluido em um tubo. Em seguida, introduzimos uma equação de balanço de força modificada com o efeito de encolhimento incluído para obter o melhor estimação da pressão minima de início de escoamento. Outro elemento essencial sobre o início de escoamento de petróleo gelificado é descobrir uma estratégia confiável para modelar matematicamente a reologia do material. Na maioria dos modelos que visam prever o comportamento reológico de petróleo gelificado, as mudanças da microestrutura durante o fluxo são consideradas tixotrópicas; dependência temporal reversível. Porém, observamos em nossos experimentos com histórias de fluxo e térmicas bem controladas que o caráter irreversível da dependência temporal é bastante evidente. Assim, na segunda parte da tese, propomos um modelo baseado no desenvolvimentos anteriores de Souza Mendes e colaboradores que considera a dependência temporal irreversível observada experimentalmente para petróleo gelificado. A capacidade preditiva do modelo proposto é então avaliada através de comparações com dados experimentais. / [en] Throughout the wax gelation, the network of parafinn crystals modifies the behavior of waxy crude oil. It changes from a low viscosity Newtonian to a high viscosity time-dependent material with yield strength. Now, it is totally challenging to find out the restart pressure for gelled crude oil ow with such a complex microstructure. Through my Master s dissertation, we investigated two viscoplastic materials, namely a hair gel with a negligible thixotropy and a quite thixotropic 2 percent aqueous suspension of Laponite to mimic the startup flow of waxy crude oils. For both materials, the minimum axial pressure gradient required for the onset of flow was measured, and the measured values were in good agreement with the prediction of a conventional force balance. On the other hand, industry cases have exhibited that the just mentioned force balance leads to an overestimation of the minimum startup pressure gradient. In some studies, an elicited explanation is the thixotropic behavior of the gelled crude, but our results above-mentioned served to falsify it. Over the first part of my PhD thesis, we aimed to verify in the laboratory that why the force balance does not hold for gelled crude oil and then we sought a physically proper explanation for this discrepancy and also a reliable way to predict the minimum startup pressure gradient. Along these lines, we show the role of gelled crude oil s shrinkage in the discordance between static yield strength and required minimum pressure gradient to onset the flow, through rheometry and fluid flow in a tube. Then, we introduce a modified force balance equation with the role of shrinkage included to best estimate the minimum restart pressure gradient. Another essential element through the restart flow of gelled waxy crude is to find out a reliable strategy to mathematically model the material s rheology. In most models that aim at predicting the rheological behavior of gelled waxy crude oil, the microstructure changes during ow are assumed to be thixotropic (reversible time dependent). But, we observed in our experiments with well-controlled flow and thermal histories that the irreversible character of time dependence is quite evident. Thus, in the second part of thesis we propose a model based on previous developments by Souza Mendes and co-workers that accounts for the irreversible time dependence observed experimentally in a waxy crude oil. The predictive capability of the proposed model is then assessed via comparisons with experimental data.