Three candidate asphaltene inhibitors have been laboratory tested for their effectiveness on a Canadian crude. One inhibitor, an oil-soluble polymeric dispersant developed by Shell Chemicals, showed superior behaviour compared to the others: flocculation titrations with n-heptane resulted in an optimum concentration of 1300 ppm. PVT calculations, however, indicated that the prevailing conditions downhole can be quite favourable with respect to the amount of effective inhibitor compared to the atmospheric laboratory titrations which appear to be quite severe tests. Therefore, lower initial concentrations were recommended for a field trial. The chemical could be continuously injected through a capillary string, thereby avoiding the lost oil production associated with solvent cleaning operations. It has proved to be very effective at concentrations as low as 66 ppm, resulting in both a technically and an economically successful trial.
Introduction
Precipitation of asphaltenes in reservoirs, wells and facilities has a severe detrimental impact on the economics of oil production because of a reduction well productivity and/or clogging of the production facilities. The nature and behaviour of asphaltenes in crude oils is complex. Asphaltenes are heterocyclic macromolecules mainly consisting of carbon and hydrogen and minor components such as sulphur, nitrogen, and oxygen. It is generally accepted that resins and maltenes (these structures are comparable to asphaltenes but with a much lower molecular weight) are responsible for keeping the asphaltene particles in dispersion. The asphaltenes are surrounded by the polar head groups of the resins and maltenes while the nonpolar alkyl tails interact with the oil phase. So, crudes with a high ratio of resins to asphaltenes are less subject to asphaltene deposition whereas crudes with large amounts of non-polar saturates compared to aromatics are more prone to exhibit asphaltene precipitation problems. At "normal" reservoir conditions the asphaltenes, resins, maltenes and oil phase are in thermodynamic equilibrium. This equilibrium can be disturbed by a number of factors: decline of the reservoir pressure towards the bubble point, change in temperature or addition of a miscible solvent to the oil as applied in various EOR techniques.
Much research has been focused on modelling the deposition behaviour of asphaltenes in reservoir crudes upon changes in pressure, temperature or composition. These models are based on the Flory-Huggins theory for colloidal systems and calculate the chemical potential for large molecules in the various phases. They require solubility parameters as input. In addition, the industry has made a substantial effort to develop pragmatic solutions to the problem of asphaltene deposition in producing wells.
Formation of highly symmetric skeletal elements in demosponges, called spicules, follows a unique biomineralization mechanism in which polycondensation of an inherently disordered amorphous silica is guided by a highly ordered proteinaceous scaffold, the axial filament. The enzymatically active proteins, silicateins, are assembled into a slender hybrid silica/protein crystalline superstructure that directs the morphogenesis of the spicules. Furthermore, silicateins are known to catalyze the formation of a large variety of other technologically relevant organic and inorganic materials. However, despite the biological and biotechnological importance of this macromolecule, its tertiary structure was never determined. Here we report the atomic structure of silicatein and the entire mineral/organic hybrid assembly with a resolution of 2.4 Å. In this work, the serial X-ray crystallography method was successfully adopted to probe the 2-µm-thick filaments in situ, being embedded inside the skeletal elements. In combination with imaging and chemical analysis using high-resolution transmission electron microscopy, we provide detailed information on the enzymatic activity of silicatein, its crystallization, and the emergence of a functional three-dimensional silica/protein superstructure in vivo. Ultimately, we describe a naturally occurring mineral/protein crystalline assembly at atomic resolution.
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